JP5622944B2 - 窒素含有化合物の変換方法 - Google Patents
窒素含有化合物の変換方法 Download PDFInfo
- Publication number
- JP5622944B2 JP5622944B2 JP2013545386A JP2013545386A JP5622944B2 JP 5622944 B2 JP5622944 B2 JP 5622944B2 JP 2013545386 A JP2013545386 A JP 2013545386A JP 2013545386 A JP2013545386 A JP 2013545386A JP 5622944 B2 JP5622944 B2 JP 5622944B2
- Authority
- JP
- Japan
- Prior art keywords
- tapso
- nitrogen
- alumino
- transition metal
- silico
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 33
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 36
- -1 transition metal cation Chemical class 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 23
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 235000013842 nitrous oxide Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 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
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 description 59
- 239000010452 phosphate Substances 0.000 description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 38
- 239000002808 molecular sieve Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 229910021529 ammonia Inorganic materials 0.000 description 19
- 239000010457 zeolite Substances 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 125000004437 phosphorous atom Chemical group 0.000 description 10
- 241000264877 Hippospongia communis Species 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000010531 catalytic reduction reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical group [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—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
- 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
- B01J21/063—Titanium; 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
- B01J23/38—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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
TAPO−5、TAPO−11およびTAPO−34はまた、それらのミクロ細孔構造に起因する、異なるプロセスでの触媒としての良好な特性の理由から、及び、高い吸着能力によって吸着剤として極めて適しているという理由から、特に適している。
さらに、それらは、30℃〜90℃の間の温度で既に可逆的に放出され、また、他の小分子を吸着するため、低い再生温度を有する。
本発明によれば、CHA構造を有するチタノ−(シリコ)−アルミノ−ホスフェートの使用が、特に適している。
本発明の方法において使用される分子篩は、例えばEP 161 488及びUS4,684,617からの従来技術において知られているように、いわゆるTAPSO−34が、極めて特に好ましい。
骨格構造内部の遷移金属カチオンは、その構造に触媒的な特性を与える。遷移金属カチオンによるH+またはNa+のイオン交換は、液体の及び固体の両方の形態で実行され、ここにおいて、また、異なる遷移金属カチオンが、複数の交換ステップにおいて同時にまたは連続して導入され得る。加えて、気相交換プロセスも知られているが、それは、産業的なプロセスとしては、高価過ぎる。現在の技術の不利点は、固体イオン交換の場合においては、チタノ−(シリコ)−アルミノ−ホスフェートの骨格に規定量の金属イオンが導入され得るが、金属イオンの均一な分布が得られないことである。これに対し、液体イオン交換の場合においては、チタノ−(シリコ)−アルミノ−ホスフェートに、均一な金属イオン分布が達成され得る。しかし、液体イオン交換の場合には、小細孔の分子篩を伴った不利点は、金属イオンが小さな細孔開口に浸透可能とするために金属イオンの水和燃料装置が余りにも大き過ぎ、これによって交換率が非常に低い、ということである。
