CN117399080A - Method for modifying and regenerating deactivated denitration catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 230
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000007788 liquid Substances 0.000 claims abstract description 94
- 238000011069 regeneration method Methods 0.000 claims abstract description 46
- 230000008929 regeneration Effects 0.000 claims abstract description 43
- 238000004073 vulcanization Methods 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 32
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 26
- 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 26
- 238000010926 purge Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract 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 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 description 23
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 235000010269 sulphur dioxide Nutrition 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000004291 sulphur dioxide Substances 0.000 description 3
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical group [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- 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
- B01D53/88—Handling or mounting catalysts
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
A method for modifying and regenerating an inactivated denitration catalyst belongs to the field of denitration catalyst regeneration. Firstly, splitting the deactivated catalyst into uniform block-shaped whole, cleaning surface area ash by high-pressure gas blowing, secondly, performing ultrasonic chemical cleaning, firstly, immersing the cleaned catalyst in the regeneration liquid A at a controlled temperature, drying and performing vulcanization treatment after the immersion is finished, and immersing the catalyst after the vulcanization treatment in the regeneration liquid B at a controlled temperature. And finally, roasting the catalyst to finish the modification and regeneration of the catalyst. The method adopts a sol-gel method to fully disperse and adhere the cerium nitrate component on the surface of the catalyst in a colloid form, and simultaneously, citric acid forms carbon with high specific surface area in the drying process, so that the specific surface area of the catalyst is enlarged. The vulcanization treatment improves the denitration performance of the cerium component on the surface of the catalyst, combines with vanadium on the surface of the catalyst, effectively improves the combined denitration and demercuration activity of the regenerated catalyst, and widens the application range of the regenerated denitration catalyst.
Description
Technical Field
The invention relates to a method for modifying and regenerating an inactivated denitration catalyst, belonging to the field of SCR denitration catalyst regeneration and utilization.
Background
The Selective Catalytic Reduction (SCR) technology is a technology for removing nitrogen oxides in gas by mainly taking a denitration catalyst as a carrier and matching NH 3. The high emission industries of nitrogen oxides represented by thermal power plants are numerous, and a large number of these industries adopt denitration catalysts to remove nitrogen oxides in tail gas.
The denitration catalyst with the largest national standard is a vanadium-titanium catalyst, titanium dioxide is used as a carrier, the main active components are vanadium pentoxide and tungsten trioxide, the service life is generally 2-3 years, a large amount of deactivated denitration catalysts are required to be treated in recent years due to various reasons, the waste SCR denitration catalyst is used as dangerous waste regulated in the national hazardous waste list, regeneration or safe treatment is encouraged, and the renewable denitration catalyst after chemical and physical analysis is regenerated, so that the recycling of the denitration catalyst is realized.
Patent CN114471746a discloses a method for regenerating an SCR denitration catalyst, which comprises immersing an inactivated catalyst in a replenishing solution for reaction, adding ammonia gas for neutralization and hydrolysis, and roasting to obtain the regenerated SCR denitration catalyst. The method not only can recycle the waste catalyst, but also can directly use the extracted effective components in the regeneration process of the deactivated catalyst, and the mechanical strength of the regenerated catalyst is improved by the supplemented carrier components, but the denitration catalyst regenerated by the method has narrow application range and poor dispersion degree of the active components, and can only be repeatedly applied to places used before regeneration.
Patent CN107597139B discloses a catalyst for synergistic denitration of mercury removal and a preparation method thereof, wherein ferric salt, manganese salt and cerium salt are loaded on graphene oxide according to a certain proportion by a hydrothermal method, and then dried and burned in nitrogen atmosphere to obtain the catalyst for synergistic denitration of mercury removal. However, the denitration catalyst prepared by the method consumes a large amount of metal salt, and graphene is used as a carrier, so that the preparation cost is high and the economic benefit is low. The graphene carrier is easy to peel off in a long-term use process, has the problems of structural change and the like, and is easy to block reactive sites due to carbon deposition, so that the graphene carrier is not suitable for large-scale production and use.
