CN103492075B - Method for regenerating exhaust gas purifying catalyst - Google Patents
Method for regenerating exhaust gas purifying catalyst Download PDFInfo
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- CN103492075B CN103492075B CN201280018573.6A CN201280018573A CN103492075B CN 103492075 B CN103492075 B CN 103492075B CN 201280018573 A CN201280018573 A CN 201280018573A CN 103492075 B CN103492075 B CN 103492075B
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- catalyst
- exhaust gas
- gas purifying
- purifying catalyst
- renovation process
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims description 51
- 230000001172 regenerating effect Effects 0.000 title description 4
- 238000011069 regeneration method Methods 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 238000004140 cleaning Methods 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 238000009418 renovation Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000005470 impregnation Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 231100000567 intoxicating Toxicity 0.000 description 24
- 230000002673 intoxicating effect Effects 0.000 description 24
- 208000005374 Poisoning Diseases 0.000 description 14
- 231100000572 poisoning Toxicity 0.000 description 14
- 230000000607 poisoning effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 239000000470 constituent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- -1 VOC Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 208000007964 Organophosphate Poisoning Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- VYOZKLLJJHRFNA-UHFFFAOYSA-N [F].N Chemical compound [F].N VYOZKLLJJHRFNA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
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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
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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
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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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a regeneration method that comprises: a step wherein a used exhaust gas purifying catalyst to which silicon or the like adheres is fired at 400-700 DEG C; and a step wherein the fired catalyst is impregnated with 1-25 wt% of an alkali solution, said alkali impregnation step being carried out at a pH of 13 or more. The alkali solution is preferably sodium hydroxide or potassium hydroxide. In addition, it is preferable that a cleaning step is added after the alkali impregnation step. The regeneration method of the present invention removes an organic silicon or the like adhering to a used exhaust gas purifying catalyst, to which silicon and phosphorus adhere, and is thus capable of sufficiently recovering the catalytic activity.
Description
Technical field
The present invention relates to the method that the exhaust gas purifying catalyst after to use regenerates, particularly relate to the method for the regeneration of the catalyst being suitable for being attached with organo-silicon compound.
Background technology
Make that the VOC (VOC) in the waste gas produced by application, printing, synthetic, food, medical treatment, chemical plant etc. is innoxious, odorless time, adopt exhaust gas purifying catalyst VOC oxidation Decomposition reduced.As this exhaust gas purifying catalyst, be knownly such as coated with at water the catalyst that (washcoat) has the noble metal such as the platinum honeycomb ceramics of the metal oxides such as aluminium oxide carried as catalyst metals.These catalyst promote the oxidation reaction speed of VOC by catalytic action, catalyst itself not change before and after reaction.Therefore, think in theory and forever can maintain catalytic activity, in the waste gas in fact as purification object, except the hydrocarbon such as VOC, be also mixed into siliceous material etc.If such silicon matter etc. are attached to catalyst surface, then catalytic activity can decline because of poisoning.Therefore, for plant gas, in order to maintain the VOC discharge rate of regulation, need removing be attached to the intoxicating material of catalyst surface and recover the technology of the catalytic activity because of poisoning decline.
Based in the catalyst recovery process of this object, if only adopt harsh treatment conditions to remove intoxicating material, then the water maintained needed for catalytic activity is coated with and catalyst metals likely can come off.Therefore, the renovation process only removing intoxicating material when not making catalyst metals etc. come off must be adopted.
In this context, record in patent document 1 and use hydrogen fluorine ammonium etc. carry out impregnation process after washing to catalyst and make the method that the drying of the catalyst after cleaning regenerates.By the method, regeneration process can be carried out under lower treatment temperature, prevent from maintaining coming off of the catalyst metals needed for activity etc.In addition, record in patent document 2 hydrotreating catalyst of mink cell focus after using is burnt till after carry out washing the catalyst recovery process of process in order to sulfuric acid or the caustic soda rinse water controlled in pH1 ~ 11.By the method, can when not removing molybdenum isoreactivity composition, attachment such as removing vanadium, nickel etc.
