DK2995367T3 - Kobberkatalysator der er understøttet af molekylsigte med små porer med bestandighed mod mager/fed aldring til reduktion af nitrogenoxider - Google Patents
Kobberkatalysator der er understøttet af molekylsigte med små porer med bestandighed mod mager/fed aldring til reduktion af nitrogenoxider Download PDFInfo
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- DK2995367T3 DK2995367T3 DK15189846.7T DK15189846T DK2995367T3 DK 2995367 T3 DK2995367 T3 DK 2995367T3 DK 15189846 T DK15189846 T DK 15189846T DK 2995367 T3 DK2995367 T3 DK 2995367T3
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- Prior art keywords
- catalyst
- cha
- molecular sieve
- scr
- chemical process
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- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 44
- 239000002808 molecular sieve Substances 0.000 claims abstract description 121
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000011148 porous material Substances 0.000 claims abstract description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 43
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- 238000001311 chemical methods and process Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 16
- 238000011069 regeneration method Methods 0.000 claims description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052676 chabazite Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003949 liquefied natural gas Substances 0.000 claims description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 2
- 101100008649 Caenorhabditis elegans daf-5 gene Proteins 0.000 claims 1
- 229910018557 Si O Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 23
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- 239000004071 soot Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 description 41
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- 230000000977 initiatory effect Effects 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
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- 229910052748 manganese Inorganic materials 0.000 description 4
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- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
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- 229910052804 chromium Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- -1 i.e. Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
- 101100382321 Caenorhabditis elegans cal-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 239000000571 coke Substances 0.000 description 1
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- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8628—Processes characterised by a specific catalyst
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- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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Claims (13)
1. Kemisk fremgangsmåde til behandling af udstødningsgas fra et køretøjs forbrændingsmotor med en mager/fed-cyklus ved anvendelse af en katalysator til selektiv katalytisk reduktion (SCR), hvilken kemisk fremgangsmåde omfatter: at danne et NH3-nitrogenholdigt reduktionsmiddel over en NOx-adsorber-kataly-sator (NAC) under periodiske fedt-regenereringshændelser, at udsætte SCR-ka-talysatoren i et NAC + (nedstrøms)-SCR-katalysatorsystem for mindst en reaktant der indbefatter nitrogenoxider, og at reducere nitrogenoxiderne med det Nhh-nitrogenholdige reduktionsmidlet der er dannet over NAC’en under de periodiske fedt-regenereringshændelser, hvilken SCR-katalysator omfatter kobber og en molekylsigte med små porer og har en maksimal ringstørrelse på otte tetraederi-ske atomer, og hvor yderligere nitrogenholdigt reduktionsmiddel kun doseres til en flydende udstødningsgas, når SCR-katalysatoren er ved over 100 °C.
2. Kemisk fremgangsmåde ifølge krav 1, hvor det nitrogenholdige reduktionsmiddel kun doseres i den flydende udstødningsgas, når SCR-katalysatoren er ved over 150 °C.
3. Kemisk fremgangsmåde ifølge krav 1 eller 2, hvor en kilde til yderligere nitrogenholdigt reduktionsmiddel er ammoniak per se, hydrazin, urinstof ((NH2)2CO)), ammoniumcarbonat, ammoniumcarbamat, ammoniumhydrogencarbonat eller ammoniumformiat.
4. Kemisk fremgangsmåde ifølge krav 1,2 eller 3, hvor molekylsigterne med små porer der indeholder en maksimal ringstørrelse på otte tetraederiske atomer er valgt fra gruppen af rammetypekoder, der indeholder CHA, LEV, ERI og DDR.
5. Kemisk fremgangsmåde ifølge krav 1,2, 3 eller 4, hvor molekylsigterne med små porer der indeholder en maksimal ringstørrelse på otte tetraederiske atomer har rammetypekoden CHA.
6. Kemisk fremgangsmåde ifølge krav 4 eller 5, hvor molekylsigten med små porer af rammetypekoden CHA er AIPO-34, [AI-As-0]-CHA, [Al-Co-P-0]-CHA, |Co|[Be-P-0]-CHA, |C03(C6N4H24)3(H2O)9[Bei8Pi8O72]-CHA, [Co-AI-P-0]-CHA, |Li-Na|[AI-Si-0]-CHA, [Mg-AI-PO]-CHA, [Si-0]-CHA, [Zn-AI-PO]-CHA, [Zn-As-O]-CHA, CoAPO-44, CoAPO-47, DAF-5, GaPO-34, K-chabazit, Linde D, Linde R, LZ-218, MeAPO-47, MeAPSO-47, (Ni(deta)2)-UT-6, Phi, SAPO-34, SAPO-47, SSZ-13, UiO-21, Willhendersonite, ZK-14 eller ZYT-6.
7. Kemisk fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor molekylsigten med små porer er en aluminosilicat-molekylsigte og har et forhold mellem siliciumdioxid og aluminiumoxid på 8 til 150.
8. Kemisk fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor det totale kobber-indhold i molekylsigten med små porer er fra 0,5 til 5 vægt-%.
9. Kemisk fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor den NOx-adsorberende katalysator omfatter et ædelmetal og et basismateriale, der er valgt fra gruppen som består af et alkalimetal, et jordal kali metal og et metal af de sjældne jordarter.
10. Kemisk fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor NH3-SCR-katalysatoren belægges på en substratmonolit.
11. Kemisk fremgangsmåde ifølge et hvilket som helst af kravene 1 til 9, hvor NH3-SCR-katalysatoren dannes som en katalysator af ekstruderet type.
12. Kemisk fremgangsmåde ifølge krav 10, hvor substratmonolitten er et filtermo-nolit-substrat.
13. Kemisk fremgangsmåde ifølge et hvilket som helst af de foregående krav, hvor udstødningsgassen er fra et køretøjs dieselmotor, benzinmotor eller en motor, der er drevet af flydende petroleumsgas eller naturgas.
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US17035809P | 2009-04-17 | 2009-04-17 | |
US31283210P | 2010-03-11 | 2010-03-11 | |
EP10715069A EP2419209A1 (en) | 2009-04-17 | 2010-04-19 | Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides |
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DK15189846.7T DK2995367T3 (da) | 2009-04-17 | 2010-04-19 | Kobberkatalysator der er understøttet af molekylsigte med små porer med bestandighed mod mager/fed aldring til reduktion af nitrogenoxider |
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US (8) | US7998443B2 (da) |
EP (2) | EP4112168A1 (da) |
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CN (2) | CN102802791A (da) |
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DK (1) | DK2995367T3 (da) |
GB (3) | GB2507902B (da) |
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US7998423B2 (en) | 2007-02-27 | 2011-08-16 | Basf Corporation | SCR on low thermal mass filter substrates |
DK3278863T3 (da) | 2007-04-26 | 2020-02-17 | Johnson Matthey Plc | Overgangsmetal/aei-zeolit-scr-katalysator |
US8512657B2 (en) * | 2009-02-26 | 2013-08-20 | Johnson Matthey Public Limited Company | Method and system using a filter for treating exhaust gas having particulate matter |
US9662611B2 (en) | 2009-04-03 | 2017-05-30 | Basf Corporation | Emissions treatment system with ammonia-generating and SCR catalysts |
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- 2013-08-05 US US13/959,369 patent/US8753598B2/en active Active
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2014
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2015
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- 2015-10-21 US US14/918,725 patent/US9802156B2/en active Active
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2018
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2020
- 2020-03-02 JP JP2020034602A patent/JP2020116573A/ja active Pending
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