CN114870907A - Regeneration method of alkali/alkaline earth metal poisoned denitration catalyst - Google Patents
Regeneration method of alkali/alkaline earth metal poisoned denitration catalyst Download PDFInfo
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- CN114870907A CN114870907A CN202210662174.9A CN202210662174A CN114870907A CN 114870907 A CN114870907 A CN 114870907A CN 202210662174 A CN202210662174 A CN 202210662174A CN 114870907 A CN114870907 A CN 114870907A
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- alkali
- alkaline earth
- earth metal
- denitration catalyst
- cleaning
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 184
- 239000003054 catalyst Substances 0.000 title claims abstract description 153
- 150000001342 alkaline earth metals Chemical class 0.000 title claims abstract description 96
- 239000003513 alkali Substances 0.000 title claims abstract description 91
- 238000011069 regeneration method Methods 0.000 title abstract description 35
- 238000004140 cleaning Methods 0.000 claims abstract description 55
- 239000012459 cleaning agent Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 206010027439 Metal poisoning Diseases 0.000 claims abstract description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000005587 bubbling Effects 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 12
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 230000001172 regenerating effect Effects 0.000 claims description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000002956 ash Substances 0.000 description 56
- 230000008569 process Effects 0.000 description 18
- 230000008929 regeneration Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000003804 effect on potassium Effects 0.000 description 2
- 230000000674 effect on sodium Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 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
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- 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
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- 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
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
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Abstract
The invention provides a regeneration method of an alkali/alkaline earth metal poisoning denitration catalyst, which comprises the following steps: (1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst; (2) preparing a first cleaning agent, namely placing the catalyst treated in the step (1) into the first cleaning agent, and carrying out compressed air bubbling cleaning, wherein the first cleaning agent is a mixed solution of sulfuric acid, ammonium fluoride, a dispersing agent, a nonionic surfactant and deionized water; (3) preparing a second cleaning agent, placing the catalyst in the second cleaning agent, and cleaning by adopting ultrasonic, wherein the second cleaning agent is a mixed solution of ammonium chloride, ammonium bicarbonate, an ion chelating agent and deionized water; (4) and drying the catalyst. The regeneration method provided by the invention can effectively remove alkali/alkaline earth metal components causing catalyst poisoning, and the loss of the original active components in the catalyst is very little, so that the regeneration method has good economic benefit.
Description
Technical Field
The invention belongs to the field of denitration catalyst regeneration, and particularly relates to a regeneration method of an alkali/alkaline earth metal poisoned denitration catalyst.
Background
With the implementation of the ultra-low emission policy in the electric power and non-electric industry in recent years, the SCR denitration technology has been widely applied to industries such as glass, cement, sludge mixed combustion, biomass incineration and the like. In the SCR process, the catalyst is deactivated due to high ash, high alkali/alkaline earth metals, and the denitration performance is deteriorated. Catalyst alkali/alkaline earth metal poisoning is a common problem facing denitration in various industries. The alkali/alkaline earth metal poisoning of catalysts in various industries under the high-alkali smoke condition has the pluralityof and the complexity, and the difficulty is caused to the activity recovery of the deactivated catalysts.
Soluble alkali metals released during fuel combustion and free alkali/alkaline earth metals in fly ash are main factors causing the poisoning and deactivation of the SCR catalyst, and particularly when fuel with high alkali/alkaline earth metal content is combusted, high-concentration alkali/alkaline earth metals can be directly adsorbed on active positions of the catalyst if directly contacted with the surface of the catalyst, occupy acid positions on the surface of the catalyst to passivate the catalyst, so that the SCR catalyst is quickly deactivated. The denitration of boiler flue gas by using biomass as fuel faces more severe catalyst alkali/alkaline earth metal poisoning inactivation, wherein the content of sylvite in biomass combustion flue gas is 2-4 times higher than that of a coal-fired power plant. Under the influence of the factors, the SCR catalyst is easy to generate a rapid inactivation phenomenon in the cement kiln, and the activity attenuation of the SCR catalyst in the cement kiln is obviously worse than that of the coal-fired power plant from the practical understanding. Due to the unique process characteristics of the glass kiln, the flue gas carries a large amount of alkaline earth metals such as Ca, Mg and the like, and the large amount of alkaline earth metals are deposited on the surface of the catalyst, so that the catalyst can be quickly deactivated. Therefore, it is important to find a method for removing alkali/alkaline earth metals on the surface of the denitration catalyst and recycling the denitration catalyst.