Patent CN104815674a discloses a modified regeneration solution for combined denitration and demercuration of deactivated vanadium-titanium-based honeycomb denitration catalyst and a preparation method thereof, the method uses ammonium metavanadate, ammonium metatungstate, oxalic acid, cerium nitrate, copper chloride and deionized water to prepare the regeneration solution, the deactivated denitration catalyst can have the combined oxidation and demercuration capability while recovering the activity through the regeneration solution, but the denitration catalyst regenerated through the regeneration solution has limited active component loading capability and can achieve corresponding effects through repeated impregnation. The active components are easy to gather in the same area, and the active sites are easy to directly cause the deactivation of the catalyst after being blocked.
In summary, the existing denitration catalyst regeneration method still takes the traditional ash removal-chemical cleaning-active loading flow as the main process, and the application range of the regenerated denitration catalyst is narrow. The method for improving the combined denitration and demercuration performance by introducing components such as cerium has the problems of low economic benefit, poor combined denitration and demercuration performance, low active component load dispersion degree and the like.
Disclosure of Invention
The invention aims to solve the problems that the application range of the denitration catalyst regenerated by the traditional ash removal-chemical cleaning-active load flow of the existing denitration catalyst regeneration method is narrow; the method for improving the combined denitration and demercuration performance by introducing components such as cerium has the problems of low economic benefit, poor combined denitration and demercuration performance, low active component load dispersion degree and the like.
The method for modifying and regenerating the deactivated denitration catalyst is characterized by comprising the steps of firstly, splitting the deactivated catalyst into uniform block-shaped integers, and cleaning surface area ash through high-pressure gas blowing; secondly, carrying out ultrasonic chemical cleaning, wherein the cleaned catalyst is firstly immersed in the regeneration liquid A at a controlled temperature, and is dried and vulcanized after the immersion is finished; the catalyst after the vulcanization treatment is immersed in the regenerated liquid B in a temperature-controlled manner; and finally, roasting the catalyst to finish the modification and regeneration of the catalyst.
Further, the bulk catalyst is of a cuboid type, and the length thereof is as follows: 20-100 mm, 20-100 mm wide and 40-200 mm high.
Further, the high-pressure gas pressure is 0.2-0.6 Mpa, and the purging time is 0.4-2.0 h.
Further, the ultrasonic chemical cleaning process is that the catalyst is sequentially subjected to ultrasonic cleaning for 5-15 min by ammonia water solution with the concentration of 3-5 mol/L, sulfuric acid solution with the concentration of 0.5-2.0 mol/L and deionized water, the ultrasonic frequency is 25-30 kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 2.5-7.5 min.
Further, the temperature control dipping process is carried out in the regenerated liquid A, the dipping temperature is 70-90 ℃, the dipping time is 2-3 hours, the regenerated liquid A is citric acid solution for dissolving cerium nitrate hexahydrate, and the adding amount of the cerium nitrate hexahydrate is 0.5-1.0 mol/L; the concentration of the citric acid solution is 1.5-3.0 mol/L.
Further, the drying process is performed in a nitrogen atmosphere at a drying temperature of 190-250 ℃ for 0.2-0.5 h, the vulcanization process is performed by placing the catalyst into a flow reactor for continuous heating and introducing flow gas, the flow gas comprises nitrogen containing 300-500 ppm sulfur dioxide and 5-10% vol oxygen, the heating temperature is 250-350 ℃ and the heating time is 1-2 h.
Further, the temperature control dipping process is carried out in the regenerated liquid B, the dipping temperature is 70-90 ℃, the dipping time is 1-3 h, the regenerated liquid B is ethanolamine solution for dissolving ammonium metavanadate, and the adding amount of the ammonium metavanadate is 0.5-1.0 mol/L; the concentration of the ethanolamine solution is 0.5-2.0 mol/L.
Further, the furnace temperature of the furnace used in the roasting process is 350-450 ℃, the roasting time is 2-4 hours, and the heating rate is 3-7 ℃/min; and the excessive load liquid is removed, and meanwhile, the sufficient adhesion of cerium and vanadium active components is achieved.
The method for modifying and regenerating the deactivated denitration catalyst shown in fig. 1 specifically comprises the following steps:
step 1: splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 20-100 mm, the width of 20-100 mm and the height of 40-200 mm;
step 2: introducing high-pressure gas of 0.2-0.6 Mpa to purge and clean the surface area ash for 0.4-2.0 h;
step 3: immersing the bulk whole catalyst subjected to ash removal into ammonia water solution with the concentration of 3-5 mol/L, sulfuric acid solution with the concentration of 0.5-2.0 mol/L and deionized water in sequence, carrying out ultrasonic cleaning for 5-15 min, wherein the ultrasonic frequency is 25-30 kHz, and turning the catalyst up and down when the ultrasonic cleaning process reaches 2.5-7.5 min so as to fully clean and remove poisoning factors which lead to deactivation of the deactivated catalyst;
step 4: preparing a citric acid solution with the concentration of 1.5-3.0 mol/L, adding cerium nitrate hexahydrate with the concentration of 0.5-1.0 mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. And (3) preparing a regenerated liquid A according to the volume of the catalyst, immersing the cleaned catalyst in the regenerated liquid A, controlling the temperature to be 70-90 ℃, and immersing for 2-3 hours to finish the loading process of the regenerated liquid A.
Step 5: after the impregnation process of the regenerated liquid A is completed, the catalyst is placed in a drying box and dried for 0.2 to 0.5 hour at the temperature of 190 to 250 ℃ under the nitrogen atmosphere, and the drying process is completed after the citric acid colloid on the surface of the catalyst is completely evaporated.
Step 6: the catalyst is vulcanized, the catalyst is placed into a flow reactor to be heated to 250-350 ℃ and continuously introduced with flowing gas, the flowing gas comprises nitrogen containing 300-500 ppm sulfur dioxide and 5-10%vol oxygen, and the flowing gas lasts for 1-2 h.
Step 7: preparing an ethanolamine solution with the concentration of 0.5-2.0 mol/L, adding ammonium metavanadate with the concentration of 0.5-1.0 mol/L, and stirring until the solution is clear, thus preparing the regenerated liquid B. Preparing a regeneration liquid B according to the volume of the catalyst, immersing the cleaned catalyst in the regeneration liquid B, controlling the temperature to be 70-90 ℃ and immersing for 1-3 h.
Step 8: after the impregnation of the regenerated liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 350-450 ℃ for roasting for 2-4 hours at the heating rate of 3-7 ℃/min. And the excessive load liquid is removed, and meanwhile, the sufficient adhesion of cerium and vanadium active components is achieved.
The technical principle of the invention is as follows:
1. when V and Ce are loaded on the deactivated catalyst during the catalyst regeneration process, V and Ce on the surface of the catalyst are finally converted into V 2 O 5 /VO 4 、CeO 2 /Ce 2 O 3 Two redox couples, ce 4+ The denitration process of (2) is shown in formulas (1) to (3). If the catalyst surface Ce 4+ Excessive, easy to promote-NH 2 Further oxidation to N 2 O, ce, in order to avoid this, promotes the reaction (4) by vulcanization 4+ Will be converted into Ce 3+ Promoting catalyst surface Ce 3+ Is rich in SO 4 2- The introduction of (2) can also cause enrichment of strong acid sites on the surface of the catalyst, so that the acidity of the surface of the catalyst is improved. V (V) 2 O 5 /VO 4 The presence of redox pairs promotes Ce at the catalyst surface 4+ Conversion to Ce 3+ 。Ce 3+ Providing more active oxygen sites, and forming higher concentration of surface adsorption oxygen on the surface of the catalyst.
NH 3 +Ce 4+ →-NH 2 +Ce 3+ +H + (1)
-NH 2 +NO(g)→N 2 +H 2 O (2)
4Ce 3+ +O 2 →4Ce 4+ +2O 2- (3)
2CeO 2 +3SO 2 +O 2 ＝Ce 2 (SO 4 ) 3 (4)
Hg in flue gas 0 The catalyst surface after V and Ce are added and vulcanized is enriched with high concentration of Ce 3+ The provided large amount of surface adsorption oxygen can obviously enhance the oxidation performance of the catalyst surface and promote Hg in the flue gas 0 Oxidation to Hg 2+ By Hg 2+ Which is removed in subsequent equipment. Surface enriched Ce 3+ More B acid sites can be generated, and the denitration performance of the catalyst is improved.
2. The cerium component is added into the citric acid solvent to form a low-viscosity solution, the cerium component and the citric acid solvent are uniformly mixed and then undergo hydrolysis and condensation chemical reaction, a stable transparent sol system is formed in the solution, the sol is gradually formed into gel through sedimentation, and the cerium component is highly uniformly dispersed in the sol in the process of converting the sol into the gel. In the drying process, citric acid volatilizes to form carbon deposit with high specific surface area, and the gel component containing cerium is dried, sintered and solidified to be finally converted into tiny cerium oxide/cerium oxide particles which are highly dispersed on the surface of the catalyst.
On the basis of the traditional catalyst regeneration method, the cerium component is adhered to the surface of the denitration catalyst in a highly dispersed way by a sol-gel method, and meanwhile, a large amount of active sites are provided for the catalyst by surface carbon deposition generated after the citric acid load solution is dried. The vulcanization reaction promotes the formation of a redox pair of cerium, and the oxidation-reduction pair of vanadium interacts with the cerium to show excellent combined denitration and demercuration performance. The regenerated catalyst can be configured in the areas containing nitrogen oxides and mercury vapor in the flue gas of thermal power plants, chemical plants and the like, and the application range of the regenerated denitration catalyst is widened. The regeneration process is simple, the economic benefit is high, and the application value is wide.
The beneficial technical effects of the invention are as follows:
1. in the process of regenerating the vanadium-titanium denitration catalyst, the active component vanadium is recovered, and cerium is loaded as a modifying element, so that the regenerated catalyst has the capabilities of denitration and zero-valent mercury oxidation, and the application range of the regenerated denitration catalyst is widened. The oxidation-reduction pair formed by the two load components after roasting can be mutually converted to form a large number of oxygen vacancies, so that the working temperature range of the denitration catalyst is effectively improved.
2. The deactivated catalyst, including small amount of active components on the surface of the catalyst and the carrier with high specific surface area, can be fully recycled, and the cost of the regenerated catalyst can be reduced. The regeneration process has the advantages of easily available raw materials and high economic benefit.
3. The vanadium and cerium active components are uniformly dispersed on the surface of the carrier in a large quantity, the active sites on the surface of the carrier are many, the combined denitration and demercuration effect is good, and the regenerated catalyst after the vulcanization treatment has strong sulfur resistance.
Drawings
FIG. 1 is a flow chart of a modified regeneration of an deactivated denitration catalyst of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It will be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention to such details as will be apparent to those skilled in the art from consideration of the specification. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims.
Example 1
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 100mm, the width of 100mm and the height of 200 mm; and high-pressure air with the air pressure of 0.6Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 2.0h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 5.0mol/L, sulfuric acid solution with the concentration of 2.0mol/L and deionized water in sequence, ultrasonically cleaned for 15min at the frequency of 30kHz, and turned upside down when the ultrasonic cleaning process is carried out for 7.5 min. Preparing a citric acid solution with the concentration of 3.0mol/L, adding cerium nitrate hexahydrate with the concentration of 1.0mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. And (3) preparing a regenerated liquid A by weighing according to the volume of the catalyst, immersing the cleaned catalyst in the regenerated liquid A, controlling the temperature to be 90 ℃, and immersing for 3 hours. After impregnation the catalyst was dried for 0.5h at 250℃under nitrogen in a dry box, then the catalyst was heated to 350℃in a flow reactor and continuously fed with nitrogen containing 500ppm sulfur dioxide and 10% vol oxygen for 2.0h. After the vulcanization process is completed, preparing 2.0mol/L ethanolamine solution, adding ammonium metavanadate with the concentration of 1.0mol/L, and stirring until the solution is clear, thus preparing regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 90 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 3.0h. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 450 ℃ at a heating rate of 7 ℃/min for roasting for 4 hours. The denitration and demercuration performance of the regenerated denitration catalyst is 88.2 percent at the temperature of 200-450 ℃.
Example 2
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 80mm, the width of 80mm and the height of 160 mm; and high-pressure air with the air pressure of 0.5Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 1.6h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 4.5mol/L, sulfuric acid solution with the concentration of 1.6mol/L and deionized water in sequence, ultrasonically cleaned for 12min at the frequency of 29kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 6.0 min. Preparing 2.7mol/L citric acid solution, adding 0.9mol/L cerium nitrate hexahydrate, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 83 ℃, and the immersing is carried out for 2.8 hours. After impregnation the catalyst was dried for 0.3h at 240℃under nitrogen in a dry box, then the catalyst was heated to 320℃in a flow reactor and continuously fed with nitrogen containing 460ppm sulfur dioxide and 9.0% vol oxygen for 1.8h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 1.6mol/L, adding ammonium metavanadate with the concentration of 0.9mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 83 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 2.6 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 430 ℃ for roasting for 3.5 hours at a heating rate of 6 ℃/min. The denitration and demercuration performance of the regenerated denitration catalyst is 86.4 percent at the temperature of 200-450 ℃.
Example 3
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 60mm, the width of 60mm and the height of 120 mm; and high-pressure air with the air pressure of 0.4Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 1.2h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 4.0mol/L, sulfuric acid solution with the concentration of 1.2mol/L and deionized water in sequence, ultrasonically cleaned for 14min at the frequency of 28kHz, and turned upside down when 7.0min is reached in the ultrasonic cleaning process. Preparing 2.3mol/L citric acid solution, adding 0.8mol/L cerium nitrate hexahydrate, and preparing the regenerated liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 76 ℃, and the immersing is carried out for 2.6 hours. After impregnation the catalyst was dried for 0.4h at 230℃under nitrogen in a dry box, then the catalyst was heated to 300℃in a flow reactor and continuously fed with nitrogen containing 440ppm sulfur dioxide and 8.5% vol oxygen for 1.6h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 1.2mol/L, adding ammonium metavanadate with the concentration of 0.8mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 76 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 2.2 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 430 ℃ for roasting for 3.0h at a heating rate of 5 ℃/min. The denitration and demercuration performance of the regenerated denitration catalyst is 83.7 percent at the temperature of 200-450 ℃.
Example 4
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 40mm, the width of 40mm and the height of 80 mm; and high-pressure air with the air pressure of 0.3Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 0.8h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 3.5mol/L, sulfuric acid solution with the concentration of 0.8mol/L and deionized water in sequence, ultrasonically cleaned for 10min at the frequency of 27kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 5.0 min. Preparing a citric acid solution with the concentration of 1.9mol/L, adding cerium nitrate hexahydrate with the concentration of 0.7mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 82 ℃, and the immersing is carried out for 2.4 hours. After impregnation the catalyst was dried for 0.2h at 220℃under nitrogen in a dry box, then the catalyst was heated to 280℃in a flow reactor and continuously fed with nitrogen containing 400ppm of sulphur dioxide and 7.5% vol of oxygen for 1.2h. Preparing an ethanolamine solution with the concentration of 0.8mol/L after the vulcanization process is finished, adding ammonium metavanadate with the concentration of 0.7mol/L, and stirring until the solution is clear, thereby finishing the preparation of the regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 82 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 7.8 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 390 ℃ at a heating rate of 4 ℃/min for roasting for 2.5 hours. The denitration and demercuration performance of the regenerated denitration catalyst is 84.3 percent at the temperature of 200-450 ℃.
Example 5
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 20mm, the width of 20mm and the height of 40 mm; and high-pressure air with the air pressure of 0.2Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 0.4h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 3.0mol/L, sulfuric acid solution with the concentration of 0.5mol/L and deionized water in sequence, ultrasonically cleaned for 8min at the frequency of 26kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 4.0 min. Preparing a citric acid solution with the concentration of 1.5mol/L, adding cerium nitrate hexahydrate with the concentration of 0.6mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 88 ℃, and the immersing is carried out for 2.2 hours. After impregnation the catalyst was dried for 0.2h at 210℃under a nitrogen atmosphere in a dry box, after which the catalyst was heated to 260℃in a flow reactor and continuously fed with nitrogen containing 350ppm sulfur dioxide and 6.5% vol oxygen for 1.0h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 0.6mol/L, adding ammonium metavanadate with the concentration of 0.5mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 88 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 1.4 hours. After the impregnation of the regenerated liquid B was completed, the catalyst was placed in a roasting furnace and heated to 370℃at a heating rate of 3℃per minute for 2.0 hours. The denitration and demercuration performance of the regenerated denitration catalyst is 81.8 percent at the temperature of 200-450 ℃.
Example 6
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 100mm, the width of 100mm and the height of 200 mm; and high-pressure air with the air pressure of 0.6Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 2.0h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 5.0mol/L, sulfuric acid solution with the concentration of 2.0mol/L and deionized water in sequence, ultrasonically cleaned for 14min at the frequency of 30kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 7.0 min. Preparing a citric acid solution with the concentration of 1.5mol/L, adding cerium nitrate hexahydrate with the concentration of 0.5mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 72 ℃, and the immersing is carried out for 3.0h. After impregnation the catalyst was dried for 0.3h at 230℃under nitrogen in a dry box, then the catalyst was heated to 350℃in a flow reactor and continuously fed with nitrogen containing 460ppm sulfur dioxide and 9.0% vol oxygen for 1.8h. Preparing an ethanolamine solution with the concentration of 0.5mol/L after the vulcanization process is finished, adding ammonium metavanadate with the concentration of 0.5mol/L, and stirring until the solution is clear, thereby finishing the preparation of the regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 72 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 2.6 hours. After the impregnation of the regeneration liquid B was completed, the catalyst was placed in a roasting furnace and heated to 430℃for 4.0 hours at a heating rate of 7℃per minute. The denitration and demercuration performance of the regenerated denitration catalyst is 80.4 percent at the temperature of 200-450 ℃.
Example 7
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 80mm, the width of 80mm and the height of 160 mm; and high-pressure air with the air pressure of 0.5Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 1.6h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 4.5mol/L, sulfuric acid solution with the concentration of 1.6mol/L and deionized water in sequence, ultrasonically cleaned for 6min at the frequency of 29kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 3.0 min. Preparing a citric acid solution with the concentration of 1.9mol/L, adding cerium nitrate hexahydrate with the concentration of 0.6mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 76 ℃, and the immersing is carried out for 2.8 hours. After impregnation the catalyst was dried for 0.3h at 220℃under nitrogen in a dry box, then the catalyst was heated to 320℃in a flow reactor and continuously fed with nitrogen containing 380ppm of sulphur dioxide and 7.0% vol of oxygen for 1.6h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 0.9mol/L, adding ammonium metavanadate with the concentration of 0.6mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 76 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 2.2 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 390 ℃ at a heating rate of 6 ℃/min for roasting for 3.5 hours. The denitration and demercuration performance of the regenerated denitration catalyst is 82.9 percent at the temperature of 200-450 ℃.
Example 8
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 60mm, the width of 60mm and the height of 120 mm; and high-pressure air with the air pressure of 0.4Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 1.2h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 4.0mol/L, sulfuric acid solution with the concentration of 1.2mol/L and deionized water in sequence, ultrasonically cleaned for 12min at the frequency of 28kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 6.0 min. Preparing 2.3mol/L citric acid solution, adding 0.7mol/L cerium nitrate hexahydrate, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 86 ℃, and the immersing is carried out for 2.6 hours. After impregnation the catalyst was dried for 0.2h at 210℃under a nitrogen atmosphere in a dry box, after which the catalyst was heated to 300℃in a flow reactor and continuously fed with nitrogen containing 400ppm of sulfur dioxide and 7.5% vol of oxygen for 1.4h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 1.3mol/L, adding ammonium metavanadate with the concentration of 0.7mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 86 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 1.8 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 390 ℃ at a heating rate of 5 ℃/min for roasting for 3.0h. The denitration and demercuration performance of the regenerated denitration catalyst is 83.1 percent at the temperature of 200-450 ℃.
Example 9
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 40mm, the width of 40mm and the height of 80 mm; and high-pressure air with the air pressure of 0.3Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 0.8h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 3.5mol/L, sulfuric acid solution with the concentration of 0.8mol/L and deionized water in sequence, ultrasonically cleaned for 10min at the frequency of 27kHz, and the catalyst is turned upside down when the ultrasonic cleaning process is carried out for 5 min. Preparing 2.7mol/L citric acid solution, adding 0.8mol/L cerium nitrate hexahydrate, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 77 ℃, and the immersing is carried out for 2.4 hours. After impregnation the catalyst was dried for 0.4h at 200℃under nitrogen in a dry box, then the catalyst was heated to 280℃in a flow reactor and continuously fed with nitrogen containing 480ppm of sulfur dioxide and 9.5% vol of oxygen for 1.2h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 1.7mol/L, adding ammonium metavanadate with the concentration of 0.8mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 77 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 1.4 hours. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 370 ℃ at a heating rate of 4 ℃/min for roasting for 2.5 hours. The denitration and demercuration performance of the regenerated denitration catalyst is 82.6 percent at the temperature of 200-450 ℃.
Example 10
Splitting the deactivated catalyst into a cuboid type bulk catalyst with the length of 20mm, the width of 20mm and the height of 40 mm; and high-pressure air with the air pressure of 0.2Mpa is introduced to purge and clean the surface area ash, and the purge is performed for 0.4h. The bulk catalyst after ash removal is immersed in ammonia water solution with the concentration of 3.0mol/L, sulfuric acid solution with the concentration of 0.5mol/L and deionized water in sequence, ultrasonically cleaned for 5min at the frequency of 25kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 2.5 min. Preparing a citric acid solution with the concentration of 3.0mol/L, adding cerium nitrate hexahydrate with the concentration of 0.9mol/L, and preparing the regeneration liquid A after the citric acid solution loaded with the cerium nitrate hexahydrate completely exists in a gel form. The regenerated liquid A is prepared by weighing the catalyst according to the volume, the cleaned catalyst is immersed in the regenerated liquid A, the temperature is controlled to be 70 ℃, and the immersing is carried out for 2.0h. After impregnation the catalyst was dried for 0.5h at 190℃under a nitrogen atmosphere in a dry box, after which the catalyst was heated to 260℃in a flow reactor and continuously fed with nitrogen containing 320ppm of sulphur dioxide and 5.5% vol of oxygen for 1.0h. After the vulcanization process is completed, preparing an ethanolamine solution with the concentration of 1.0mol/L, adding ammonium metavanadate with the concentration of 0.9mol/L, and stirring until the solution is clear, thereby completing the preparation of a regenerated liquid B. The regenerated liquid B is prepared according to the volume of the catalyst, the temperature is controlled to be 70 ℃, and the cleaned catalyst is immersed in the regenerated liquid B for 1.0h. After the impregnation of the regeneration liquid B is completed, the catalyst is placed in a roasting furnace and is heated to 350 ℃ at a heating rate of 3 ℃/min for roasting for 2.0h. The denitration and demercuration performance of the regenerated denitration catalyst at 200-450 ℃ is 84.1%.
