CN113600248A - Thallium-poisoned denitration catalyst regeneration method - Google Patents
Thallium-poisoned denitration catalyst regeneration method Download PDFInfo
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- CN113600248A CN113600248A CN202110953086.XA CN202110953086A CN113600248A CN 113600248 A CN113600248 A CN 113600248A CN 202110953086 A CN202110953086 A CN 202110953086A CN 113600248 A CN113600248 A CN 113600248A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 238000011069 regeneration method Methods 0.000 title claims abstract description 37
- 239000012459 cleaning agent Substances 0.000 claims abstract description 56
- 238000004140 cleaning Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- 208000026015 thallium poisoning Diseases 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 230000005587 bubbling Effects 0.000 claims description 22
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl betaine Chemical compound 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000001172 regenerating effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 3
- YZYASTRURKBPPS-UHFFFAOYSA-N C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] Chemical compound C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] YZYASTRURKBPPS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 2
- 229910052716 thallium Inorganic materials 0.000 abstract description 19
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 239000013543 active substance Substances 0.000 abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 6
- 150000001340 alkali metals Chemical class 0.000 abstract description 6
- 208000005374 Poisoning Diseases 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 abstract description 4
- 239000010937 tungsten Substances 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000004568 cement Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052935 jarosite Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 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
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
- B01J23/90—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention provides a thallium poisoning denitration catalyst regeneration method, which comprises the following steps: (1) pretreating a thallium-poisoned denitration catalyst; (2) cleaning the thallium poisoning denitration catalyst treated in the step (1) by using a first cleaning agent, wherein the first cleaning agent comprises a mixed solution of sulfuric acid, a dispersing agent and a nonionic surfactant; (3) cleaning the thallium poisoning denitration catalyst treated in the step (2) by using a second cleaning agent, wherein the second cleaning agent comprises a mixed solution of nitric acid, ammonium nitrate and an ion chelating agent; (4) and (4) drying and baking the denitration catalyst treated in the step (3). The regeneration method provided by the invention has little loss of active substances vanadium and tungsten in the catalyst, can not only cover micropores with ash and recover the inactivation caused by the occupation of active sites by alkali metal, but also recover the poisoning caused by thallium element, does not need to load active substances, and has good economic benefit; the cleaning process does not involve heating and other processes, and the energy consumption is low.
Description
Technical Field
The invention belongs to the field of catalyst regeneration, and particularly relates to a regeneration method of a thallium-poisoned denitration catalyst.
Background
Currently, with the national emphasis on environmental protection, ultra-low emission requirements are moving from the power industry to the non-power industry. In the non-electric industry, cement is a nitrogen oxide emission standard, and the outlet nitrogen oxide can be controlled to 200mg/m through the conventional SNCR method control3The following. However, with the push of ultra-low emission requirements, nitrogen oxides are reduced to 50mg/m3Hereinafter, only the SCR process is usually adopted. In the SCR process, the catalyst is deactivated due to high ash, high alkali metal or the like, and in addition, heavy metal element "thallium" carried from pyrite, which is a cement raw material, also causes catalyst poisoning, resulting in deterioration of denitration performance.
Thallium (Tl) is a heavy metal element and is contained in mineral raw materials such as mica, potassium feldspar, manganese ores, alunite, jarosite and the like with high content, and in the service process of the catalyst, thallium can enter a catalyst pore channel, and is enriched in the catalyst to occupy and destroy an active site of the catalyst, and finally thallium exists on the surface of the catalyst in a layered covering mode of thallium trioxide and thallium sulfate, so that the catalyst is inactivated.
The SCR denitration catalyst thallium poisoning is irreversible, and a conventional regeneration method can only clean conventional ash and alkali metal but cannot regenerate the thallium poisoning catalyst. However, in the prior patent documents, only a method specially aimed at thallium-poisoned catalyst regeneration cannot effectively clean the conventionally deactivated part, and the active material needs to be re-loaded.
The patent application with publication number CN111715210A discloses a regeneration method of thallium poisoning SCR denitration catalyst of cement kiln, which comprises the steps of dedusting, cleaning, soaking, rinsing, drying thallium poisoning SCR denitration catalyst, implanting titanium-vanadium-tungsten soluble active substance for subsequent calcination, thereby recovering the activity of the catalyst, and loading the active substance again; and the concentration of the used sulfuric acid is higher, so that a certain amount of active components of the catalyst are lost, and the operation safety is influenced.
