CN114984947A - Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst - Google Patents
Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 28
- 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 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004140 cleaning Methods 0.000 claims abstract description 34
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- 230000002195 synergetic effect Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000000703 Cerium Chemical class 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- HZADGDCWYTUEDJ-UHFFFAOYSA-M cerium(3+);hydroxide Chemical compound [OH-].[Ce+3] HZADGDCWYTUEDJ-UHFFFAOYSA-M 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 abstract description 7
- 239000010937 tungsten Substances 0.000 abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 238000004056 waste incineration Methods 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
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Abstract
The invention discloses a method for preparing a denitration and dioxin-removal catalyst by using a waste SCR denitration catalyst, which relates to the technical field of waste catalyst resource recovery and comprises the following steps: s1, ash removal and cleaning of the waste SCR catalyst, wherein the waste SCR catalyst is subjected to ash removal under negative pressure firstly, then is subjected to cleaning with clear water, cleaning with special cleaning solution and secondary washing with clear water in sequence, and is crushed and ground for later use after being dried; the method of acid liquor high-temperature high-pressure hydrothermal treatment is used to leach the active components on the original catalyst into the solution, and the active components and the precursors of vanadium, tungsten and cerium added subsequently are subjected to sufficient interaction, so that the performance of the catalyst is improved.
Description
Technical Field
The invention relates to the technical field of waste catalyst resource recovery, in particular to a method for preparing a denitration and dioxin-removal catalyst by using a waste SCR denitration catalyst.
Background
The Selective Catalytic Reduction (SCR) technology is widely applied to nitrogen oxide treatment of flue gas of various industries such as thermal power generation, steel smelting, printing and dyeing textile, cement chemical industry, mining manufacturing, leather tanning, food and beverage, and the like, such as super-large, medium and small coal-fired, fuel oil and gas-fired boilers, smelting furnaces, sintering machines and the like. With the effective implementation of the national 'blue sky guard war' about atmospheric environment treatment, obvious effect has been achieved on the pollution treatment of nitrogen oxides in industrial flue gas. But with a large number of obsolete spent SCR denitration catalysts. The industrial SCR denitration catalyst is generally a vanadium tungsten titanium catalyst (V) 2 O 5 -WO 3 /TiO 2 ) Mainly, the life is usually about 3 years. The retired waste SCR denitration catalyst needs to be harmlessly treated as solid hazardous waste, otherwise, the environment is seriously harmed by random treatment. The catalyst after the harmless treatment can be regenerated for continuous use or can be recycled as a raw material for preparing a new denitration catalyst.
The waste SCR denitration catalyst is generally subjected to harmless treatment through the steps of negative pressure blowing and ash removal, water washing, special cleaning liquid washing and the like, and then is regenerated and used as a raw material for preparing a new catalyst. For example, chinese patent CN202011230286.4 discloses a method for regenerating an inactivated SCR denitration catalyst and using the regenerated inactivated SCR denitration catalyst for preparing a denitration and dioxin removal catalyst, which comprises the steps of cleaning ash and cleaning the inactivated SCR denitration catalyst, then deeply cleaning poisons on the surface of the catalyst with a cleaning solution, and finally drying and calcining the loaded active component to obtain the denitration and dioxin removal catalyst. However, the denitration and dioxin removal catalyst prepared by the method has the defect that the active components are similarly impregnated on the carrier step by step, and the active components on the load cannot generate sufficient interaction with the active components in the original catalyst, so that the synergistic denitration and dioxin removal effect of the catalyst is not ideal. Because the conventional cleaning method cannot completely remove the toxic and harmful species on the surface of the catalyst, the regenerated catalyst obtained by the treatment process cannot be used as a whole carrier, and a proper amount of fresh titanium dioxide is usually added to be used as the carrier to achieve a good catalytic effect.
Based on the current situation of a large amount of retired waste SCR denitration catalysts in the current market and the current trend of recycling the waste SCR denitration catalysts, the invention bases on the regeneration and preparation technology of the catalytic catalyst, sequentially carries out alkali treatment, acid treatment and third active component loading on the recovered waste vanadium-tungsten-titanium denitration catalysts, and finally prepares the flue gas synergistic denitration and dioxin removal catalyst suitable for the solid waste incineration industry.
