WO2015072567A1 - 脱硝触媒、およびその製造方法 - Google Patents
脱硝触媒、およびその製造方法 Download PDFInfo
- Publication number
- WO2015072567A1 WO2015072567A1 PCT/JP2014/080370 JP2014080370W WO2015072567A1 WO 2015072567 A1 WO2015072567 A1 WO 2015072567A1 JP 2014080370 W JP2014080370 W JP 2014080370W WO 2015072567 A1 WO2015072567 A1 WO 2015072567A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber sheet
- catalyst
- denitration catalyst
- slurry
- zirconium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 41
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 32
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 73
- 239000000835 fiber Substances 0.000 claims description 25
- 239000003365 glass fiber Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 19
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 17
- 239000010419 fine particle Substances 0.000 claims description 17
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 150000003754 zirconium Chemical class 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003513 alkali Substances 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000004689 octahydrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—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
- 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
-
- 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
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a denitration catalyst used for denitration treatment of combustion exhaust gas from, for example, a coal-fired boiler, and a manufacturing method thereof.
- the cause of deterioration of the denitration catalyst applied to the exhaust gas of coal-fired boilers is the attachment of trace amounts of heavy metals and arsenic contained in coal and clogging due to fly ash. Therefore, in recent years, there are increasing examples of regenerating and reusing denitration catalysts that have deteriorated over time.
- denitration catalysts produced by conventional methods described in Patent Document 1 and Patent Document 2 below use silica sol as a binder for maintaining the catalyst shape, but silica sol is inferior in alkali resistance.
- the silica as a binder cannot be eluted and the shape cannot be maintained, so that there is a problem that the regeneration treatment cannot be performed.
- Patent Document 3 use of zirconia is proposed as an inorganic binder other than silica sol.
- Patent Document 4 use of zirconia sol is proposed as an inorganic binder material.
- Japanese Patent No. 4881716 Japanese Patent No. 5022697 JP-A 61-234935 JP-A-11-216370
- Patent Document 3 zirconium crystals are formed by calcination.
- a denitration catalyst sintering of titania, which is a catalyst component, and aggregation of vanadium occur, so that the catalytic activity is significantly reduced.
- the zirconia sol used as the inorganic binder material in Patent Document 4 has a problem of increasing the cost.
- the object of the present invention is to solve the above-mentioned problems of the prior art and to have sufficient mechanical strength to maintain the catalyst shape in the alkali treatment performed to regenerate the performance of the denitration catalyst that has deteriorated over time.
- the present inventors have studied a method capable of maintaining the shape without elution of the binder in the alkali treatment carried out to regenerate the performance of the aged catalyst.
- a slurry containing titania and ammonium metavanadate is prepared using a water-soluble zirconium compound, and this slurry is applied to an inorganic fiber sheet or a honeycomb structure comprising the same, or fired after being dried and dried.
- the present inventors have found that a denitration catalyst that satisfies the requirements can be obtained at low cost, and have completed the present invention.
- the invention of claim 1 is a denitration catalyst based on a honeycomb structure made of an inorganic fiber sheet, wherein the honeycomb structure includes titania, vanadium oxide and / or tungsten oxide. And a zirconium compound (excluding crystalline zirconium dioxide) as a shape maintaining binder is supported.
- the invention according to claim 2 is the denitration catalyst according to claim 1, wherein the element ratio of the zirconium compound (excluding crystalline zirconium dioxide) as the shape maintaining binder is 1 to 20 in terms of oxide. It is characterized by weight percent.
- the invention of claim 3 is the denitration catalyst according to claim 1, characterized in that the inorganic fiber sheet is a glass fiber sheet or a ceramic fiber sheet.
- the invention of claim 4 is a method for producing a denitration catalyst based on a honeycomb structure made of an inorganic fiber sheet, in which ammonium titanate powder or metavanadate acid is suspended in a slurry in which titania fine particles are suspended in a zirconium salt aqueous solution. Ammonium powder and ammonium metatungstate powder are added, and a honeycomb structure made of an inorganic fiber sheet is immersed in the obtained slurry. After the honeycomb structure is taken out from the slurry, it is dried and fired at 550 ° C. or lower. .
- the invention of claim 5 is a method for producing a denitration catalyst based on a honeycomb structure made of an inorganic fiber sheet, wherein ammonium titanate powder or metavanadate acid is suspended in a slurry of titania fine particles suspended in a zirconium salt aqueous solution. Ammonium powder and ammonium metatungstate powder are added, and the inorganic fiber sheet is immersed in the obtained slurry, and after removing it from the slurry, it is dried or applied to the inorganic fiber sheet, A corrugated catalyst-containing fiber sheet is produced from a part of the obtained flat catalyst-containing fiber sheet through a shaping step, and the flat and corrugated catalyst-containing fiber sheet is fired at 550 ° C. or less. The fired flat sheet and corrugated fired catalyst-containing fiber sheets are alternately laminated to form a catalyst-supporting honeycomb structure. It is characterized in that formed.