However, the existing regeneration method for the denitration catalyst poisoned by the alkali/alkaline earth metal can only clean the conventional ash and trace alkali/alkaline earth metal, but can not regenerate the denitration catalyst poisoned by the alkali/alkaline earth metal in high-alkali flue gas, and has the problems of complex operation, long cleaning time, high loss rate of active components and the like.
Disclosure of Invention
The present invention has been made to solve at least one of the technical problems of the related art to a certain extent. Therefore, the invention provides a method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst.
The technical scheme adopted by the invention is as follows:
the invention provides a regeneration method of an alkali/alkaline earth metal poisoned denitration catalyst, which comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent, namely placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into the first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the first cleaning agent is a mixed solution of sulfuric acid, ammonium fluoride, a dispersing agent, a nonionic surfactant and deionized water;
(3) preparing a second cleaning agent, placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into the second cleaning agent, and cleaning under an ultrasonic condition, wherein the second cleaning agent is a mixed solution of ammonium chloride, ammonium bicarbonate, an ion chelating agent and deionized water;
(4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3);
the alkali/alkaline earth metal poisoned denitration catalyst is an alkali metal and/or alkaline earth metal poisoned denitration catalyst.
According to the regeneration method of the alkali/alkaline earth metal poisoning denitration catalyst provided by the embodiment of the invention, two different cleaning agents are directionally prepared to clean the alkali/alkaline earth metal poisoning denitration catalyst in a grading manner, so that the alkali/alkaline earth metal in the catalyst is further efficiently and directionally removed on the basis of removing substances such as silicon and aluminum in conventional ash scale, the inactivation caused by the occupation of active sites by the alkali/alkaline earth metal can be recovered, the loss of original active components in the catalyst is less, and the regeneration method has good economic benefits and application prospects.
In some embodiments, in the first cleaning agent, the mass content of the sulfuric acid is 0.1-1 wt%, the mass content of the ammonium fluoride is 0.2-0.5 wt%, the mass content of the dispersing agent is 1-1.5 wt%, and the mass content of the nonionic surfactant is 1-1.8 wt%, wherein the sulfuric acid is used as a main acid source of the cleaning agent, is ion-exchanged with the ammonium fluoride, and can partially dissolve vermicular deposited ash scale components in catalyst micro-pores; the dispersing agent can ensure that ash scale stripped from the catalyst is not easy to agglomerate, keeps dispersion and is more beneficial to cleaning and removal; the nonionic surfactant is used as an effective component of the detergent, can change the contact performance of the ash scale on the surface of the catalyst and promote the stripping and removal of the ash scale on the surface of the pore channel.
In some embodiments, the dispersant is one or a combination of two or more of ethylene oxide condensate, sodium carboxymethylcellulose, polyethylene glycol and polyacrylic acid, and the nonionic surfactant is one of alkylphenol ethoxylates, polyoxyethylene fatty acid or a mixture thereof.
In some embodiments, in the second cleaning agent, the mass content of ammonium chloride is 0.5-1 wt%, the mass content of ammonium bicarbonate is 0.2-0.5 wt%, and the mass content of the ion chelating agent is 0.01-0.1 wt%, wherein ammonium chloride is used as a main source of ammonium ions, has a good replacement effect on potassium and sodium in the catalyst, and can efficiently realize comprehensive and rapid removal and dissolution of alkali metals in the catalyst; the ammonium bicarbonate can react with alkaline earth metal chemically, and the alkaline earth metal is removed under the action of subacidity of the solution; the ion chelating agent can be complexed with various metal impurities, so that the alkali/alkaline earth metal components in the catalyst can be effectively removed.
In some embodiments, the ion-chelating agent is one or a combination of two or more of glycolic acid, ethylenediaminetetraacetic acid, amino acids, citric acid, oxalic acid.
In some embodiments, in the step (2), the temperature during cleaning is 30-40 ℃, the cleaning time is 60-120 min, the first cleaning agent can play a better role within the temperature range of 30-40 ℃, and gas needs to be introduced to perform a bubbling process during the cleaning process, so that the contact surface of the first cleaning agent and the catalyst is promoted, the solution fluidity is enhanced, and the taking-out of the ash scale in the catalyst is accelerated.