Prior art document
Patent document
Patent document 1: Japanese Patent Laid No. 2659802 publication
Patent document 2: Japanese Patent Laid No. 3715893 publication
The summary of invention
Invent technical problem to be solved
But, in the renovation process that above-mentioned document is recorded, according to the kind of intoxicating material being attached to catalyst, likely cannot fully remove intoxicating material, cannot become to recycle by regeneration, in exhaust-gas treatment, there is enough active catalyst.Particularly intoxicating material be organosilicon or organophosphor when, the method recorded by patent document 1 cannot remove organosilicon and organophosphor completely, and catalytic activity is not easily recovered.On the other hand, containing organosilyl material, there is the excellent character such as heat resistance, cold resistance, weatherability, water repellency, electrical characteristics, so also increase to the discharge rate in waste gas, thus require to be attached with these organosilyl catalyst also renewable, technology that can reuse catalyst.
So, the object of the present invention is to provide and not only prevent the coming off of catalyst component, but also by regenerating the method regenerated the exhaust gas purifying catalyst being attached with silicon or phosphorus fully recovering catalytic activity.
The technical scheme that technical solution problem adopts
The present invention solved the problem relates to the renovation process of following exhaust gas purifying catalyst: be included in 400 ~ 700 DEG C to the firing process that burns till of catalyst after using with make the catalyst soakage burnt till in the alkali steeping operation of the aqueous slkali of 1 ~ 25wt%, alkali steeping operation is implemented under the condition of more than pH13.Described regeneration methods of the invention be to the use being attached with silicon or phosphorus after the method that regenerates of catalyst.
If adopt method of the present invention, then can regenerate the catalyst of the oxidation Decomposition for VOC (volatile hydrocarbon) composition contained in plant gas etc., recover the activity needed for waste gas purification.As intoxicating material, can the catalyst being attached with organo-silicon compound, organic phosphorus compound etc. be regenerated.Be particularly suitable for the regeneration of the catalyst being attached with organo-silicon compound.In the present invention, the formation as the catalyst of regeneration object can adopt the formation of the catalyst metals base materials such as the honeycomb ceramics scribbling aluminium oxide, zirconia, titanium oxide, cerium oxide etc. at water carrying the noble metals such as platiniferous, palladium, rhodium, ruthenium, iridium, gold, silver.As exhaust gas purifying catalyst, generally also adopt the formation also carrying the co-catalysts such as vanadium, nickel, molybdenum except catalyst metals, but be better not containing these co-catalysts as the catalyst of regeneration object of the present invention.This is because the co-catalysts such as vanadium easily come off from catalyst in the alkali steeping operation etc. of following explanation, thus exist be difficult to by regeneration return to poisoning before the tendency of catalytic activity.
The feature of the method for the present invention that these catalyst regenerate being, by making catalyst soakage in aqueous slkali, by being attached to the intoxicating substance dissolves removings such as the silicon of catalyst, before alkali steeping, implementing firing process.In firing process, the burned removing of the organic principle in intoxicating material, only remains the inorganic constituents in intoxicating material in catalyst.Therefore, inorganic constituents can be removed efficiently in the alkali steeping of subsequent handling.Firing process, 400 ~ 700 DEG C of enforcements, is better 500 ~ 600 DEG C of enforcements.During lower than 400 DEG C, the burning removing of the organic principle in intoxicating material cannot fully be carried out, if more than 700 DEG C, it is inorganization that the oxidation that intoxicating material then occurs causes, the removal rate of the intoxicating material in alkali steeping operation improves, but catalyst component generation aggegation, noble metal Large stone, specific area declines.Therefore, according to the kind of VOC, catalytic activity likely declines.As the pretreatment of firing process, can be cleaned by air blast, pure water or running water etc. catalyst.In addition, this cleaning can be boiled and be implemented.By cleaning before burning till, the water-soluble intoxicating materials such as segregative dust and sulphur compound can be removed efficiently in advance, improving the removing efficiency of the silicon in alkali steeping operation etc.