- the invention of claim 6 is the method for producing a denitration catalyst according to claim 4 or 5, characterized in that the calcination is performed at 300 to 550 ° C.
- the invention of claim 7 is the method for producing a denitration catalyst according to claim 4 or 5, characterized in that the zirconium salt aqueous solution is an aqueous solution of zirconium acetate, zirconium chloride or zirconium nitrate.
- a denitration catalyst used for denitration treatment of combustion exhaust gas such as a coal-fired boiler retains the catalyst shape in alkali treatment performed to regenerate the performance of a denitration catalyst that has deteriorated over time.
- the present invention has an effect that the catalyst performance is superior to a conventional denitration catalyst having zirconium oxide crystals.
- a denitration catalyst having sufficient mechanical strength and excellent catalyst performance as described above can be produced, and a zirconia sol as a conventional zirconia material can be produced. Since it is not used, the production cost of the denitration catalyst is reduced.
- a denitration catalyst according to the present invention is a denitration catalyst based on a honeycomb structure made of an inorganic fiber sheet.
- the honeycomb structure includes titania, vanadium oxide and / or tungsten oxide, and a zirconium compound as a shape maintaining binder ( (Except for crystalline zirconium dioxide).
- the zirconium compound of the present invention is characterized by having no crystalline zirconium dioxide crystal structure, as shown in the X-ray diffraction analysis of FIG. 2 described later. Therefore, in the description in the present specification, the “zirconium compound (excluding crystalline zirconium dioxide)” means a substance that does not substantially contain crystalline zirconium dioxide. In the present invention, it is particularly preferable to be supported in the state of an amorphous zirconium compound. Specifically, it is preferably supported on the denitration catalyst as amorphous zirconium oxide, amorphous zirconium acetate, amorphous zirconium chloride, and amorphous zirconium nitrate.
- the element ratio in the catalyst of the zirconium compound (excluding crystalline zirconium dioxide) as the shape maintaining binder is preferably 1 to 20% by weight in terms of oxide.
- the element ratio in the catalyst of the zirconium compound (excluding crystalline zirconium dioxide) is less than 1% by weight in terms of oxide, it is difficult to maintain the shape, and the wear strength also decreases. It is not preferable.
- the element ratio of the zirconium compound (excluding crystalline zirconium dioxide) in the catalyst exceeds 20% by weight in terms of oxide, the amount of the catalyst component is reduced and the activity is lowered, which is not preferable.
- the element ratio in the catalyst of the zirconium compound (excluding crystalline zirconium dioxide) as the shape maintaining binder is 12 to 18% by weight in terms of oxide.
- the element ratio in the catalyst of the zirconium compound (excluding crystalline zirconium dioxide) is 12% by weight or more in terms of oxide, shape maintenance is more preferable.
- the element ratio in the catalyst of a zirconium compound (except for crystalline zirconium dioxide) is 18% by weight or less in terms of oxide.
- the inorganic fiber sheet is preferably a glass fiber sheet or a ceramic fiber sheet.
- a method for producing a denitration catalyst according to the present invention is a method for producing a denitration catalyst based on a honeycomb structure made of an inorganic fiber sheet, and ammonium metavanadate powder in a slurry in which titania fine particles are suspended in an aqueous zirconium salt solution, Alternatively, an ammonium metavanadate powder and ammonium metatungstate are added, and a honeycomb structure made of an inorganic fiber sheet is immersed in the obtained slurry, which is taken out of the slurry, dried, and fired at 550 ° C. or less. It is said.
- a method for producing a denitration catalyst according to the present invention is a method for producing a denitration catalyst based on a honeycomb structure made of inorganic fiber sheets, in a slurry in which titania fine particles are suspended in an aqueous zirconium salt solution.
- Ammonium metavanadate powder is added and stirred, and a honeycomb structure made of an inorganic fiber sheet is immersed in the obtained slurry. After removing the honeycomb structure from the slurry, it is dried and fired at 550 ° C. or lower to obtain a honeycomb structure.
- Titania and vanadium oxide and a zirconium compound excluding crystalline zirconium dioxide
- a method for producing a denitration catalyst according to the present invention is a method for producing a denitration catalyst based on a honeycomb structure made of inorganic fiber sheets, in which titania fine particles are suspended in a zirconium salt aqueous solution.
- Ammonium metavanadate powder and ammonium metatungstate were added to the slurry, and a honeycomb structure made of an inorganic fiber sheet was immersed in the slurry. After removing the honeycomb structure from the slurry, the honeycomb structure was dried and fired at 550 ° C. or lower.
- titania, vanadium oxide, and tungsten oxide, and a zirconium compound (excluding crystalline zirconium dioxide) as a shape maintaining binder are supported.