Claims (8)
1. The method for modifying and regenerating the deactivated denitration catalyst is characterized by comprising the steps of firstly, splitting the deactivated catalyst into uniform block-shaped integers, and cleaning surface area ash through high-pressure gas blowing; secondly, carrying out ultrasonic chemical cleaning, wherein the cleaned catalyst is firstly immersed in the regeneration liquid A at a controlled temperature, and is dried and vulcanized after the immersion is finished; the catalyst after the vulcanization treatment is immersed in the regenerated liquid B in a temperature-controlled manner; and finally, roasting the catalyst to finish the modification and regeneration of the catalyst.
2. The method for modifying and regenerating an inactivated denitration catalyst according to claim 1, wherein the bulk catalyst is a rectangular solid, and has a length of: 20-100 mm, 20-100 mm wide and 40-200 mm high.
3. The method for modifying and regenerating the deactivated denitration catalyst according to claim 1, wherein the high-pressure gas pressure is 0.2-0.6 Mpa, and the purging time is 0.4-2.0 h.
4. The method for modifying and regenerating the deactivated denitration catalyst according to claim 1, wherein the ultrasonic chemical cleaning process is characterized in that the catalyst is sequentially subjected to ultrasonic cleaning for 5-15 min by ammonia water solution with the concentration of 3-5 mol/L, sulfuric acid solution with the concentration of 0.5-2.0 mol/L and deionized water, the ultrasonic frequency is 25-30 kHz, and the catalyst is turned up and down when the ultrasonic cleaning process is carried out for 2.5-7.5 min.
5. The method for modifying and regenerating the deactivated denitration catalyst according to claim 1, wherein the temperature is controlled in a process of immersing in a regenerating solution A, the immersing temperature is 70-90 ℃, the immersing time is 2-3 hours, the regenerating solution A is a citric acid solution for dissolving cerium nitrate hexahydrate, and the adding amount of the cerium nitrate hexahydrate is 0.5-1.0 mol/L; the concentration of the citric acid solution is 1.5-3.0 mol/L.
6. The method for modifying and regenerating the deactivated denitration catalyst according to claim 1, wherein the drying process atmosphere is nitrogen, the drying temperature is 190-250 ℃, the drying time is 0.2-0.5 h, the vulcanization process is to put the catalyst into a flow reactor for continuous heating and to introduce flowing gas, the flowing gas consists of nitrogen containing 300-500 ppm sulfur dioxide and 5-10% vol oxygen, the heating temperature is 250-350 ℃, and the heating time is 1-2 h.
7. The method for modifying and regenerating the deactivated denitration catalyst according to claim 1, wherein the temperature control is carried out in a process of immersing in a regeneration liquid B at 70-90 ℃ for 1-3 hours, wherein the regeneration liquid B is an ethanolamine solution for dissolving ammonium metavanadate, and the adding amount of the ammonium metavanadate is 0.5-1.0 mol/L; the concentration of the ethanolamine solution is 0.5-2.0 mol/L.
8. The method for modifying and regenerating the deactivated denitration catalyst as claimed in claim 1, wherein the furnace temperature of the furnace used in the roasting process is 350-450 ℃, the roasting time is 2-4 hours, the heating rate is 3-7 ℃/min, and the sufficient adhesion of cerium and vanadium active components is achieved while the excessive load liquid is removed.
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