上記した方法に加えて、水溶液含浸またはインシピエント・ウェットネス(incipient wetness)法によって、1以上の金属カチオンを用いて、ドーピングや修飾が実行され得る。これらドーピングや修飾は、従来技術において知られている。ドーピングや修飾が、水溶液のイオン交換によって1以上の金属化合物によって実行されることが好ましく、ここにおいて、金属塩及び金属複合体の両方が、イオンを供給するために使用される。
[(TixAlySizPq)O2]−a[M b+ ] a/b 、
ここにおいて、使用された符号及び添え字は、以下の意味を有する:x+y+z+q=1;0.010≦x≦0.110;0.400≦y≦0.550;0≦z<0.090;0.350≦q≦0.450;a=y−q(ただし、yは、好ましくはqよりも大きく);Mb+は、b+の電荷を帯びたカチオンを表し、ここにおいて、bは、1以上の整数であり、好ましくは1、2、3または4であり、さらに好ましくは1、2または3であり、最も好ましくは1または2である。
500gのCuTAPSO−34(5.3重量%のCu、製造者はズードケミーAG)が、100gのプラル(Pural)SB(Sasol ドイツ GmbH)、133.3gのH2O、16.7gの濃HNO3、10.7gのグリセロール(65% p.a. メルク)及び270.3gのチロース溶液(1000gの脱塩水に、70gのチロース MH50 G4 DEAC 098000(信越))を用いて、約1.6mmの直径及び0.5〜5mmの長さを有する糸状の押出成形物を形成した。押出成形物は、それから、120℃で16時間乾燥され、空気中で500℃(加熱速度は1℃/分)で5時間焼成された。
実施例1の押出成形物が、700℃まで加熱され、水蒸気雰囲気(10体積%のH2O)において、この温度で24時間のエージングを行った。
CuZSM−5(4重量%のCu、製造者はミズサワ)が、100gのプラル(Pural)SB(Sasol ドイツ GmbH)、133.3gのH2O、16.7gの濃HNO3、10.7gのグリセロール(65% p.a. メルク)及び242gのチロース溶液(2000gの脱塩水に、140gのチロース MH50 G4 DEAC 098000(信越))を用いて、約1.6mmの直径及び0.5〜5mmの長さを有する糸状の押出成形物を形成した。押出成形物は、それから、120℃で16時間乾燥され、空気中で500℃(加熱速度は1℃/分)で5時間焼成された。
ウォッシュコートは、100gの脱イオン水、100gの銅含有TAPSO−34(5.3重量%のCu、製造者はズードケミーAG)、22.6gのBindzil 2034DI(EKA ケミカルズ)、及び、4.4gの65%硝酸(Merck)から製造された。セラミック物質(75mm×100mm、200cpsi、Rauschert製)が、ウォッシュコートに浸された。乾燥後、ハニカムは、空気中で4時間の間に40℃から550℃まで加熱され、この温度で3時間保った。
ウォッシュコートは、800gの脱イオン水、666.5gの銅含有ゼオライトベータ(3.8重量%のCu、製造者はズードケミーAG)、160gのBindzil 2034DI(EKA ケミカルズ)、及び、26.5gの65%硝酸(Merck)から製造された。コーディエライトハニカム(φ20mm、75mm、200cpsi、Rauschert製)が、ウォッシュコートに浸された。乾燥後、ハニカムは、空気中で4時間の間に40℃から550℃まで加熱され、この温度で3時間保った。
ウォッシュコートは、100gの脱イオン水、111.1gの銅含有SAPO−34(5.6重量%のCu、製造者はズードケミーAG)、22.65gのBindzil 2034DI(EKA ケミカルズ)から製造された。セラミック物質(75mm×100mm、200cpsi、Rauschert製)が、ウォッシュコートに浸された。乾燥後、ハニカムは、空気中で4時間の間に40℃から550℃まで加熱され、この温度で3時間保った。
図1、2及び表3は、SCR反応における、実施例1及び比較例1で製造された触媒サンプルの、NOx及びNH3によって測定される変換を示す。NOx及びNH3の両方に関して、実施例1のために測定された変換は、比較例1の場合よりも高かった。両サンプルは、笑気ガスの形成が測定可能ではないことを示す。
Claims (16)
- 排出ガス流における窒素含有化合物の選択的、触媒的な変換のための方法であって、
ここにおいて、少なくとも1つの遷移金属カチオンで修飾されたTAPSO−34を含有する触媒が使用される。 - 前記窒素含有化合物の変換が、窒素酸化物の還元である請求項1に記載の方法。
- NH3、尿素、一酸化炭素、または、炭水化物化合物が、還元剤として使用される請求項2に記載の方法。
- 前記窒素含有化合物の変換が、窒素−水素化合物、及び/または、窒素含有有機化合物の酸化である請求項1に記載の方法。
- 酸素含有ガス、空気、または、笑気ガスが、酸化剤として使用される請求項4に記載の方法
- 前記TAPSO−34が、200〜1200m2/gの範囲内のBET比表面積を有する請求項1〜5のいずれかに記載の方法。
- 前記TAPSO−34が、以下の式を有する請求項1に記載の方法:
[(TixAlySizPq)O2]−a[M b+ ] a/b 、
ここにおいて、使用された符号及び添え字は、以下の意味を有する:x+y+z+q=1;0.010≦x≦0.110;0.400≦y≦0.550、0≦z<0.090、0.350≦q≦0.450;a=y−q;Mb+は、b+の電荷を帯びた少なくとも1つの遷移金属カチオンを表し、ここにおいて、bは、1以上の整数である。 - 前記少なくとも1つの遷移金属カチオンが、鉄、銅、クロム、マンガン、コバルト、プラチナ、パラジウム、ロジウム、銀、金からなる群から選択されるカチオンである請求項1に記載の方法。