- the calcination is preferably performed at 300 to 550 ° C. for 1 to 4 hours.
- an aqueous zirconium salt solution is zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ], zirconium chloride [ZrO (Cl 2 ) ⁇ H 2 O], or zirconium nitrate [ZrO ( An aqueous solution of NO 3 ) 2 ] is preferred.
- the honeycomb (honeycomb) structure refers to an integrated structure composed of a plurality of through holes (cells) partitioned by partition walls and through which exhaust gas can flow, and the partition walls.
- the cross-sectional shape (cell cross-sectional shape) of the through hole is not particularly limited, and examples thereof include a circular shape, an arc shape, a square shape, a rectangular shape, and a hexagonal shape.
- a method of immersing a honeycomb structure in which an inorganic fiber sheet is assembled in a honeycomb (honeycomb) structure in advance A
- a method (B) of immersing the inorganic fiber sheet, which is the material of the honeycomb structure, in the sheet state A
- a honeycomb shape in which ammonium metavanadate powder is added to a slurry in which titania fine particles are suspended in a zirconium salt aqueous solution and stirred, and an inorganic fiber sheet is assembled in advance into a honeycomb structure in the resulting slurry.
- the structure was dipped, taken out from the slurry, dried at 100 to 200 ° C. for 1 to 2 hours, and further fired at 300 to 550 ° C. for 1 to 4 hours.
- a denitration catalyst is manufactured by supporting titania and vanadium oxide and a zirconium compound (excluding crystalline zirconium dioxide) as a shape-maintaining binder on the structure.
- ammonium metavanadate powder and ammonium metatungstate are added to a slurry in which titania fine particles are suspended in a zirconium salt aqueous solution, and a honeycomb-shaped structure in which inorganic fiber sheets are assembled in a honeycomb structure in advance is immersed in this slurry. After removing this from the slurry, it was dried at 100 to 200 ° C. for 1 to 2 hours, and further fired at 300 to 550 ° C. for 1 to 4 hours to give titania, A denitration catalyst is produced by supporting vanadium oxide and tungsten oxide and a zirconium compound (excluding crystalline zirconium dioxide) as a shape maintaining binder.
- the inorganic fiber sheet is preferably a glass fiber sheet or a ceramic fiber sheet.
- the above method (B) is a method for producing a denitration catalyst based on a honeycomb structure made of a glass fiber sheet, and ammonium metavanadate in a slurry in which titania fine particles are suspended in an aqueous zirconium salt solution.
- the catalyst-containing slurry is applied to the glass fiber sheet, and then the catalyst-containing slurry-coated glass fiber sheet is shaped by a corrugating die and a holding jig, and the shaped corrugated catalyst-containing slurry-coated glass fiber sheet is 100 to 200. Drying under conditions of 1 to 2 hours at °C, peeled off from the mold, on the other hand, flat catalyst slurry coated glass not shaped into corrugated plate The fiber sheet is dried at 100 to 200 ° C.
- a denitration catalyst is manufactured by forming a fiber sheet and laminating the fired catalyst-supported flat glass fiber sheet and the catalyst-supported corrugated glass fiber sheet to form a catalyst-supported honeycomb structure.
- ammonium metavanadate powder is added to a slurry in which titania fine particles are suspended in an aqueous zirconium salt solution and stirred. Then, ammonium metatungstate or an aqueous solution thereof is further added to the resulting slurry, and then a glass fiber sheet is added to the slurry. Is taken out from the slurry and dried at 100 to 200 ° C. for 1 to 2 hours, or the catalyst-containing slurry is applied to the glass fiber sheet, and then the catalyst-containing slurry-coated glass fiber is applied.
- the sheet is shaped with a corrugating die and a holding jig, and the shaped corrugated catalyst-containing slurry-coated glass fiber sheet is dried at 100 to 200 ° C. for 1 to 2 hours.
- a flat-plate-like catalyst slurry-coated glass fiber sheet that is not shaped into a corrugated plate is applied to 100 to 20
- the glass fiber sheet is coated with a corrugated catalyst-containing slurry and a glass fiber sheet coated with a flat catalyst slurry at 300 to 550 ° C. for 1 to 4 hours.
- a catalyst-supported flat glass fiber sheet and a catalyst-supported corrugated glass fiber sheet on which calcined titania, vanadium oxide, and tungsten oxide and a zirconium compound (excluding crystalline zirconium dioxide) as a shape-maintaining binder are supported The catalyst-supported flat glass fiber sheet and the catalyst-supported corrugated glass fiber sheet after being fired are laminated to form a catalyst-supported honeycomb structure, thereby producing a denitration catalyst.
- Example 1 The denitration catalyst according to the present invention was produced as follows. First, a slurry in which titania fine particles are suspended in an aqueous solution of 20% by weight of zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ] (trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.) 10 g of ammonium metavanadate powder per 1 kg of slurry was added to the weight ratio of zirconium acetate and titania; 20:80), and the whole was stirred for 1 hour.