In some embodiments, in the step (3), the temperature during cleaning is 30-40 ℃, and the cleaning time is 10-60 min; the frequency of the ultrasound is 20-80 Hz, the ultrasound process is easy to generate heat, the water temperature needs to be kept not to be excessively increased, and the temperature is kept at 30-40 ℃.
In some embodiments, before the step (4), the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3) is washed by bubbling clean water for 10-60 min.
In some embodiments, in the step (4), the temperature of the drying treatment is 150-300 ℃, the temperature rising rate of the drying is not more than 6 ℃/min, and the temperature reduction rate is not more than 6 ℃/min.
In some embodiments, in step (1), the step of dry ash removal is: firstly removing floating ash on the surface of the alkali/alkaline earth metal poisoning denitration catalyst, and then blowing by using compressed air; the wet ash removal method comprises the following steps: spraying deionized water to the catalyst subjected to dry ash removal treatment for washing and ash removal; the step of softening the ash scale comprises the following steps: soaking the catalyst subjected to wet ash removal treatment in desalted water, and simultaneously cleaning the catalyst by bubbling compressed air.
The invention has the advantages and beneficial effects that:
according to the regeneration method of the alkali/alkaline earth metal poisoning denitration catalyst provided by the embodiment of the invention, a graded cleaning mode is adopted, firstly, a first cleaning agent is used for cleaning substances such as silicon and aluminum in the conventional ash scale of the alkali/alkaline earth metal poisoning denitration catalyst, meanwhile, a small amount of conventional deactivated parts such as alkali/alkaline earth metal are removed, secondly, the alkali/alkaline earth metal is directionally removed with high efficiency through a second cleaning agent, the regeneration method not only can efficiently remove alkali/alkaline earth metal components causing catalyst poisoning, but also has the advantages of extremely small loss of original active components in the catalyst, obvious recovery of the activity of the regenerated catalyst, prolonging of the service life of the regenerated catalyst, and good economic benefits, and the regeneration method is simple in process, low in energy consumption and good in popularization prospect.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The invention provides a regeneration method of an alkali/alkaline earth metal poisoned denitration catalyst, which comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent, namely placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into the first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the first cleaning agent is a mixed solution of sulfuric acid, ammonium fluoride, a dispersing agent, a nonionic surfactant and deionized water;
(3) preparing a second cleaning agent, placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into the second cleaning agent, and cleaning under an ultrasonic condition, wherein the second cleaning agent is a mixed solution of ammonium chloride, ammonium bicarbonate, an ion chelating agent and deionized water;
(4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3);
the alkali/alkaline earth metal poisoned denitration catalyst is an alkali metal and/or alkaline earth metal poisoned denitration catalyst.
According to the regeneration method of the alkali/alkaline earth metal poisoning denitration catalyst provided by the embodiment of the invention, two different cleaning agents are directionally prepared to clean the alkali/alkaline earth metal poisoning denitration catalyst in a grading manner, so that the alkali/alkaline earth metal in the catalyst is further efficiently and directionally removed on the basis of removing substances such as silicon and aluminum in conventional ash scale, the inactivation caused by the occupation of active sites by the alkali/alkaline earth metal can be recovered, the loss of original active components in the catalyst is less, and the regeneration method has good economic benefits and application prospects.
In some embodiments, the first cleaning agent comprises 0.1-1 wt% of sulfuric acid, 0.2-0.5 wt% of ammonium fluoride, 1-1.5 wt% of dispersant and 1-1.8 wt% of nonionic surfactant, wherein the sulfuric acid is used as a main acid source of the cleaning agent and is ion-exchanged with the ammonium fluoride, so that the vermicular accumulated ash scale components in the catalyst micro-pores can be partially dissolved; the dispersing agent can ensure that ash scale stripped from the catalyst is not easy to agglomerate, keeps dispersion and is more beneficial to cleaning and removal; the nonionic surfactant is used as an effective component of the detergent, can change the contact performance of the ash scale on the surface of the catalyst and promote the stripping and removal of the ash scale on the surface of the pore channel.
In some embodiments, the dispersant is one or a combination of two or more of ethylene oxide condensate, sodium carboxymethylcellulose, polyethylene glycol and polyacrylic acid, and the nonionic surfactant is one or a mixture of alkylphenol ethoxylates and polyoxyethylene oleic acid.
In some embodiments, in the second cleaning agent, the mass content of ammonium chloride is 0.5-1 wt%, the mass content of ammonium bicarbonate is 0.2-0.5 wt%, and the mass content of the ion chelating agent is 0.01-0.1 wt%, wherein the ammonium chloride is used as a main source of ammonium ions, has a good replacement effect on potassium and sodium in the catalyst, and can efficiently realize comprehensive and rapid removal and dissolution of alkali metals in the catalyst; the ammonium bicarbonate can react with alkaline earth metal chemically, and the alkaline earth metal is removed under the action of subacidity of the solution; the ion chelating agent can be complexed with various metal impurities, so that the alkali/alkaline earth metal components in the catalyst can be effectively removed.
In some embodiments, the ion chelating agent is one or a combination of two or more of glycolic acid, ethylenediaminetetraacetic acid, amino acids, citric acid, oxalic acid.
In some embodiments, in the step (2), the temperature during cleaning is 30-40 ℃, the cleaning time is 60-120 min, the first cleaning agent can play a better role within the temperature range of 30-40 ℃, and gas needs to be introduced to perform a bubbling process during the cleaning process, so that the contact surface of the first cleaning agent and the catalyst is promoted, the solution fluidity is enhanced, and the taking-out of the ash scale in the catalyst is accelerated.
In some embodiments, in the step (3), the temperature during cleaning is 30-40 ℃, and the cleaning time is 10-60 min; the frequency of the ultrasound is 20-80 Hz, the ultrasound process is easy to generate heat, the water temperature needs to be kept at 30-40 ℃ without excessive rise.
In some embodiments, before the step (4), the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3) is washed by bubbling clean water for 10-60 min.
In some embodiments, in the step (4), the temperature of the drying treatment is 150-300 ℃, the temperature rising rate of the drying is not more than 6 ℃/min, and the temperature reduction rate is not more than 6 ℃/min.
In some embodiments, in step (1), the step of dry ash removal is: firstly removing floating ash on the surface of the alkali/alkaline earth metal poisoning denitration catalyst, and then blowing by using compressed air; the wet ash removal method comprises the following steps: spraying deionized water to the catalyst subjected to dry ash removal treatment for washing and ash removal; the step of softening the ash scale comprises the following steps: soaking the catalyst subjected to wet ash removal treatment in desalted water, and simultaneously cleaning the catalyst by bubbling compressed air.
In embodiments 1 to 3 of the present invention, the dry ash removal specifically comprises the following steps: the catalyst module which needs to be subjected to a regeneration process is cleaned manually to remove floating ash on the outer surface of the catalyst frame, then the catalyst module is placed in an automatic soot blowing equipment room, and compressed air sprayed by a compressed air spray head is utilized to sweep the catalyst unit bodies one by one from the windward side and the leeward side of the catalyst unit bodies; during blowing, the area where the airflow carries the fly ash back splash is judged to be blocked by the deposited ash, and at the moment, the compressed air nozzle is slightly shaken at 10 degrees left and right respectively by taking the connecting line of the flow channel and the nozzle as an axis to carry out repeated blowing until no fly ash back splash exists.
In embodiments 1 to 3 of the present invention, the wet ash removal specifically comprises the following steps: transferring the catalyst module subjected to dry ash removal treatment to a regeneration spraying system, and spraying deionized water by using a high-pressure water gun to perform preliminary automatic cleaning on the catalyst; after the automatic washing is finished, manually washing the catalyst by using a high-pressure water gun to remove ash, removing all windward surfaces and shell ash deposits, removing loose ash deposits attached or blocked in most of flue gas runners, and removing and loosening hard ash deposits in part of the flue gas runners; in the cleaning process, whether the catalyst pore channel is blocked by dust deposition or not is judged by visual observation or a water splashing area is encountered, the catalyst pore channel is judged to be the dust deposition blocking area, and the water guns are slightly shaken at 10 degrees respectively from left to right by taking a connecting line of the flow channel and the water guns as an axis until the catalyst pore channel is completely dredged; if there is a harder deposit, the flushing is continued for at least 30 seconds in an effort to soften the deposit for easy removal.
In embodiments 1 to 3 of the present invention, the specific steps of softening the ash scale are as follows: and completely immersing the catalyst module subjected to wet ash removal treatment into a desalting water tank, and cleaning the catalyst module by adopting compressed air bubbling disturbance, wherein the cleaning process lasts for 60min to soften dirt.
The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst of the present invention will be described in further detail below by way of specific examples.
Example 1
The embodiment provides a method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst, which comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.8 wt% of sulfuric acid, 0.4 wt% of ammonium fluoride, 1.1 wt% of ethylene oxide condensation compound and 1.5 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, and standing; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into a first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the temperature is kept at 30 ℃ during cleaning, and the cleaning process lasts for 120 min;
(3) preparing a second cleaning agent: adding 0.8 wt% of ammonium chloride, 0.3 wt% of ammonium bicarbonate and 0.06 wt% of glycolic acid into deionized water, and uniformly stirring at normal temperature; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into a second cleaning agent, and cleaning under an ultrasonic condition, wherein the ultrasonic frequency is 40Hz, the temperature during cleaning is kept at 30 ℃, and the cleaning process lasts for 60 min; after cleaning, carrying out clean water bubbling washing on the catalyst, and removing surface residues for 30 min;
(4) and (4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3), wherein the drying temperature is 220 ℃.
Example 2
The embodiment provides a method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst, which comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.5 wt% of sulfuric acid, 0.3 wt% of ammonium fluoride, 1.2 wt% of sodium carboxymethylcellulose and 1.5 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, and standing; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into a first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the temperature is kept at 30 ℃ during cleaning, and the cleaning process lasts for 120 min;
(3) preparing a second cleaning agent: adding 0.8 wt% of ammonium chloride, 0.3 wt% of ammonium bicarbonate and 0.06 wt% of glycolic acid into deionized water, and uniformly stirring at normal temperature; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into a second cleaning agent, and cleaning under an ultrasonic condition, wherein the ultrasonic frequency is 40Hz, the temperature during cleaning is kept at 30 ℃, and the cleaning process lasts for 60 min; after cleaning, carrying out clean water bubbling washing on the catalyst, and removing surface residues for 30 min;
(4) and (4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3), wherein the drying temperature is 220 ℃.
Example 3
The embodiment provides a method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst, which comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.8 wt% of sulfuric acid, 0.4 wt% of ammonium fluoride, 1.1 wt% of ethylene oxide condensation compound and 1.5 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, and standing; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into a first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the temperature is kept at 30 ℃ during cleaning, and the cleaning process lasts for 120 min;
(3) preparing a second cleaning agent: adding 0.6 wt% of ammonium chloride, 0.2 wt% of ammonium bicarbonate and 0.04 wt% of EDTA into deionized water, and uniformly stirring at normal temperature; placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into a second cleaning agent, and cleaning under an ultrasonic condition, wherein the ultrasonic frequency is 40Hz, the temperature during cleaning is kept at 30 ℃, and the cleaning process lasts for 60 min; after cleaning, carrying out clean water bubbling washing on the catalyst, and removing surface residues for 30 min;
(4) and (4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3), wherein the drying temperature is 220 ℃.
Experimental example 1
After an SCR denitration system under certain high-alkali flue gas operates for one year, ammonia consumption on a reaction site is increased, ammonia escape is increased, and denitration performance is reduced. A single alkali/alkaline earth metal poisoning denitration catalyst sample monomer is selected for regeneration, the monomer has 18 x 18 holes, and the length is 980 mm. The alkali/alkaline earth metal poisoned denitration catalyst sample monomer was regenerated in the laboratory by the above regeneration method, and the sample before regeneration (alkali/alkaline earth metal poisoned denitration catalyst without any treatment) and after regeneration (catalyst obtained after regeneration treatment in examples 1 to 3) was subjected to physicochemical analysis and activity test, and the detection results were as follows:
test 1
And (3) detecting activity: according to DL/T1286-. The simulated smoke comprises the following components: the smoke volume is 180m 3 /h，O 2 (3vol.％)、H 2 O (5 vol.%), nitrogen as carrier gas, NO (350 mg/Nm) 3 ) Ammonia gas is introduced at the ammonia nitrogen molar ratio of 1:1, the test temperature is 380 ℃, and the activity detection results are shown in table 1:
TABLE 1 Activity of catalyst before and after regeneration (unit m/h)
Activity results: as shown in Table 1, the activity of the alkali/alkaline earth metal poisoned denitration catalyst before regeneration was 36 m/h; after regeneration, the activity of the alkali/alkaline earth metal poisoned denitration catalyst of the embodiment 1, the embodiment 2 and the embodiment 3 of the invention is respectively recovered to 40.0m/h, 39.2m/h and 38.7m/h, and the activity of the catalyst is improved after regeneration, which shows that the overall performance of the catalyst after regeneration is improved well.
Test 2
Detecting the microscopic specific surface area: the specific surface area of the catalyst is measured by using an ASAP 2460BET specific surface instrument, and the detection results are shown in Table 2:
TABLE 2 micro specific surface area (unit m) of catalyst before and after regeneration 2 /mg)
Specific surface area results: as shown in table 2, the micro specific surface area of the alkali/alkaline earth metal poisoned denitration catalyst before regeneration was: 39.73m 2 Per mg; after regeneration, the micro specific surface areas of the alkali/alkaline earth metal poisoned denitration catalysts of the examples 1, 2 and 3 of the present invention were raised to 42.85m 2 /mg、41.26m 2 /mg、42.33m 2 And/mg, which shows that the micro-pore channel of the regenerated catalyst is well dredged and the reaction area is recovered.
Test 3
XRF was used to detect other components in the catalyst samples before and after regeneration, as detailed in table 3:
TABLE 3 composition table of catalyst before and after regeneration (unit:%)
As can be seen from Table 3 above, active material V in the regenerated catalyst sample 2 O 5 、WO 3 、MoO 3 Little loss and ash scale as the main component SiO 2 、Al 2 O 3 、CaO、MgO、Na 2 O、K 2 The O content is significantly reduced, thus proving that the regeneration effect is good.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to 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. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) sequentially carrying out dry-method ash removal, wet-method ash removal and ash scale softening on the alkali/alkaline earth metal poisoned denitration catalyst;
(2) preparing a first cleaning agent, namely placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (1) into the first cleaning agent, and cleaning under the bubbling condition of compressed air, wherein the first cleaning agent is a mixed solution of sulfuric acid, ammonium fluoride, a dispersing agent, a nonionic surfactant and deionized water;
(3) preparing a second cleaning agent, placing the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (2) into the second cleaning agent, and cleaning under an ultrasonic condition, wherein the second cleaning agent is a mixed solution of ammonium chloride, ammonium bicarbonate, an ion chelating agent and deionized water;
(4) and (4) drying the alkali/alkaline earth metal poisoned denitration catalyst treated in the step (3).
2. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the first cleaning agent, the mass content of sulfuric acid is 0.1-1 wt%, the mass content of ammonium fluoride is 0.2-0.5 wt%, the mass content of dispersing agent is 1-1.5 wt%, and the mass content of nonionic surfactant is 1-1.8 wt%.
3. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1 or 2, characterized in that: the dispersing agent is one or the combination of more than two of ethylene oxide condensate, sodium carboxymethylcellulose, polyethylene glycol and polyacrylic acid, and the nonionic surfactant is one or the mixture of alkylphenol polyoxyethylene and polyoxyethylene fatty acid.
4. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the second cleaning agent, the mass content of the ammonium chloride is 0.5-1 wt%, the mass content of the ammonium bicarbonate is 0.2-0.5 wt%, and the mass content of the ion chelating agent is 0.01-0.1 wt%.
5. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1 or 4, characterized in that: the ion chelating agent is one or the combination of more than two of glycolic acid, ethylene diamine tetraacetic acid, amino acid, citric acid and oxalic acid.
6. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the step (2), the temperature during cleaning is 30-40 ℃, and the cleaning time is 60-120 min.
7. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the step (3), the temperature during cleaning is 30-40 ℃, and the cleaning time is 10-60 min; the frequency of the ultrasonic wave is 20-80 Hz.
8. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: before the step (4), carrying out clean water bubbling washing on the alkali/alkaline earth metal poisoning denitration catalyst treated in the step (3) for 10-60 min.
9. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the step (4), the temperature of the drying treatment is 150-300 ℃, the drying temperature rise rate is not more than 6 ℃/min, and the temperature reduction rate is not more than 6 ℃/min.
10. The method for regenerating an alkali/alkaline earth metal poisoned denitration catalyst according to claim 1, characterized in that: in the step (1), the dry ash removal step is as follows: firstly removing floating ash on the surface of the alkali/alkaline earth metal poisoning denitration catalyst, and then blowing by using compressed air; the wet ash removal method comprises the following steps: spraying deionized water to the catalyst subjected to dry ash removal treatment for washing and ash removal; the step of softening the ash scale comprises the following steps: soaking the catalyst subjected to wet ash removal treatment in desalted water, and simultaneously cleaning the catalyst by bubbling compressed air.
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