Disclosure of Invention
The invention aims to provide a thallium-poisoned denitration catalyst regeneration method to solve the problems that a conventional deactivated part cannot be effectively cleaned and active substances need to be reloaded.
In order to achieve the purpose, the invention adopts the technical scheme that:
a thallium-poisoned denitration catalyst regeneration method comprises the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
(2) preparing a first cleaning agent, and cleaning the thallium poisoning denitration catalyst treated in the step (1) by using the first cleaning agent, wherein the first cleaning agent comprises a mixed solution of sulfuric acid, a dispersing agent and a nonionic surfactant;
(3) preparing a second cleaning agent, and cleaning the thallium poisoning denitration catalyst treated in the step (2) by using the second cleaning agent, wherein the second cleaning agent comprises a mixed solution of nitric acid, ammonium nitrate and an ion chelating agent;
(2) (4) drying and baking the denitration catalyst treated in the step (3), wherein the drying and baking steps are preferably as follows: the denitration catalyst is dried for 4-6h at the temperature of 120-140 ℃, and then calcined for 4-6h at the temperature of 350-450 ℃ to complete the regeneration. The calcined catalyst has higher mechanical strength and better wear resistance.
Preferably, in the step (2), the dispersing agent comprises one or more of ethylene oxide condensate, sodium diisooctyl succinate sulfonate and alkyl betaine, and the nonionic surfactant comprises one or more of alkylphenol ethoxylate, long-chain fatty alcohol ethoxylate, high-carbon fatty alcohol ethoxylate, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine.
Preferably, in the step (2), in the first cleaning agent: the mass content of the sulfuric acid is 0.5-0.6 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%.
Preferably, in step (3), the ion chelating agent comprises one or more of glycolic acid, organic polyphosphonic acid, fumaric acid (fumaric acid) -propylene sulfonic acid copolymer, ammonium citrate.
Preferably, in the step (3), in the second cleaning agent: the mass content of the nitric acid is 0.1-0.15 wt%, the mass content of the ammonium nitrate is 1.5-4 wt%, and the mass content of the ion chelating agent is 1.5-3 wt%.
Preferably, in the step (2), the soaking time of the thallium-poisoned denitration catalyst treated in the step (1) in the first cleaning agent is 1-2 hours, and preferably 1.5 hours.
Preferably, in the step (3), the soaking time of the thallium-poisoned denitration catalyst treated in the step (2) in the second cleaning agent is 0.5-2 hours, and preferably 0.5 hour.
Preferably, before the step (3), the thallium-poisoned denitration catalyst treated in the step (2) is subjected to a clean water bubbling washing for 0.05 to 0.2 hours, preferably 0.1 hour.
Preferably, before the step (4), the thallium-poisoned denitration catalyst treated in the step (3) is subjected to a clean water bubbling washing for 0.4 to 0.6 hours, preferably 0.5 hours.
Preferably, in the step (1), the pretreatment step comprises dry ash removal, wet ash removal and clean water bubbling, wherein in the dry ash removal step, floating ash on the surface of the thallium-poisoned denitration catalyst is removed firstly, and then high-pressure air is used for purging; in the wet ash removal step, spraying deionized water on the catalyst subjected to dry ash removal treatment for cleaning; in the step of bubbling clean water, the catalyst subjected to wet ash removal treatment is soaked in clean water, and compressed air is adopted for bubbling.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the regeneration method provided by the invention, a graded cleaning mode is adopted, firstly, the conventionally-deactivated part of the thallium-poisoned denitration catalyst is cleaned by the first cleaning agent, and secondly, the thallium-poisoned part is cleaned by the second cleaning agent, so that the loss of active substances vanadium and tungsten in the catalyst is very little, not only can the deactivation recovery caused by micropores covered by ash and active sites occupied by alkali metal be realized, but also the poisoning recovery caused by thallium element can be realized, and in addition, the active substances do not need to be loaded, the catalyst surface thallium removal rate is higher, and the method has good economic benefits; the process is simple, the cleaning process does not involve heating and other processes, and the energy consumption is low; the operation is safe, the service life of the regenerated catalyst is prolonged, and the method has good popularization prospect.