- ZrO (C 2 H 3 O 2 ) 2 trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.
- a honeycomb-shaped structure in which ceramic fiber sheets are preliminarily assembled into a honeycomb structure is immersed, and after this is taken out of the slurry, dried at 110 ° C. for 1 hour, and further fired at 400 ° C. for 1 hour,
- the honeycomb structure was loaded with titania and vanadium oxide and a zirconium compound (excluding crystalline zirconium dioxide) as a shape maintaining binder to obtain a denitration catalyst according to the present invention.
- the denitration catalyst according to the present invention was produced as follows.
- ammonium metavanadate powder was added to a slurry (weight ratio of zirconium acetate and titania; 20:80) in which titania fine particles were suspended in a 20 wt% zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ] aqueous solution. 10 g per kg of slurry was added and the whole was stirred for 1 hour. To the above slurry, 28 ml of ammonium metatungstate aqueous solution (3.88 mol / l) was added per 1 kg of the slurry, and the whole was stirred for 1 hour.
- a honeycomb-shaped structure in which ceramic fiber sheets are preliminarily assembled into a honeycomb structure is immersed, and after this is taken out of the slurry, dried at 110 ° C. for 1 hour, and further fired at 400 ° C. for 1 hour,
- the honeycomb structure was loaded with titania, vanadium oxide, and tungsten oxide and a zirconium compound (excluding crystalline zirconium dioxide) as a shape-maintaining binder to obtain a denitration catalyst according to the present invention.
- Example 3 The denitration catalyst according to the present invention was produced as follows.
- slurry of ammonium metavanadate in a slurry (weight ratio of zirconium acetate to titania; 20:80) in which titania fine particles are suspended in an aqueous solution of 20 wt% zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ]. 10 g per kg was added and the whole was stirred for 1 hour. Further, 28 ml of ammonium metatungstate aqueous solution (3.88 mol / l) per 1 kg of the slurry was added to the slurry, and the whole was stirred for 1 hour.
- the slurry is applied to a flat glass fiber sheet, the catalyst-containing slurry-coated glass fiber sheet is corrugated, dried at 110 ° C., and baked at 400 ° C. for 1 hour, thereby producing titania, vanadium oxide, and oxidation.
- Example 4 In Example 3, instead of zirconium acetate, zirconium oxychloride [ZrOCl 2 ⁇ H 2 O (trade name: zirconium oxychloride (octahydrate), manufactured by Kishida Chemical Co., Ltd.)] was used. Thus, a denitration catalyst according to the present invention was obtained. (Example 5) In Example 3, instead of zirconium acetate, zirconium nitrate [ZrO (NO 3 ) 2 ] (trade name: zirconium nitrate (IV), manufactured by Mitsuwa Chemicals Co., Ltd.) was used. By the method, a denitration catalyst according to the present invention was obtained.
- Example 6 titania fine particles were suspended in an aqueous solution of 20% by weight of zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ] (trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.).
- ZrO (C 2 H 3 O 2 ) 2 trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.
- a denitration catalyst according to the present invention was obtained in the same manner as in Example 1 except that the weight ratio of zirconium acetate to titania in the slurry was changed to 5:80.
- Example 7 titania fine particles were suspended in an aqueous solution of 20% by weight of zirconium acetate [ZrO (C 2 H 3 O 2 ) 2 ] (trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.).
- ZrO (C 2 H 3 O 2 ) 2 trade name: Zircosol ZA-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.
- a denitration catalyst according to the present invention was obtained in the same manner as in Example 1, except that the weight ratio of zirconium acetate to titania in the slurry was changed to 1.25: 80.
- a denitration catalyst was produced as follows.
- the denitration catalysts obtained in Examples 1 to 7 of the present invention retain the catalyst shape in the alkali treatment (immersion in 1N NaOH aqueous solution), and the present invention
- the catalyst wear depth test in which coal-fired boiler ash was sprayed on each of the denitration catalysts obtained in Examples 1 to 7, sufficient wear resistance was obtained, and therefore, for example, combustion exhaust gas from a coal-fired boiler, etc.
- the denitration catalyst used in the denitration treatment has sufficient mechanical strength that can maintain the catalyst shape in the alkali treatment carried out to regenerate the performance of the denitration catalyst that has deteriorated over time.
- the conventional denitration catalyst using silica sol was not able to maintain the catalyst shape because silica was eluted in the alkali treatment.
- the zirconium compound as the shape-maintaining binder is a zirconium compound (excluding crystalline zirconium dioxide).
- the zirconium compound as the shape maintaining binder is a crystalline zirconium oxide.
- a peak attributed to tetragonal ZrO 2 (zirconia) (around 2 ⁇ 30) was obtained, and the denitration performance of this comparative denitration catalyst was denitration with the denitration performance of the catalyst of Comparative Example 1 taken as 1. The performance ratio was 0.7, and the denitration performance was poor.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
(実施例1)
本発明による脱硝触媒を、つぎのようにして製造した。まず、20重量%の酢酸ジルコニウム〔ZrO(C2H3O2)2〕(商品名:ジルコゾールZA-20、第一稀元素化学工業社製)の水溶液にチタニア微粒子を懸濁させたスラリー(酢酸ジルコニウムとチタニアの重量比率;20:80)に、メタバナジン酸アンモニウム粉末をスラリー1kg当たり10g添加し、全体を1時間撹拌した。上記スラリーに、予めセラミック繊維シートをハニカム構造に組み立てたハニカム形状の構造体を浸漬し、これをスラリーから取り出した後、110℃で1時間乾燥し、さらに400℃で1時間焼成することで、ハニカム構造体に、チタニアおよび酸化バナジウムと、形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)とを担持させることにより、本発明による脱硝触媒を得た。
(実施例2)
本発明による脱硝触媒を、つぎのようにして製造した。まず、20重量%の酢酸ジルコニウム〔ZrO(C2H3O2)2〕水溶液にチタニア微粒子を懸濁させたスラリー(酢酸ジルコニウムとチタニアの重量比率;20:80)に、メタバナジン酸アンモニウム粉末をスラリー1kg当たり10g添加し、全体を1時間撹拌した。上記スラリーに、さらにメタタングステン酸アンモニウム水溶液(3.88mol/l)をスラリー1kg当たり28mlを添加し、全体を1時間撹拌した。上記スラリーに、予めセラミック繊維シートをハニカム構造に組み立てたハニカム形状の構造体を浸漬し、これをスラリーから取り出した後、110℃で乾燥1時間し、さらに400℃で1時間焼成することで、ハニカム構造体に、チタニア、酸化バナジウム、および酸化タングステンと、形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)とを担持させることにより、本発明による脱硝触媒を得た。
(実施例3)
本発明による脱硝触媒を、つぎのようにして製造した。まず、20重量%の酢酸ジルコニウム〔ZrO(C2H3O2)2〕水溶液にチタニア微粒子を懸濁させたスラリー(酢酸ジルコニウムとチタニアの重量比率;20:80)にメタバナジン酸アンモニウム粉末をスラリー1kg当たり10g添加し、全体を一時間撹拌した。上記スラリーに更にメタタングステン酸アンモニウム水溶液(3.88mol/l)をスラリー1kg当たり28mlを添加し、全体を一時間撹拌した。上記スラリーを平板状のガラス繊維シートに塗布し、触媒含有スラリー塗布ガラス繊維シートを波付け処理した後、110℃で乾燥し、400℃で1時間焼成することで、チタニア、酸化バナジウム、および酸化タングステンと、形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)とが担持した触媒担持波板状ガラス繊維シートを得た。一方、上記スラリーを平板状のガラス繊維シートに塗布した後、110℃で乾燥し、400℃で1時間焼成することで、チタニア、酸化バナジウム、および酸化タングステンと、形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)とが担持した触媒担持平板状ガラス繊維シートを得た。上記焼成後の触媒担持平板状ガラス繊維シートおよび触媒担持波板状ガラス繊維シートを波板触媒と平板触媒を交互に積層することで、本発明による脱硝触媒を得た。
(実施例4)
実施例3において、酢酸ジルコニウムに代えてオキシ塩化ジルコニウム〔ZrOCl2・H2O(商品名:オキシ塩化ジルコニウム(8水和物)、キシダ化学社製)を使用する以外は、実施例3と同様の方法で、本発明による脱硝触媒を得た。
(実施例5)
実施例3において、酢酸ジルコニウムに代えて硝酸ジルコニウム〔ZrO(NO3)2〕(商品名:硝酸酸化ジルコニウム(IV)、三津和化学薬品社製)を使用する以外は、実施例3と同様の方法で、本発明による脱硝触媒を得た。
(実施例6)
実施例1において、20重量%の酢酸ジルコニウム〔ZrO(C2H3O2)2〕(商品名:ジルコゾールZA-20、第一稀元素化学工業社製)の水溶液にチタニア微粒子を懸濁させたスラリー中の酢酸ジルコニウムとチタニアの重量比率を5:80に変更する以外は,実施例1と同様の方法で、本発明による脱硝触媒を得た。
(実施例7)
実施例1において、20重量%の酢酸ジルコニウム〔ZrO(C2H3O2)2〕(商品名:ジルコゾールZA-20、第一稀元素化学工業社製)の水溶液にチタニア微粒子を懸濁させたスラリー中の酢酸ジルコニウムとチタニアの重量比率を1.25:80に変更する以外は,実施例1と同様の方法で、本発明による脱硝触媒を得た。
(比較例1)
比較のために、脱硝触媒を、つぎのようにして製造した。まず、20重量%のシリカゾルにチタニア微粒子を懸濁させたスラリー(シリカとチタニアの重量比率;20:80)にメタバナジン酸アンモニウム粉末をスラリー1kg当たり10g添加し、全体を一時間撹拌した。上記スラリーに、予めセラミック繊維シートをハニカム構造に組み立てたハニカム形状の構造体を浸漬し、これをスラリーから取り出した後、110℃で1時間乾燥し、400℃で1時間焼成することで、比較用の脱硝触媒を得た。
(比較例2)
実施例3における焼成温度を、600℃で行うこと以外は、実施例3と同様の方法で、比較用の脱硝触媒を得た。なお、この場合は、焼成温度が高いために、ハニカム構造体に、チタニア、酸化バナジウム、および酸化タングステンと、結晶性のジルコニウム化合物とが担持された比較用の脱硝触媒が得られた。
(評価)