Disclosure of Invention
In order to solve the defects mentioned in the background art, the invention aims to provide a method for preparing a denitration and dioxin-removal catalyst by using a waste SCR denitration catalyst, wherein the method comprises the steps of sequentially removing ash by negative pressure, washing by water, cleaning by a cleaning solution and carrying out high-temperature and high-pressure hydrothermal treatment by alkali liquor to fully remove toxic and harmful substances in the waste catalyst, and the treated catalyst can be directly used for preparing a new catalyst without adding a fresh titanium dioxide carrier; the method of acid liquor high-temperature high-pressure hydrothermal treatment is used for leaching the active components on the original catalyst into the solution and generating sufficient interaction with the precursors of vanadium, tungsten and cerium which are added subsequently, thereby improving the performance of the catalyst.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing a denitration and dioxin removal catalyst by using a waste SCR denitration catalyst comprises the following steps:
s1, ash removal and cleaning of the waste SCR catalyst, wherein the waste SCR catalyst is subjected to ash removal under negative pressure, then is cleaned by clean water, cleaned by special cleaning liquid and washed by clean water for the second time in sequence, and is crushed and ground for later use after being dried;
s2, carrying out alkaline water hot-pressing treatment on the waste SCR catalyst, immersing the waste SCR catalyst powder obtained in the step S1 in an alkaline aqueous solution with a certain concentration, transferring the solution to a closed high-pressure reaction kettle, carrying out high-temperature high-pressure hydrothermal treatment for a certain time, naturally cooling, taking out, filtering and cleaning to be nearly neutral;
s3, carrying out acid water hot-pressing treatment on the waste SCR catalyst, immersing the waste SCR catalyst obtained in the step S2 in an acid water solution with a certain concentration, transferring the acid water solution to a closed high-pressure reaction kettle, carrying out high-temperature high-pressure hydrothermal treatment for a period of time, naturally cooling, and taking out for later use;
s4, loading and activating an active component precursor, adding a certain amount of ammonium metavanadate, ammonium metatungstate and a cerium salt precursor into the solid-liquid mixture containing the catalyst obtained in the step S3, fully stirring and dissolving, removing excessive water through reduced pressure distillation to keep a certain water content of the mixture, and then sequentially drying and calcining at high temperature to obtain the synergistic denitration and dioxin removal catalyst.
Further, the waste SCR denitration catalyst in S1 is a honeycomb type vanadium tungsten titanium denitration catalyst, and its main component is V 2 O 5 -WO 3 /TiO 2 The amount of water used for cleaning the waste SCR denitration catalyst in the S1 is 1-2 times of the mass of the waste catalyst, the concentration of main components in the special cleaning liquid in the S1 is 5-20%, the amount of the cleaning liquid is 1.5-3 times of the mass of the waste catalyst, the amount of clear water used for secondarily washing the waste catalyst in the S1 is 12 times of the mass of the waste catalyst, and the amount of clear water used for secondarily washing the waste catalyst in the S1 is 1-2 times of the mass of the waste catalystThe drying mode is hot air blast drying, the drying temperature is 90-110 ℃, the drying time is 1-2 h, and the waste catalyst in the S1 is crushed and ground into powder of less than 200 meshes.
Further, the alkaline aqueous solution in the S2 is one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution and ammonia water, the concentration of alkali is 5-15%, the use amount of the alkaline aqueous solution in the S2 is 2-6 times of the mass of the waste catalyst, the temperature of the high-temperature hot-pressing water treatment in the S2 is 120-200 ℃, and the treatment time is 4-12 hours.
Further, the acidic solution in the S3 is one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid and oxalic acid aqueous solutions, the concentration of acid is 0.1-1 mol/L, the use amount of the acidic aqueous solution in the S3 is 2-4 times of the mass of the waste catalyst, the temperature of the high-temperature hot-pressing water treatment in the S3 is 120-200 ℃, and the treatment time is 4-12 hours.
Further, the cerium salt precursor in S4 is cerium nitrate hexahydrate (Ce (NO) 3 ) 3 ·6H 2 O), cerium oxide (CeO) 2 ) Cerium hydroxide (Ce (OH)) 4 ) Cerous hydroxide (Ce (OH)) 3 ) Cerium acetate (Ce (C) 2 H 3 O 2 ) 3 ·nH 2 O) and the like, according to all active components (respectively as V) in the S4 2 O 5 、WO 3 、CeO 2 Calculated) ammonium metavanadate, ammonium metatungstate and a cerium salt precursor accounting for 10-15% of the total mass of the catalyst, and V in all active components after the ammonium metavanadate, the ammonium metatungstate and the cerium salt precursor are added in S4 2 O 5 、WO 3 、CeO 2 The catalyst comprises 4-5%, 3-5% and 3-5% of the total mass of the catalyst respectively, the water content of the mixture is kept at 30-50% after the water is removed by vacuum distillation in S4, the drying temperature in S4 is 90-130 ℃, the drying time is 5-10 hours, the calcining temperature in S4 is 400-600 ℃, and the calcining time is 5-10 hours.