Detailed Description
The invention will be further described with reference to the examples shown below.
The embodiment provides a thallium-poisoned denitration catalyst regeneration method, preferably aiming at an SCR denitration deactivation catalyst in the cement industry, which comprises the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
the pretreatment step comprises the following steps of dry ash removal, wet ash removal and clean water bubbling in sequence, wherein the dry ash removal step is carried out firstly: firstly, conveying the inactivated thallium poisoning catalyst into an ash removal room, manually removing floating ash on the surface of the thallium poisoning catalyst, and blowing by using high-pressure air to remove ash in macroscopic pore channels as much as possible; and then carrying out wet ash removal: spraying deionized water on the catalyst subjected to dry ash removal treatment for cleaning, for example, moving the thallium poisoning catalyst to a regeneration spraying system, and spraying deionized water on the thallium poisoning catalyst by using a high-pressure water gun with appropriate pressure for primary cleaning; then, carrying out clear water bubbling: soaking the catalyst subjected to wet ash removal treatment in clean water, and simultaneously bubbling the catalyst by using compressed air, specifically placing the catalyst in a regeneration cleaning tank, soaking the catalyst in the clean water for 0.5-2 hours (preferably 1 hour), and simultaneously bubbling the catalyst in the bottom of the cleaning tank by using the compressed air to soften dirt.
(3) Preparing a first cleaning agent, and cleaning the thallium poisoning denitration catalyst treated in the step (1) by using the first cleaning agent, wherein the cleaning process is as follows: and (3) moving the pretreated thallium poisoning denitration catalyst into an ultrasonic tank, adding a prepared first cleaning agent, starting ultrasonic sound waves (good ultrasonic cleaning effect), and cleaning comprehensively for 1-2 hours, preferably for 1.5 hours.
The first cleaning agent comprises a mixed solution of sulfuric acid, a dispersing agent and a nonionic surfactant, and when the first cleaning agent is prepared: adding sulfuric acid, a dispersant and a nonionic surfactant with preset weight into deionized water, stirring uniformly at normal temperature, and standing.
Wherein, the dispersant comprises one or more of ethylene oxide condensate, sodium diisooctyl succinate sulfonate and alkyl betaine, and the ethylene oxide condensate is preferably used only. The nonionic surfactant comprises one or more of alkylphenol polyoxyethylene, long-chain fatty alcohol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene, fatty acid polyoxyethylene and polyoxyethylene alkylamine, preferably only alkylphenol polyoxyethylene is adopted.
In the first cleaning agent: the mass content of the sulfuric acid is 0.5-0.6 wt%, the mass content of the dispersing agent is 1-3 wt%, and the mass content of the nonionic surfactant is 1-4 wt%.
The sulfuric acid is used as a main acid source of the cleaning agent and can partially dissolve ash and scale components in the pores of the thallium-poisoned denitration catalyst. The condensate of the dispersant (such as ethylene oxide) has better dispersion performance, 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 (such as alkylphenol ethoxylates) is used as an effective component of the detergent, can change the contact performance of the ash and dirt on the surface of the catalyst, and promotes the stripping and removal of the ash and dirt on the surface of the pore channel.
Preferably, the thallium-poisoned denitration catalyst treated in the step (2) is subjected to clean water bubbling flushing to remove residues of the first cleaning agent on the surface for 0.05-0.2 hours, preferably 0.1 hour.
(4) Preparing a second cleaning agent, and cleaning the thallium-poisoned denitration catalyst treated in the step (2) by using the second cleaning agent, wherein the cleaning process is as follows: and moving the thallium-poisoned denitration catalyst into an ultrasonic tank, adding a prepared second cleaning agent, starting ultrasonic sound waves (good ultrasonic cleaning effect), and cleaning comprehensively for 0.5-2 hours, preferably for 1 hour.
The second cleaning agent comprises a mixed solution of nitric acid, ammonium nitrate and an ion chelating agent, and when the second cleaning agent is prepared, nitric acid, ammonium nitrate and the ion chelating agent with preset weight are added into deionized water, and the mixture is stirred uniformly at normal temperature and then stands.