本発明による実施例1~7、および比較例1と2の各脱硝触媒中のジルコニウム含有量(蛍光エックス線分析装置での酸化物換算での測定結果)を、蛍光X線分析装置(商品名SEA1200VX、セイコーインスツルメンツ社製)で測定した。また各脱硝触媒の結晶構造の分析は、X線回折分析装置(商品名MALTIFLEX、リガク社製)を用いて行った。得られた結果を、下記の表1にまとめて示した。
Claims (7)
- 無機繊維シートよりなるハニカム構造体を基材とする脱硝触媒であって、ハニカム構造体に、チタニア、酸化バナジウムおよび/または酸化タングステンと、形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)とが担持されていることを特徴とする、脱硝触媒。
- 形状維持バインダーとしてのジルコニウム化合物(結晶性の二酸化ジルコニウムを除く)の触媒中の元素割合が、酸化物換算で1~20重量%であることを特徴とする、請求項1に記載の脱硝触媒。
- 無機繊維シートが、ガラス繊維シート、またはセラミック繊維シートであることを特徴とする、請求項1に記載の脱硝触媒。
- 無機繊維シートよりなるハニカム構造体を基材とする脱硝触媒の製造方法であって、ジルコニウム塩水溶液にチタニア微粒子を懸濁させたスラリーにメタバナジン酸アンモニウム粉末、またはメタバナジン酸アンモニウム粉末およびメタタングステン酸アンモニウム粉末を添加し、得られたスラリーに無機繊維シートよりなるハニカム構造体を浸漬し、これをスラリーから取り出した後、乾燥および550℃以下で焼成することを特徴とする、脱硝触媒の製造方法。
- 無機繊維シートよりなるハニカム構造体を基材とする脱硝触媒の製造方法であって、ジルコニウム塩水溶液にチタニア微粒子を懸濁させたスラリーにメタバナジン酸アンモニウム粉末、またはメタバナジン酸アンモニウム粉末およびメタタングステン酸アンモニウム粉末を添加し、得られたスラリーに無機繊維シートを浸漬し、これをスラリーから取り出した後、乾燥するか、もしくは、無機繊維シートに当該スラリーを塗布し、次いで、得られた平板状の触媒含有繊維シートの一部から、形付け工程を経て波板状の触媒含有繊維シートを作製し、平板状および波板状の触媒含有繊維シートを550℃以下で焼成し、焼成後の平板状および波板状の焼成触媒含有繊維シートを交互に積層して、触媒担持ハニカム構造体を形成することを特徴とする、脱硝触媒の製造方法。
- 焼成を、300~550℃で行うことを特徴とする、請求項4または5に記載の脱硝触媒の製造方法。
- ジルコニウム塩水溶液が、酢酸ジルコニウム、塩化ジルコニウム、または硝酸ジルコニウムの水溶液であることを特徴とする、請求項4または5に記載の脱硝触媒の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/034,988 US20160271587A1 (en) | 2013-11-18 | 2014-11-17 | Denitration catalyst and method for producing same |
EP14861599.0A EP3072585A4 (en) | 2013-11-18 | 2014-11-17 | Denitration catalyst and method for producing same |
CN201480056199.8A CN105764607B (zh) | 2013-11-18 | 2014-11-17 | 脱硝催化剂及其制造方法 |
KR1020167012823A KR102306141B1 (ko) | 2013-11-18 | 2014-11-17 | 탈질촉매 및 그 제조방법 |
US16/291,640 US20190193054A1 (en) | 2013-11-18 | 2019-03-04 | Denitration catalyst and method for producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013237922A JP6047477B2 (ja) | 2013-11-18 | 2013-11-18 | 脱硝触媒、およびその製造方法 |
JP2013-237922 | 2013-11-18 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/034,988 A-371-Of-International US20160271587A1 (en) | 2013-11-18 | 2014-11-17 | Denitration catalyst and method for producing same |
US16/291,640 Continuation US20190193054A1 (en) | 2013-11-18 | 2019-03-04 | Denitration catalyst and method for producing same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015072567A1 true WO2015072567A1 (ja) | 2015-05-21 |
Family
ID=53057499
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/080370 WO2015072567A1 (ja) | 2013-11-18 | 2014-11-17 | 脱硝触媒、およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (2) | US20160271587A1 (ja) |
EP (1) | EP3072585A4 (ja) |
JP (1) | JP6047477B2 (ja) |
KR (1) | KR102306141B1 (ja) |
CN (1) | CN105764607B (ja) |
WO (1) | WO2015072567A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017035848A1 (zh) * | 2015-08-28 | 2017-03-09 | 山东天璨环保科技有限公司 | 烟气脱硝催化剂及其制备方法 |