- 前記TAPSO−34に存在している前記少なくとも1つの遷移金属カチオンは、前記TAPSO−34の総重量に対して0.01重量%〜20重量%の範囲内に存在する請求項1〜8のいずれかに記載の方法。
- 前記TAPSO−34は、(Ti)/(Al+P)モル比または(Si+Ti)/(Al+P)モル比として0.01〜0.5の範囲を有する請求項1〜9のいずれかに記載の方法。
- 前記TAPSO−34は、Si/Ti比として0〜20の範囲を有し、及び/または、前記TAPSO−34は、Al/P比として1〜1.5の範囲を有する請求項1〜10のいずれかに記載の方法。
- 前記TAPSO−34は、全て押出成形物として、または、コーティングの形態における担体上に存在している請求項1〜11のいずれかに記載の方法。
- 前記変換が、50℃〜550℃の範囲内の温度で生じる請求項1〜12のいずれかに記載の方法。
- 窒素含有化合物の選択的、触媒的な変換のための、少なくとも1つの遷移金属カチオンで修飾されたTAPSO−34の使用。
- 排出ガス精製触媒成分の製造のための、少なくとも1つの遷移金属カチオンで修飾されたTAPSO−34の使用。
- 少なくとも1つの遷移金属カチオンで修飾されたTAPSO−34を含有する排出ガス精製触媒成分。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010055728A DE102010055728A1 (de) | 2010-12-22 | 2010-12-22 | Verfahren zur Umsetzung stickstoffhaltiger Verbindungen |
DE102010055728.5 | 2010-12-22 | ||
PCT/EP2011/073693 WO2012085157A1 (de) | 2010-12-22 | 2011-12-21 | Verfahren zur umsetzung stickstoffhaltiger verbindungen |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014501612A JP2014501612A (ja) | 2014-01-23 |
JP5622944B2 true JP5622944B2 (ja) | 2014-11-12 |
Family
ID=45524487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013545386A Expired - Fee Related JP5622944B2 (ja) | 2010-12-22 | 2011-12-21 | 窒素含有化合物の変換方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20140072508A1 (ja) |
EP (1) | EP2654928B1 (ja) |
JP (1) | JP5622944B2 (ja) |
DE (1) | DE102010055728A1 (ja) |
WO (1) | WO2012085157A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9772317B2 (en) | 2012-07-26 | 2017-09-26 | Sensirion Ag | Method for operating a portable electronic device |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015044720A (ja) * | 2013-08-29 | 2015-03-12 | 三菱樹脂株式会社 | 金属含有Cu−SAPOゼオライト |
US10850265B2 (en) | 2014-06-18 | 2020-12-01 | Basf Corporation | Molecular sieve catalyst compositions, catalytic composites, systems, and methods |
US9764313B2 (en) | 2014-06-18 | 2017-09-19 | Basf Corporation | Molecular sieve catalyst compositions, catalyst composites, systems, and methods |
US9889437B2 (en) | 2015-04-15 | 2018-02-13 | Basf Corporation | Isomorphously substituted catalyst |
CN105879673A (zh) * | 2014-09-24 | 2016-08-24 | 北京美斯顿科技开发有限公司 | 一种钢厂焦炉烟气的脱硝方法及装置 |
CN105561774B (zh) * | 2015-12-15 | 2018-07-27 | 武汉大学 | 一种燃煤电厂前置sco强化烟气脱硝脱汞系统 |
CN107233932A (zh) | 2016-03-29 | 2017-10-10 | 巴斯夫公司 | 用于scr催化剂的脱硫方法 |
DE102018116058A1 (de) * | 2018-07-03 | 2020-01-09 | Interkat Catalyst Gmbh | Verwendung eines Katalysators zur selektiven katalytischen Oxidation von stickstoffhaltigen organischen Verbindungen |
CN109289911B (zh) * | 2018-10-11 | 2021-06-08 | 中国科学院大学 | 一种处理含氮挥发性有机污染物的催化剂及方法 |