Wherein the ion chelating agent comprises one or more of glycolic acid, organic polyphosphonic acid, fumaric acid (fumaric acid) -propylene sulfonic acid copolymer, and ammonium citrate, preferably only glycolic acid is used.
In the second cleaning agent: the mass content of the nitric acid is 0.1-0.3 wt%, the mass content of the ammonium nitrate is 1.5-4 wt%, and the mass content of the ion chelating agent is 1.5-3 wt%.
Preferably, the thallium-poisoned denitration catalyst treated in the step (3) is subjected to clean water bubbling flushing to remove residues of the first cleaning agent on the surface for 0.4-0.6 hour, preferably 0.5 hour.
The nitric acid is used as an acid auxiliary source, has extremely strong dissolving performance on the metal thallium, and can efficiently realize comprehensive and rapid removal and dissolution of the metal thallium in the catalyst; the ammonium nitrate has stronger oxidizability, can carry out a complex reaction with the metal thallium, and enhances the removal of the washed metal thallium; the ion chelating agent (such as glycolic acid) has ion chelating performance, can be complexed with various metal impurities, and can effectively remove the thallium metal component in the catalyst.
(5) Drying and baking the denitration catalyst treated in the step (3), wherein the drying and baking steps are preferably as follows: the denitration catalyst is dried for 4-6h at the temperature of 120-140 ℃, and then calcined for 4-6h at the temperature of 350-450 ℃ to complete the regeneration.
The regeneration method adopts two cleaning agent grades, and can carry out full-process regeneration on the thallium poisoning catalyst: firstly, cleaning a thallium-poisoned denitration catalyst by using a first cleaning agent, and simultaneously removing poisoning of conventional metals such as alkali metals and the like in the thallium-poisoned denitration catalyst on the basis of mainly removing substances such as silicon, aluminum, calcium, magnesium and the like in conventional ash scale on the thallium-poisoned denitration catalyst; and cleaning the cleaned thallium poisoning denitration catalyst by using a second cleaning agent, and mainly removing thallium metal and other heavy metals with high efficiency.
Example one
This example provides a method for regenerating a thallium-poisoned denitration catalyst, which includes the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.55 wt% of sulfuric acid, 1.3 wt% of ethylene oxide condensation compound and 1.4 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, standing, cleaning the thallium poisoning denitration catalyst treated in the step (1) by using a first cleaning agent, and carrying out clean water bubbling washing on the catalyst after cleaning to remove surface residues for 0.1 hour;
(3) preparing a second cleaning agent: adding 0.13 wt% of nitric acid, 2.5 wt% of ammonium nitrate, 2.4 wt% of glycolic acid and deionized water, stirring uniformly at normal temperature, and cleaning the thallium poisoning denitration catalyst treated in the step (2) by using a second cleaning agent; after cleaning, carrying out clean water bubbling washing on the catalyst to remove surface residues for 0.5 hour;
(4) and (4) drying and baking the denitration catalyst treated in the step (3).
Example two
This example provides a method for regenerating a thallium-poisoned denitration catalyst, which includes the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.5 wt% of sulfuric acid, 0.9 wt% of ethylene oxide condensation compound and 1.1 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, standing, cleaning the thallium poisoning denitration catalyst treated in the step (1) by using a first cleaning agent, and carrying out clean water bubbling washing on the catalyst after cleaning to remove surface residues for 0.1 hour;
(3) preparing a second cleaning agent: adding 0.2 wt% of nitric acid, 4 wt% of ammonium nitrate, 3 wt% of glycolic acid and deionized water, stirring uniformly at normal temperature, and cleaning the thallium poisoning denitration catalyst treated in the step (2) by using a second cleaning agent; after cleaning, carrying out clean water bubbling washing on the catalyst to remove surface residues for 0.5 hour;
(4) and (4) drying and baking the denitration catalyst treated in the step (3).