The invention has the beneficial effects that: according to the invention, toxic and harmful substances in the waste catalyst are fully removed by using a method of negative-pressure ash removal, water washing, cleaning by using a cleaning solution and alkali liquor high-temperature high-pressure hydrothermal treatment in sequence, and the treated catalyst can be directly used for preparing a new catalyst without adding a fresh titanium dioxide carrier; the method of acid liquor high-temperature high-pressure hydrothermal treatment is used to leach the active components on the original catalyst into the solution, and the active components and the precursors of vanadium, tungsten and cerium added subsequently are subjected to sufficient interaction, so that the performance of the catalyst is improved.
Drawings
The invention will be further described with reference to the accompanying drawings.
Fig. 1 shows the performance test results of the synergistic denitration and dioxin removal catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A method for preparing a denitration and dioxin removal catalyst by using a waste SCR denitration catalyst comprises the steps of cutting 500g of block honeycomb type waste vanadium tungsten titanium denitration catalyst subjected to negative pressure ash removal treatment, washing the catalyst with 500g of water, deeply cleaning the catalyst with 750g of special cleaning solution with the mass concentration of 15%, continuously cleaning with 500g of clean water after cleaning, drying for 2h by blowing hot air at 90 ℃, crushing and grinding the catalyst until the catalyst is completely sieved by a 200-mesh sieve, fully mixing catalyst powder obtained in S1 with 1L of ammonia water solution with the concentration of 15%, transferring the mixture into a 1L high-pressure reaction kettle, stirring at 120 ℃ for hydrothermal treatment for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, filtering and washing to be nearly neutral, dispersing a filter cake of the catalyst obtained in S2 into 2L of oxalic acid solution with the concentration of 1mol/L, transferring the mixture into a closed high-pressure reaction kettle, stirring at 200 deg.C for hydrothermal treatment for 8 hr, naturally cooling to room temperature, taking out, and subjecting the catalyst obtained in S3 to V 2 O 5 、WO 3 、TiO 2 Measuring the content according to the total active component ratio of 15％，V 2 O 5 、WO 3 、CeO 2 Adding a proper amount of ammonium metavanadate, ammonium metatungstate and cerous nitrate hexahydrate into the mixed solution of S3 according to the proportion of 5%, fully stirring and dissolving, and removing excessive moisture by reduced pressure distillation to keep the moisture of the mixture at about 50%; and then drying the catalyst at 130 ℃ for 5h, and calcining the catalyst at 500 ℃ for 7.5h to obtain the synergistic denitration and dioxin removal catalyst.
Example two
A method for preparing a denitration and dioxin removal catalyst by using a waste SCR denitration catalyst comprises the steps of cutting 500g of block honeycomb type waste vanadium tungsten titanium denitration catalyst subjected to negative pressure ash removal treatment, washing the catalyst with 750g of water, deeply washing the catalyst with 1500g of special cleaning solution with the mass concentration of 5%, continuously washing the catalyst with 1000g of clean water after the washing is finished, subsequently drying the catalyst for 1 hour by using 110 ℃ hot air blast, and finally crushing and grinding the catalyst until the catalyst is completely sieved by a 200-mesh sieve; fully mixing the catalyst powder obtained in S1 with 3L of 5% sodium hydroxide aqueous solution, transferring the mixture into a 5L high-pressure reaction kettle, stirring at 200 ℃ for hydrothermal treatment for 4h, naturally cooling to room temperature after the hydrothermal treatment is finished, filtering and washing to be nearly neutral, dispersing the catalyst filter cake obtained in S2 into 1L of 0.1mol/L sulfuric acid solution, transferring the solution into a closed high-pressure reaction kettle, stirring at 120 ℃ for hydrothermal treatment for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, taking out for later use, and carrying out V treatment on the catalyst obtained in S3 2 O 5 、WO 3 、TiO 2 Measuring the content of V according to the result of measurement and the proportion of the total active components of 12 percent 2 O 5 、WO 3 、CeO 2 The percentage of the ammonium metavanadate, the ammonium metatungstate and the cerous nitrate hexahydrate are respectively 4.5%, 4% and 3.5%, a proper amount of ammonium metavanadate, ammonium metatungstate and cerous nitrate hexahydrate are added into the mixed solution of S3, and after the ammonium metavanadate, the ammonium metatungstate and the cerous nitrate hexahydrate are fully stirred and dissolved, redundant moisture is removed through reduced pressure distillation, so that the moisture of the mixture is kept at about 30%; and then drying at 100 ℃ for 7h, and calcining at 600 ℃ for 5h to obtain the synergistic denitration and dioxin removal catalyst.