EP3278875A4 (en) * | 2015-03-31 | 2019-01-02 | Hitachi Zosen Corporation | Catalyst treatment device and method for manufacturing same |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6534328B2 (ja) * | 2015-09-29 | 2019-06-26 | 株式会社日本触媒 | アクリル酸製造用触媒の製造方法とその触媒、ならびに該触媒を用いたアクリル酸の製造方法 |
US20200254424A1 (en) * | 2016-10-05 | 2020-08-13 | Hitachi Zosen Corporation | Catalyst support structure and method for manufacturing same |
CN112166213A (zh) | 2018-04-04 | 2021-01-01 | 尤尼弗瑞克斯 I 有限责任公司 | 活化的多孔纤维和包括该纤维的产品 |
CN113058614A (zh) * | 2021-03-31 | 2021-07-02 | 沈阳航空航天大学 | 一种失活烟气脱硝催化剂模板再生方法 |
CN115301227B (zh) * | 2022-09-06 | 2023-10-13 | 浙江省环境科技有限公司 | 含钛高炉渣制备脱硝脱氯苯催化剂的方法、催化剂和应用 |
CN115624968B (zh) * | 2022-11-14 | 2024-02-02 | 国能龙源环保有限公司 | 利用废旧风电叶片制备脱硝催化剂的方法和应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61234935A (ja) | 1985-04-09 | 1986-10-20 | Mazda Motor Corp | エンジンの排気ガス浄化用触媒 |
JPH0522697B2 (ja) | 1984-09-10 | 1993-03-30 | Showa Denko Kk | |
JPH11216370A (ja) | 1998-02-03 | 1999-08-10 | Nichias Corp | 触媒及びその製造方法 |
JP2004298728A (ja) * | 2003-03-31 | 2004-10-28 | Sumitomo Chem Co Ltd | 触媒繊維およびその製造方法 |
JP2005087815A (ja) * | 2003-09-12 | 2005-04-07 | Mitsubishi Heavy Ind Ltd | 排ガス処理方法 |
JP4881716B2 (ja) | 2006-12-25 | 2012-02-22 | 日立造船株式会社 | 脱硝触媒の製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5022697B1 (ja) | 1969-09-19 | 1975-08-01 | ||
US6395665B2 (en) * | 1998-07-24 | 2002-05-28 | Mitsubishi Heavy Industries, Ltd. | Methods for the regeneration of a denitration catalyst |
EP1754526B1 (en) * | 1999-10-15 | 2010-11-24 | Lummus Technology Inc. | Conversion of nitrogen oxides in the presence of catalyst supported on a mesh-like structure |
EP1815909A4 (en) * | 2004-07-29 | 2010-04-28 | N E Chemcat Corp | NOx REDUCTION CATALYST HAVING EXCELLENT LOW TEMPERATURE CHARACTERISTICS |
US7491676B2 (en) * | 2004-10-19 | 2009-02-17 | Millennium Inorganic Chemicals | High activity titania supported metal oxide DeNOx catalysts |
JP5683111B2 (ja) * | 2007-02-27 | 2015-03-11 | ビーエーエスエフ コーポレーション | 銅chaゼオライト触媒 |
CN101912775A (zh) * | 2010-09-03 | 2010-12-15 | 中国汽车技术研究中心 | 一种用于脱除柴油车尾气中氮氧化物的选择性催化剂及其制备方法 |
JP5723646B2 (ja) * | 2011-03-25 | 2015-05-27 | 日立造船株式会社 | 脱硝触媒の調製方法 |
-
2013
- 2013-11-18 JP JP2013237922A patent/JP6047477B2/ja active Active
-
2014
- 2014-11-17 EP EP14861599.0A patent/EP3072585A4/en active Pending
- 2014-11-17 KR KR1020167012823A patent/KR102306141B1/ko active IP Right Grant
- 2014-11-17 CN CN201480056199.8A patent/CN105764607B/zh active Active
- 2014-11-17 WO PCT/JP2014/080370 patent/WO2015072567A1/ja active Application Filing
- 2014-11-17 US US15/034,988 patent/US20160271587A1/en not_active Abandoned
-
2019
- 2019-03-04 US US16/291,640 patent/US20190193054A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0522697B2 (ja) | 1984-09-10 | 1993-03-30 | Showa Denko Kk | |
JPS61234935A (ja) | 1985-04-09 | 1986-10-20 | Mazda Motor Corp | エンジンの排気ガス浄化用触媒 |
JPH11216370A (ja) | 1998-02-03 | 1999-08-10 | Nichias Corp | 触媒及びその製造方法 |
JP2004298728A (ja) * | 2003-03-31 | 2004-10-28 | Sumitomo Chem Co Ltd | 触媒繊維およびその製造方法 |
JP2005087815A (ja) * | 2003-09-12 | 2005-04-07 | Mitsubishi Heavy Ind Ltd | 排ガス処理方法 |
JP4881716B2 (ja) | 2006-12-25 | 2012-02-22 | 日立造船株式会社 | 脱硝触媒の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3072585A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3278875A4 (en) * | 2015-03-31 | 2019-01-02 | Hitachi Zosen Corporation | Catalyst treatment device and method for manufacturing same |
WO2017035848A1 (zh) * | 2015-08-28 | 2017-03-09 | 山东天璨环保科技有限公司 | 烟气脱硝催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20190193054A1 (en) | 2019-06-27 |
KR102306141B1 (ko) | 2021-09-27 |
JP2015097977A (ja) | 2015-05-28 |
KR20160087808A (ko) | 2016-07-22 |
EP3072585A1 (en) | 2016-09-28 |
US20160271587A1 (en) | 2016-09-22 |
JP6047477B2 (ja) | 2016-12-21 |
EP3072585A4 (en) | 2017-09-13 |
CN105764607A (zh) | 2016-07-13 |
CN105764607B (zh) | 2019-05-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015072567A1 (ja) | 脱硝触媒、およびその製造方法 | |
JP6703537B2 (ja) | 排気システム用の一酸化二窒素除去触媒 | |
US7220702B2 (en) | Exhaust gas purification catalyst | |
JP5401049B2 (ja) | 脱硝触媒製造用スラリー、同スラリーの製造方法、同スラリーを用いる脱硝触媒の製造方法および同方法により製造された脱硝触媒 | |
JP5864444B2 (ja) | 排気ガス浄化用触媒及び排気ガス浄化用触媒構成体 | |
JP4505046B2 (ja) | 排気ガス浄化用触媒及びその製造方法 | |
JP6329245B2 (ja) | 窒素酸化物除去用のナノ触媒フィルター | |
KR102090726B1 (ko) | 코팅 슬러리를 이용한 선택적 촉매 환원용 금속 구조체 기반 탈질 촉매 및 이의 제조방법 | |
JP2008155133A (ja) | 脱硝触媒の製造方法 | |
JP5791439B2 (ja) | 排気ガス浄化用触媒及び担体 | |
KR20160141104A (ko) | 평판형 선택적촉매환원 촉매용 나노복합 이산화티타늄의 제조방법 | |
JP2021532974A (ja) | バナジウムに基づく選択的触媒還元触媒 | |
TWI647010B (zh) | 金屬汞之氧化反應及氮氧化物之還原反應用觸媒、以及排氣之淨化方法 | |
JP4989545B2 (ja) | 窒素酸化物接触還元用触媒 | |
JP2019534776A (ja) | メタン酸化触媒、それを調製するプロセス、およびそれを使用する方法 | |
JP2023543697A (ja) | Scr触媒組成物及び該触媒組成物を含むscr触媒物品 | |
CN114364447A (zh) | 选择性催化还原催化剂组合物、包含其的催化制品和制备催化制品的方法 | |
JP2006231281A (ja) | 排ガスの処理用触媒、その製造方法、及び排ガスの処理方法 | |
JP2020062627A (ja) | アンモニア浄化触媒 | |
JP5156173B2 (ja) | 窒素酸化物除去用触媒の製造法 | |
JP2013198888A (ja) | 排ガス浄化用触媒担体、それを用いた窒素酸化物浄化用触媒、及びそれらの製造方法 | |
JP2002361092A (ja) | 排ガス脱硝用触媒スラリ、脱硝用触媒およびそれらの製造方法 | |
JP5956496B2 (ja) | 排ガス浄化用触媒、それを用いた排ガス浄化フィルタ及び排ガス浄化方法 | |
JP3632739B2 (ja) | 酸化チタン−リン酸チタン系粉末、排ガス浄化用触媒担体及び排ガス浄化用触媒 | |
JP2009233602A (ja) | 粒子状物質浄化用触媒及びそれを用いた粒子状物質浄化方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14861599 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15034988 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20167012823 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014861599 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014861599 Country of ref document: EP |