EXAMPLE III
This example provides a method for regenerating a thallium-poisoned denitration catalyst, which includes the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
(2) preparing a first cleaning agent: adding 0.6 wt% of sulfuric acid, 1.8 wt% of ethylene oxide condensation compound and 2.0 wt% of alkylphenol polyoxyethylene into deionized water, stirring uniformly at normal temperature, standing, cleaning the thallium poisoning denitration catalyst treated in the step (1) by using a first cleaning agent, and carrying out clean water bubbling washing on the catalyst after cleaning to remove surface residues for 0.1 hour;
(3) preparing a second cleaning agent: adding 0.10 wt% of nitric acid, 1.8 wt% of ammonium nitrate, 1.5 wt% of glycolic acid and deionized water, stirring uniformly at normal temperature, and cleaning the thallium poisoning denitration catalyst treated in the step (2) by using a second cleaning agent; after cleaning, carrying out clean water bubbling washing on the catalyst to remove surface residues for 0.5 hour;
(4) and (4) drying and baking the denitration catalyst treated in the step (3).
Comparative example
The thallium-poisoned denitration catalyst provided in the present example is different from the first example in that: this comparative example only pretreats the thallium-poisoned denitration catalyst.
After an SCR denitration system of a certain cement plant operates for one year, the ammonia consumption of a reaction site is increased, the ammonia escape is increased, and the denitration performance is poor. A thallium poisoning denitration catalyst sample monomer is selected in the reactor, the monomer is 13 multiplied by 13 holes, and the length is 980 mm. The thallium-poisoned denitration catalyst sample monomer is regenerated in a laboratory by using the regeneration method, and the sample before regeneration (comparative example) and after regeneration (example) is subjected to physicochemical analysis and activity test, a full-size Chinese-style bench is adopted, and the detection results are as follows:
test 1
And (3) detecting activity: according to DL/T1286-. The simulated gas composition was: flue gas amount 168m3/h,O2(2.5vol.%)、HO2(7vol.%)N2As a carrier gas, NO (350 mg/Nm)3) NH is introduced into the reactor in a molar ratio of 1 to 1 of ammonia nitrogen3The test temperature was 240 ℃.
Activity results: the activity of the catalyst of the comparative example (before regeneration) was 20.5m/h, and the activity of the catalysts of examples one to three (after regeneration) was restored to 28.6m/h, 28.0m/h and 28.1m/h, respectively, as shown in Table 1. The activity of the regenerated catalyst is greatly improved, which shows that the overall performance of the regenerated catalyst is well recovered.
TABLE 1 catalyst of comparative example (before regeneration), catalyst of examples one to three (after regeneration) Activity (in m/h)
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.
Specific surface area results: the catalyst of the comparative example (before regeneration) had a microscopic specific surface area of: 45.23m2The microscopic specific surface area of the catalysts of examples one to three (after regeneration) was raised to 56.85m2/mg、57.91m2Mg and 56.80m2In mg, see Table 2. The micro pore channel of the regenerated catalyst is well dredged, and the reaction area is recovered.
Table 2 microscopic specific surface area (unit m) of catalyst of comparative example (before regeneration), catalyst of examples one to three (after regeneration)2/mg)
Test 3
The detection results of the main components are as follows:
(1) the thallium concentration in the catalyst sample was measured using ICP, and the thallium concentration in the catalyst of comparative example (before regeneration) was 7.4%, and the thallium concentrations in the catalysts of examples one to three (after regeneration) were 0.70%, 0.79%, and 0.95%, respectively, as shown in table 3. Indicating that a large amount of thallium metal is removed after regeneration.
Table 3 thallium concentration table (unit%)
(2) XRF was used to detect other components in the catalyst sample, detailed in the table below:
table 4 composition table (unit%)
Composition (I) | Comparative example | Example one | Example two | EXAMPLE III |
TiO2 | 72.48 | 73.30 | 71.89 | 72.64 |
MoO3 | 7.69 | 7.49 | 7.34 | 7.07 |
WO3 | 3.29 | 3.10 | 3.15 | 3.09 |
V2O5 | 2.30 | 2.12 | 2.15 | 2.06 |
SiO2 | 8.94 | 3.24 | 4.17 | 3.31 |
CaO | 3.94 | 0.80 | 1.10 | 0.82 |
SO3 | 2.96 | 0.91 | 1.13 | 0.92 |
Al2O3 | 2.31 | 0.49 | 0.61 | 0.45 |
MgO | 1.15 | 0.35 | 0.40 | 0.37 |
Na2O | 1.23 | 0.26 | 0.34 | 0.22 |
K2O | 1.45 | 0.17 | 0.26 | 0.15 |
As can be seen from Table 4 above, active material V in the regenerated catalyst sample2O5、WO3、MoO3Little loss, foreign material SiO2、CaO、Al2O3、MgO、Na2O、K2The O is clearly removed, thus demonstrating good regeneration.
The activity and the surface area of the catalyst regenerated by the regeneration method are remarkably recovered, the influence on active components vanadium and tungsten is small, multiple losses are avoided, additional active substances do not need to be supplemented, and the method has good economic benefit.
According to the regeneration method provided by the invention, a graded cleaning mode is adopted, firstly, the conventional deactivated part of the thallium-poisoned denitration catalyst is cleaned, and secondly, the thallium-poisoned part is cleaned, so that the loss of active substances vanadium and tungsten in the catalyst is very little, not only can the deactivation recovery caused by that micropores are covered by ash and alkali metal occupies active sites, but also the poisoning recovery caused by thallium element can be realized, and active substances do not need to be loaded; the process is simple, the cleaning process does not involve heating and other processes, and the energy consumption is low.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A thallium-poisoned denitration catalyst regeneration method is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreating a thallium-poisoned denitration catalyst;
(2) preparing a first cleaning agent, and cleaning the thallium poisoning denitration catalyst treated in the step (1) by using the first cleaning agent, wherein the first cleaning agent comprises a mixed solution of sulfuric acid, a dispersing agent and a nonionic surfactant;
(3) preparing a second cleaning agent, and cleaning the thallium poisoning denitration catalyst treated in the step (2) by using the second cleaning agent, wherein the second cleaning agent comprises a mixed solution of nitric acid, ammonium nitrate and an ion chelating agent;
(4) and (4) drying and baking the denitration catalyst treated in the step (3).
2. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (2), the dispersing agent comprises one or more of an ethylene oxide condensate, sodium diisooctyl succinate sulfonate and alkyl betaine, and the nonionic surfactant comprises one or more of alkylphenol ethoxylates, long-chain fatty alcohol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine.
3. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (2), in the first cleaning agent: the mass content of the sulfuric acid ranges from 0.5 to 0.6 wt%, the mass content of the dispersing agent ranges from 1 to 3 wt%, and the mass content of the nonionic surfactant ranges from 1 to 4 wt%.
4. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (3), the ion chelating agent comprises one or more of glycolic acid, organic polyphosphonic acid, fumaric acid (fumaric acid) -propylene sulfonic acid copolymer and ammonium citrate.
5. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (3), in the second cleaning agent: the mass content of the nitric acid is 0.1-0.3 wt%, the mass content of the ammonium nitrate is 1.5-4 wt%, and the mass content of the ion chelating agent is 1.5-3 wt%.
6. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (2), the soaking time of the thallium poisoning denitration catalyst treated in the step (1) in the first cleaning agent is 1-2 hours.
7. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (3), the soaking time of the thallium poisoning denitration catalyst treated in the step (2) in the second cleaning agent is 0.5-2 hours.
8. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: and (3) before the step (3), carrying out clean water bubbling washing on the thallium-poisoned denitration catalyst treated in the step (2) for 0.05-0.2 hour.
9. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: and (4) before the step (4), carrying out clean water bubbling washing on the thallium-poisoned denitration catalyst treated in the step (3) for 0.4-0.6 hour.
10. The method for regenerating a thallium-poisoned denitration catalyst according to claim 1, characterized in that: in the step (1), the pretreatment step comprises dry ash removal, wet ash removal and clean water bubbling, wherein in the dry ash removal step, floating ash on the surface of the thallium poisoning denitration catalyst is removed firstly, and then high-pressure air is used for blowing; in the wet ash removal step, spraying deionized water on the catalyst subjected to dry ash removal treatment for cleaning; in the step of bubbling clean water, the catalyst subjected to wet ash removal treatment is soaked in clean water, and compressed air is adopted for bubbling.
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