EXAMPLE III
Method for preparing denitration and dioxin removal catalyst by using waste SCR denitration catalyst, cutting 500g of denitration and dioxin removal catalyst, and performing negative-pressure ash removal treatmentThe blocky honeycomb type waste vanadium, tungsten and titanium denitration catalyst is washed by 1000g of water, deeply washed by 1000g of special cleaning solution with the mass concentration of 10%, continuously washed by 750g of clean water after washing, dried by blowing hot air at 100 ℃ for 1.5h, finally crushed and ground into powder until all the catalyst passes through a 200-mesh sieve, the catalyst powder obtained in S1 is fully mixed with 2L of 10% potassium hydroxide aqueous solution and then transferred to a 5L high-pressure reaction kettle, hydrothermal treatment is carried out by stirring at 160 ℃ for 8h, after the hydrothermal treatment is finished, natural cooling is carried out to room temperature, filtration and washing are carried out to the neutrality, the catalyst filter cake obtained in S2 is dispersed into 1.5L of 0.5mol/L hydrochloric acid solution and then transferred to a closed high-pressure reaction kettle, hydrothermal treatment is carried out by stirring at 160 ℃ for 4h, after the hydrothermal treatment is finished, natural cooling is carried out to the room temperature, taking out the catalyst for standby, and subjecting the catalyst obtained in S3 to V 2 O 5 、WO 3 、TiO 2 Measuring the content, according to the measuring result, according to the total active component accounting for 12.5 percent and V 2 O 5 、WO 3 、CeO 2 Adding a proper amount of ammonium metavanadate, ammonium metatungstate and cerium nitrate hexahydrate into the mixed solution of S3, fully stirring and dissolving, and removing excessive moisture by reduced pressure distillation to keep the moisture of the mixture at about 40%; then drying at 90 ℃ for 10h, and calcining at 400 ℃ for 10h to obtain the synergistic denitration and dioxin removal catalyst.
According to the catalyst formulas calculated in S4 of example 1, example 2, and example 3, respectively, ammonium metavanadate, ammonium metatungstate, and cerium precursors are mixed with a titanium dioxide mixed aqueous solution, and then the mixture is subjected to vacuum distillation to remove water, and then the same drying and calcining processes are performed to obtain the synergistic denitration and dioxin removal catalyst prepared from fresh compounds of vanadium, tungsten, titanium, cerium, and the like.
Catalyst test conditions: the test temperature is 180 ℃, NO is introduced into the reactor with the concentration of 500ppm, NH 3 The introduction concentration of 500ppm and the introduction concentration of 5ng-TEQ/Nm of dioxin 3 ，O 2 7% (v/v), Ar is balance gas, and the gas volume space velocity is 6000h -1 . The denitration efficiency is calculated by detecting the concentration of NO at the inlet and the outlet of the catalyst through a nitrogen oxide detectorThe dioxin removal efficiency is calculated by quantitatively analyzing the concentrations of the dioxins at the inlet and the outlet of the catalyst through gas chromatography, the analysis result is shown in figure 1, and as can be seen from figure 1, compared with the catalyst prepared by using fresh vanadium, tungsten, titanium, cerium and other compounds as raw materials, the synergistic denitration and dioxin removal catalyst prepared by adopting the method provided by the invention has similar synergistic denitration and dioxin removal performance.