CN109316952B (zh) * | 2018-10-11 | 2021-06-01 | 浙江浙能催化剂技术有限公司 | 一种非电领域的烟气超低排放设备及工艺 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4440871A (en) | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
US4500651A (en) * | 1983-03-31 | 1985-02-19 | Union Carbide Corporation | Titanium-containing molecular sieves |
US4684617A (en) | 1984-04-13 | 1987-08-04 | Union Carbide Corporation | Titanium-aluminum-phosphorus-silicon-oxide molecular sieves |
US4929576A (en) * | 1988-01-04 | 1990-05-29 | Mobil Oil Corporation | Reactivating catalysts containing noble metals on molecular sieves containing oxides of aluminum and phosphorus |
US4874590A (en) * | 1988-04-07 | 1989-10-17 | Uop | Catalytic reduction of nitrogen oxides |
US4867954A (en) * | 1988-04-07 | 1989-09-19 | Uop | Catalytic reduction of nitrogen oxides |
US4961917A (en) * | 1989-04-20 | 1990-10-09 | Engelhard Corporation | Method for reduction of nitrogen oxides with ammonia using promoted zeolite catalysts |
DE4228883A1 (de) | 1992-08-29 | 1994-03-03 | Basf Ag | Phillips-Katalysator zur Polymerisation von â-Olefinen |
US5417949A (en) * | 1993-08-25 | 1995-05-23 | Mobil Oil Corporation | NOx abatement process |
DK1142833T3 (da) * | 2000-04-06 | 2010-04-19 | Dalian Chemical Physics Inst | Molekylære sigter |
US6632767B2 (en) * | 2000-12-19 | 2003-10-14 | Praxair Technology, Inc. | Stabilization of molecular sieves by salt addition |
AU2003242437A1 (en) * | 2002-05-24 | 2003-12-12 | Mitsubishi Gas Chemical Company, Inc. | Crystalline silicoaluminophosphate salt molecular sieve having octaoxygen-membered ring pore, process for producing the same and process for producing methylamine with the molecular sieve as catalyst |
JP4182330B2 (ja) * | 2002-07-17 | 2008-11-19 | 三菱瓦斯化学株式会社 | シャバサイト型結晶質シリコアルミノリン酸塩モレキュラーシーブの圧縮打錠成型体及び成型方法 |
US7316727B2 (en) | 2004-03-19 | 2008-01-08 | The Regents Of The University Of Colorado | High-selectivity supported SAPO membranes |
US7998423B2 (en) * | 2007-02-27 | 2011-08-16 | Basf Corporation | SCR on low thermal mass filter substrates |
US8636959B2 (en) * | 2007-05-09 | 2014-01-28 | N.E. Chemcat Corporation | Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same |
DE102007030895A1 (de) * | 2007-07-03 | 2009-01-08 | Süd-Chemie AG | Abgaskatalysator für Salzsäure-haltige Abgase |
EP2269733A1 (en) * | 2009-06-08 | 2011-01-05 | Basf Se | Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34) |
WO2011061838A1 (ja) * | 2009-11-19 | 2011-05-26 | イビデン株式会社 | ハニカム構造体およびハニカム構造体の製造方法 |
DE102010046245A1 (de) * | 2010-09-22 | 2012-03-22 | Süd-Chemie AG | Herstellung von Alumo-Phosphaten unter Rückgewinnung von Templaten |
-
2010