After firing process, make catalyst soakage in the aqueous slkali of concentration 1 ~ 25wt%, implement alkali steeping operation.As mentioned above, by alkali steeping operation, the inorganic constituents deriving from intoxicating material be also attached on catalyst can be dissolved removing after firing process.As aqueous slkali, can use NaOH or potassium hydroxide, be better use NaOH.Alkali concn is better 5 ~ 12.5wt%.During lower than 1wt%, the dissolving of inorganic constituents removing efficiency is not enough, even if more than 25wt%, the removing efficiency of intoxicating material also improves seldom, but thereafter for needing a large amount of water in carrying out cleaning with in operation.In addition, when aqueous slkali employing NaOH, if alkali concn is more than 25wt%, then may produce water-containing crystal under low temperature, winter etc. not easily process.
Above-mentioned alkali steeping operation is implemented under the condition of pH value of solution more than 13, is better to implement under the condition of more than pH13.5.If pH is lower than 13, then there is the tendency being difficult to fully dissolve removing inorganic constituents.
Liquid temperature during alkali steeping is better 0 ~ 90 DEG C, is more preferably 30 ~ 60 DEG C.If liquid temperature is too low, then the dissolving removing efficiency of inorganic constituents is not enough, if more than 90 DEG C, then the evaporation capacity of aqueous slkali increases, and is difficult to the alkali concn remaining on regulation, also needs pump-down process.Dip time is better 1 minute ~ 24 hours, is more preferably 1 hour ~ 16 hours.When being less than 1 minute, the dissolving removing efficiency of inorganic constituents is not enough, even if more than 24 hours, the dissolving removing efficiency of inorganic constituents also improves hardly, and the stripping etc. of catalyst component may occur.During the intoxicating material concentration height of the catalyst after using, in dipping process, alkali concn or liquid temperature can be improved or extend dip time to improve regeneration efficiency.As mentioned above, the alkali concn of dipping process, liquid temperature and time adjust according to the attachment concentration of intoxicating material.
After alkali steeping, it is better the matting the pH implementing to carry out cleaning to cleaning solution reaches near neutral.Matting is better utilize pure water or running water to carry out, and can utilize pure water or running water cleaning near neutral, be adjusted to neutrality with acid solution.The cleaning of running water is particularly adopted to be better use acid solution afterwards.During cleaning, likely catalyst adheres to alkali metal component (Na, K etc.) in running water or alkaline earth metal component (Ca etc.) etc., but by using acid solution, these attached components can be removed.In addition, when using acid solution, easily can reach near neutral, therefore can reduce the amount of pure water needed for cleaning or running water.
As acid solution, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, formic acid etc. can be used, particularly preferably nitric acid.This is because nitric acid can not make catalyst component poisoning, can easily pass through dry or burn till removing.In addition, the concentration of acid solution is better 0.3 ~ 3.0wt%.During lower than 0.3wt%, the removing effect of alkali metal component and alkaline earth metal component is not enough, if reach 3.0wt%, then fully can remove alkali metal component etc., even if adopt higher concentration, removing effect also improves seldom.When using acid solution, be better make the pH of solution be 0.2 ~ 1.5, particularly preferably make pH in the scope of 0.2 ~ 1.0.If within the scope of above-mentioned pH, then fully can remove alkali metal component etc.
After matting, be better the drying process implementing to make catalyst drying, heating-up temperature is better 100 ~ 700 DEG C.This is to remove moisture remaining in the catalyst after cleaning and sour composition etc.
When implementing matting with pure water, be better make baking temperature be 100 DEG C ~ 250 DEG C.This is because lower than 100 DEG C time, be difficult to the moisture fully removed in catalyst carrier, the removing of moisture does not need the temperature higher than 250 DEG C.
On the other hand, when using acid solution in matting, be better make baking temperature be 300 ~ 600 DEG C, particularly preferably 450 ~ 550 DEG C.During lower than 300 DEG C, be difficult to, completely except disacidify composition, by being set to 600 DEG C, fully to remove disacidify composition.
The catalyst regenerated by above renovation process, compared with the catalyst before regeneration, significantly can reduce the content of silicon and phosphorus.Silicon in catalyst after regeneration or the content of phosphorus are better respectively at below 1.5wt%.If at below 1.5wt%, the catalytic activity before regeneration fully can be returned to.If particularly silicone content is at below 1.5wt%, then the activity of the catalyst after regeneration easily improves.Because the content that there is silicon or phosphorus is lower, then therefore the tendency that the catalytic activity after regeneration is higher can be content 0wt%.
The effect of invention
If employing regeneration methods of the invention, then can the exhaust gas purifying catalyst after the use being attached with silicon or phosphorus be regenerated.
The simple declaration of accompanying drawing
Fig. 1 is the ethanol cleaning test result of the regenerated catalyst of embodiment 2.
Fig. 2 is the toluene cleaning test result of the regenerated catalyst of embodiment 3.
The mode carried out an invention
Below, the preferred embodiment of the present invention is described.
[embodiment 1]
For the exhaust gas purifying catalyst poisoning because of organo-silicon compound and VOC, with various regeneration condition removing intoxicating material, compare the catalytic performance etc. after regeneration.
embodiment 1
As catalyst, be used in the catalyst stainless steel honeycomb ceramics (φ 56mm × 50mmL) that water scribbles the gamma-alumina of 80g/L carrying the Pt of 2g/L.As intoxicating material, organo-silicon compound adopt organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI (SHIN-ETSU HANTOTAI シ リ コ ー Application) dimethicone KF96, VOC composition processed to adopt toluene.The solution that organo-silicon compound and toluene are obtained by mixing with the ratio of 1:1 with air quantity 125L/ minute, catalyst inlet temperature 350 DEG C, 340 μ L/ minute condition liquor charging, make it within poisoning 21 minutes, lose activity completely to catalyst.The organosilicon amount of liquor charging is 3500 μ L.
Catalyst after above-mentioned use is regenerated by following method.First, after cleaning 1 hour with 500mL boiling tap water, water is brushed removing, carry out 1 hour burn till at 500 DEG C.After burning till, impregnated in 12.5wt% sodium hydroxide solution 400ml, stir 6 hours at 60 DEG C.Catalyst pure water cleaning after alkali steeping reaches near neutral to pH, regenerates 120 DEG C of dryings.
embodiment 2 ~ 6
Be used as the catalyst of the regeneration object identical with embodiment 1, the method replacing NaOH by using potassium hydroxide in alkali steeping operation and method alkali concn being changed into 5wt% or 25wt% regenerate (table 1) catalyst.Other condition is identical with embodiment 1.
embodiment 7
Be used as the catalyst of the regeneration object identical with embodiment 1, the solution temperature of alkali steeping operation be set to 30 DEG C catalyst is regenerated.Other condition is identical with embodiment 1.
embodiment 8 ~ 9
Be used as the catalyst of the regeneration object identical with embodiment 1, firing temperature be set to 600 DEG C, 700 DEG C and catalyst is regenerated.Other condition is identical with embodiment 1.
embodiment 10 ~ 12
After alkali steeping, add nitric acid with after running water cleaning.Concentration of nitric acid is set to 0.4wt% (pH1.1), 0.6wt% (pH0.9), 3.0wt% (pH0.2).Baking temperature after cleaning is set to 500 DEG C.Other condition is identical with embodiment 1.
embodiment 13 ~ 14
Baking temperature after cleaning is set to 450 DEG C, 550 DEG C regenerate catalyst.Other condition is identical with embodiment 11.
embodiment 15
After using potassium hydroxide to carry out alkali steeping, with nitric acid cleaning, catalyst is regenerated.Firing temperature, solution concentration etc. adopt the condition shown in table 1.
comparative example 1,2
Be used as the catalyst of the regeneration object identical with embodiment 1, after catalyst is boiled cleaning, do not burn till, implement alkali steeping operation with the NaOH of 12.5wt% and 5wt%.Except not burning till, identical with embodiment 1.
The mensuration of zero Si amount
For the catalyst of above-described embodiment and comparative example, determine the adhesion amount of the Si of the catalyst before and after relative to regeneration.In the mensuration of Si amount, stainless steel honeycomb body being disintegrated, cut out its part, by using the simple quantitative analysis of fluorescent X-ray, the Si amount being attached to catalyst surface being measured.Measure as a result, the attachment Si before regeneration in fouled catalyst measures as about 10wt%.
Zero toluene cleaning test
For the catalyst after regeneration, measure toluene purifying rate.The mensuration of purifying rate is with SV60000h
-1, toluene 300ppm, air balance condition carry out.Toluene purifying rate during catalyst inlet temperature 200 DEG C is shown in table 1.
[table 1]
Catalyst attachment Si amount before ※ regeneration: about 10wt%
Above as a result, carry out in the regenerated catalyst (embodiment 1 ~ 15) burnt till before alkali steeping, attachment Si amount significantly reduces, and toluene purifying rate is also high.Firing temperature is higher, then Si removal amount is more, and toluene purifying rate is higher (embodiment 1,8,9) also.Alkali concn in alkali steeping and liquid temperature higher, then Si removal amount is more, and toluene purifying rate is higher (embodiment 1 ~ 7) also.No matter when using any in NaOH and potassium hydroxide as aqueous slkali, all can Si be removed, the recovery (embodiment 1 ~ 6) of visible toluene purifying rate.
In addition, in matting, use the situation (embodiment 10 ~ 15) of nitric acid also same with the situation of cleaning with pure water (embodiment 1 ~ 9) with after running water cleaning, attachment Si amount reduces, and toluene purifying rate is also high.No matter to use in NaOH and potassium hydroxide any all obtains same result as when aqueous slkali for this.
On the other hand, the Si removal rate of not carrying out the regenerated catalyst of firing process before alkali steeping is low, and the recovery of toluene purifying rate also insufficient (comparative example 1,2).
[embodiment 2]
As intoxicating material, to being attached with organic phosphorus compound but not the catalyst of organo-silicon compound regenerates, the test of the catalyst performance after regenerating.
As poisoning front catalyst, use the catalyst identical with embodiment 1.Use containing toluene 500ppm and as the triethyl phosphate 280ppm of organophosphor gas with 45 minutes, the condition of inlet temperature 300 DEG C makes above-mentioned catalyst poisoning.Poisoning catalyst regenerates with the condition identical with the renovation process of embodiment 1.For above-mentioned regenerated catalyst, by ethanol cleaning test assess performance.
Zero ethanol cleaning test
With SV=60000h
-1, ethanol 300ppm, air balance condition test.For the catalyst before poisoning front catalyst and poisoning rear regeneration, test similarly.Result is shown in Fig. 1.
Above as a result, regenerate catalyst before treatment, because of organophosphorus poisoning, ethanol purifying rate declines to a great extent, and in catalyst after regeneration process, the ethanol purifying rate that have dropped recovers completely.Therefore, known regeneration methods of the invention is also suitable for the regeneration of the fouled catalyst because of organic phosphorus compound.
[embodiment 3]
The catalyst used actual in factory is regenerated, the test of the catalyst performance after regenerating.
As poisoning front catalyst, use the catalyst identical with embodiment 1.After this catalyst being used for the VOC removing of the waste gas purification apparatus adopting factory, be used as the catalyst as regeneration object.Regeneration condition is identical with embodiment 1.For the catalyst before and after regeneration, measure the intoxicating amount of substance of attachment.In the mensuration of intoxicating material, stainless steel honeycomb body is disintegrated, cut out its part, for arbitrary 3 places, carry out simple quantitative analysis by EPMA and calculate mean value.In addition, toluene cleaning test is carried out with the condition identical with embodiment 1.Result is shown in table 2 and Fig. 2.
[table 2]
After catalyst poisoning before regeneration (wt%)
| 1 | 2 | 3 | Mean value | |
| C | 4.57 | 3.67 | 4.48 | 4.24 |
| O | 33.74 | 32.65 | 31.00 | 32.46 |
| Al | 34.10 | 33.29 | 32.89 | 33.42 |
| Si | 3.51 | 3.57 | 3.59 | 3.55 |
| P | 0.28 | 0.23 | 0.21 | 0.24 |
| Ca | 0 | 0 | 0.12 | 0.04 |
| Pt | 7.18 | 6.90 | 6.69 | 6.92 |
After catalyst regeneration (wt%)
| 1 | 2 | 2 | Mean value | |
| C | 0 | 0 | 0 | 0 |
| O | 35.32 | 29.826 | 32.46 | 32.54 |
| Al | 42.55 | 36.512 | 38.815 | 39.29 |
| Si | 0.878 | 0.948 | 1.07 | 0.97 |
| P | 0 | 0 | 0 | 0 |
| Ca | 0 | 0 | 0 | 0 |
| Pt | 8.756 | 7.788 | 8.218 | 8.25 |
As shown in Table 2, by regeneration, when not making to come off as the Pt of catalyst component, C, Si, P, the Ca as intoxicating material can be removed.In addition, as shown in Figure 2, regenerate catalyst before treatment because of poisoning and purifying rate declines to a great extent, and in catalyst after regeneration process, the purifying rate that have dropped recovers completely.Therefore, knownly to be used in the factory by reality, for because of organosilicon or organic phosphorus compound and fouled catalyst, also by above-mentioned renovation process activity recovery.
Claims (11)
1. the renovation process of exhaust gas purifying catalyst, it be at least any one the use be attached with in silicon or phosphorus after the method that regenerates of catalyst, it is characterized in that,
Be included in 400 ~ 700 DEG C of firing process that the exhaust gas purifying catalyst after use is burnt till,
With the alkali steeping operation of the catalyst soakage making to burn till in the aqueous slkali of 1 ~ 25wt%,
Alkali steeping operation is implemented under the condition of more than pH13.
2. the renovation process of exhaust gas purifying catalyst as claimed in claim 1, is characterized in that, to be attached with the exhaust gas purifying catalyst of organo-silicon compound for regeneration object.
3. the renovation process of exhaust gas purifying catalyst as claimed in claim 1, it is characterized in that, aqueous slkali is NaOH or potassium hydroxide.
4. the renovation process of exhaust gas purifying catalyst as claimed in claim 2, it is characterized in that, aqueous slkali is NaOH or potassium hydroxide.
5. the renovation process of exhaust gas purifying catalyst as claimed in claim 1, is characterized in that, also comprise the matting after alkali steeping operation.
6. the renovation process of exhaust gas purifying catalyst as claimed in claim 5, is characterized in that, in matting, after pure water or running water cleaning, uses acid solution to clean.
7. the renovation process of exhaust gas purifying catalyst as claimed in claim 6, it is characterized in that, acid solution is the salpeter solution of 0.3 ~ 3.0wt%.
8. the renovation process of exhaust gas purifying catalyst as claimed in claim 6, is characterized in that, after using the matting of acid solution, is also included in the drying process that 300 ~ 600 DEG C make catalyst drying.
9. the renovation process of exhaust gas purifying catalyst as claimed in claim 7, is characterized in that, after using the matting of acid solution, is also included in the drying process that 300 ~ 600 DEG C make catalyst drying.
10. the renovation process of the exhaust gas purifying catalyst as described in any one in claim 1 ~ 9, is characterized in that, the silicon of the exhaust gas purifying catalyst after regeneration or the content of phosphorus are respectively at below 1.5wt%.
The renovation process of 11. exhaust gas purifying catalysts as described in any one in claim 1 ~ 9, it is characterized in that, exhaust gas purifying catalyst is scribble the catalyst base material of more than a kind in aluminium oxide, zirconia, titanium oxide, cerium oxide carrying catalyst metals at water, and described catalyst metals is formed by noble metal more than 1 in platinum, palladium, rhodium, ruthenium, iridium, gold, silver kind.
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| JP2011090652A JP4989771B1 (en) | 2011-04-15 | 2011-04-15 | Regeneration method of exhaust gas purification catalyst |
| PCT/JP2012/060107 WO2012141283A1 (en) | 2011-04-15 | 2012-04-13 | Method for regenerating exhaust gas purifying catalyst |
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| GB201407158D0 (en) * | 2014-04-23 | 2014-06-04 | Johnson Matthey Plc | Precious metal recovery |
| CN105907975B (en) * | 2016-06-21 | 2017-12-29 | 中南大学 | A kind of carbon containing petroleum chemical industry of comprehensive reutilization gives up Pd/Al2O3The method of catalyst |
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