The working principle is as follows: compared with the prior art of recycling waste SCR denitration catalysts, the method has the advantages that toxic and harmful substances in the waste catalysts are fully removed by using the methods of negative-pressure ash removal, water washing, cleaning liquid cleaning and alkali liquor high-temperature high-pressure hydrothermal treatment in sequence, and the treated catalysts can be directly used for preparing new catalysts without adding fresh titanium dioxide carriers; the method of acid liquor high-temperature high-pressure hydrothermal treatment is used to leach the active components on the original catalyst into the solution, and the active components and the precursors of vanadium, tungsten and cerium added subsequently are subjected to sufficient interaction, so that the performance of the catalyst is improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (5)
1. A method for preparing a denitration and dioxin removal catalyst by using a waste SCR denitration catalyst is characterized by comprising the following steps:
s1, ash removal and cleaning of the waste SCR catalyst, wherein the waste SCR catalyst is subjected to ash removal under negative pressure, then is cleaned by clean water, cleaned by special cleaning liquid and washed by clean water for the second time in sequence, and is crushed and ground for later use after being dried;
s2, carrying out alkaline water hot-pressing treatment on the waste SCR catalyst, immersing the waste SCR catalyst powder obtained in the step S1 in an alkaline aqueous solution with a certain concentration, transferring the solution to a closed high-pressure reaction kettle, carrying out high-temperature high-pressure hydrothermal treatment for a certain time, naturally cooling, taking out, filtering and cleaning to be nearly neutral;
s3, carrying out acid water hot-pressing treatment on the waste SCR catalyst, immersing the waste SCR catalyst obtained in the step S2 in an acid water solution with a certain concentration, transferring the acid water solution to a closed high-pressure reaction kettle, carrying out high-temperature high-pressure hydrothermal treatment for a period of time, naturally cooling, and taking out for later use;
s4, loading and activating an active component precursor, adding a certain amount of ammonium metavanadate, ammonium metatungstate and a cerium salt precursor into the solid-liquid mixture containing the catalyst obtained in the step S3, fully stirring and dissolving, removing excessive water through reduced pressure distillation to keep a certain water content of the mixture, and then sequentially drying and calcining at high temperature to obtain the synergistic denitration and dioxin removal catalyst.
2. The method of claim 1, wherein the spent SCR denitration catalyst in S1 is a honeycomb vanadium tungsten titanium denitration catalyst comprising V 2 O 5 -WO 3 /TiO 2 The amount of water for cleaning the waste SCR denitration catalyst in the S1 is 1-2 times of the mass of the waste catalyst, the concentration of main components in the special cleaning liquid in the S1 is 5-20%, the amount of the cleaning liquid is 1.5-3 times of the mass of the waste catalyst, the amount of clear water for secondary washing of the waste catalyst in the S1 is 12 times of the mass of the waste catalyst, the drying mode in the S1 is hot air blast drying, the drying temperature is 90-110 ℃, the drying time is 1-2 hours, and the waste catalyst in the S1 is brokenPulverizing to powder below 200 meshes.
3. The method of claim 1, wherein the alkaline aqueous solution in the step S2 is one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution and ammonia water, the concentration of alkali is 5-15%, the amount of the alkaline aqueous solution in the step S2 is 2-6 times of the mass of the waste catalyst, the temperature of the high-temperature hot-pressing water treatment in the step S2 is 120-200 ℃, and the treatment time is 4-12 hours.
4. The method of claim 1, wherein the acidic solution in S3 is one of aqueous solutions of sulfuric acid, hydrochloric acid, nitric acid, acetic acid and oxalic acid, the concentration of the acid is 0.1-1 mol/L, the amount of the acidic aqueous solution in S3 is 2-4 times of the mass of the waste catalyst, the temperature of the high-temperature hot-pressing water treatment in S3 is 120-200 ℃, and the treatment time is 4-12 h.
5. The method of claim 1, wherein the cerium salt precursor in S4 is cerium nitrate hexahydrate (Ce (NO) nitrate 3 ) 3 ·6H 2 O), cerium oxide (CeO) 2 ) Cerium hydroxide (Ce (OH)) 4 ) Cerous hydroxide (Ce (OH)) 3 ) Cerium acetate (Ce (C) 2 H 3 O 2 ) 3 ·nH 2 O) and the like, according to all active components (respectively as V) in the S4 2 O 5 、WO 3 、CeO 2 Calculated) account for 10-15% of the total mass of the catalyst, ammonium metavanadate, ammonium metatungstate and a cerium salt precursor are added, and after the ammonium metavanadate, ammonium metatungstate and the cerium salt precursor are added in S4, V in all active components 2 O 5 、WO 3 、CeO 2 Respectively accounting for 4-5%, 3-5% and 3-5% of the total mass of the catalyst, the water content of the mixture is maintained at 30-50% after water removal by vacuum distillation in S4, and the drying temperature in S4 is 90-130 DEG CThe drying time is 5-10h, the calcining temperature in S4 is 400-600 ℃, and the calcining time is 5-10 h.
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