- 2010-12-22 DE DE102010055728A patent/DE102010055728A1/de not_active Withdrawn
-
2011
- 2011-12-21 EP EP11811343.0A patent/EP2654928B1/de not_active Not-in-force
- 2011-12-21 WO PCT/EP2011/073693 patent/WO2012085157A1/de active Application Filing
- 2011-12-21 US US13/997,109 patent/US20140072508A1/en not_active Abandoned
- 2011-12-21 JP JP2013545386A patent/JP5622944B2/ja not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9772317B2 (en) | 2012-07-26 | 2017-09-26 | Sensirion Ag | Method for operating a portable electronic device |
Also Published As
Publication number | Publication date |
---|---|
US20140072508A1 (en) | 2014-03-13 |
JP2014501612A (ja) | 2014-01-23 |
EP2654928A1 (de) | 2013-10-30 |
EP2654928B1 (de) | 2018-07-04 |
DE102010055728A1 (de) | 2012-06-28 |
WO2012085157A1 (de) | 2012-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5622944B2 (ja) | 窒素含有化合物の変換方法 | |
JP7068301B2 (ja) | Eri/cha連晶骨格型を有する結晶性ゼオライト | |
JP6176891B2 (ja) | 新規鉄含有アルミノケイ酸塩ゼオライト、ならびにその作製方法および使用方法 | |
JP6402336B2 (ja) | アンモニア分解触媒 | |
CN110546108B (zh) | 具有低碱金属含量的含铜小孔沸石、其制备方法以及它们作为scr催化剂的用途 | |
EP2736637B1 (en) | Low phosphorus chabazites | |
EP3411332B1 (en) | Method for the direct synthesis of iron-containing aei-zeolite catalyst | |
KR20150074107A (ko) | 저온 수행성의 개선을 위해 추진제를 갖는 8-고리 소공 분자체 | |
KR20190056422A (ko) | AEI 및 Cu-AEI 제올라이트의 합성 | |
KR20150121074A (ko) | NOx 트랩 조성물 | |
KR20190027392A (ko) | 선택적 접촉 환원 물품 및 시스템 | |
US20190275504A1 (en) | Method for the Removal of Nitrous Oxide from Off Gas in Presence of Catalyst Comprising an Fe-AEI Zeolite Material Essentially Free of Alkali Metal | |
EP3393972B1 (en) | Process for preparing iron(iii)-exchanged zeolite composition | |
KR20190091362A (ko) | 바나듐 산화물 및 철을 함유하는 분자체를 함유하는 scr 촉매 장치 | |
JP6987766B2 (ja) | アルカリ金属を本質的に含まないfe−aeiゼオライト材料を含むscr触媒の存在下での選択触媒還元による排気ガスからの窒素酸化物の除去方法 | |
US11865517B2 (en) | Catalyst for reducing ammonia emissions | |
WO2018131196A1 (ja) | 排気ガス浄化用組成物 | |
JP2012051782A (ja) | 結晶性シリカアルミノフォスフェートおよびその合成方法 | |
JP6339306B1 (ja) | 排気ガス浄化用組成物 | |
EP2870996A1 (en) | Exhaust gas control catalyst | |
JP7450727B2 (ja) | 炭化水素吸着材、排ガス浄化触媒及び排ガス浄化システム | |
CN117957196A (zh) | Cha沸石材料的合成、能够由其获得的cha沸石材料和包含其的scr催化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140428 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140516 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140729 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140822 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140922 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5622944 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |