JP6365340B2 - 排ガス浄化触媒 - Google Patents
排ガス浄化触媒 Download PDFInfo
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- JP6365340B2 JP6365340B2 JP2015033040A JP2015033040A JP6365340B2 JP 6365340 B2 JP6365340 B2 JP 6365340B2 JP 2015033040 A JP2015033040 A JP 2015033040A JP 2015033040 A JP2015033040 A JP 2015033040A JP 6365340 B2 JP6365340 B2 JP 6365340B2
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- 238000000746 purification Methods 0.000 title claims description 150
- 239000003054 catalyst Substances 0.000 title claims description 92
- 239000002245 particle Substances 0.000 claims description 75
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 62
- 229910052709 silver Inorganic materials 0.000 claims description 62
- 239000004332 silver Substances 0.000 claims description 62
- 230000001737 promoting effect Effects 0.000 claims description 26
- 210000002421 cell wall Anatomy 0.000 claims description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 18
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 9
- 210000004027 cell Anatomy 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 89
- 239000007789 gas Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 22
- 239000003638 chemical reducing agent Substances 0.000 description 17
- 239000000446 fuel Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000003795 desorption Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical class O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation 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
- B01D53/92—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
- 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
-
- 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
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/66—Silver or gold
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- 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
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/21—Organic compounds not provided for in groups B01D2251/206 or B01D2251/208
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/91—NOx-storage component incorporated in the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
以下、本発明の第1実施形態について、図に基づき説明する。図1に示す排ガス浄化システムは、エンジン100、微粒子捕集装置(DPF)110、DPF再生装置(再生用DOC)120、NOx浄化触媒130、還元剤浄化装置140および還元剤供給弁150を備える。排ガス浄化システムは車両に搭載されるものであり、当該車両は、エンジン100の出力を動力源として走行する。
NOx浄化率(%)=((排出NOx量−浄化後吸着量)/浄化前吸着量)×100
一方、高温環境下におけるNOx浄化触媒130の浄化率測定に関しては、900℃の雰囲気において10時間おき、数1を用いてNOx浄化率を求める。以下、300℃雰囲気下におけるNOx浄化率を耐熱試験前浄化率とよび、900℃雰囲気下におけるNOx浄化率を耐熱試験後浄化率とよぶ。
耐熱層135において、銀を担持させる担体としてセリアを用いた理由を説明する。耐熱層135における担体としてセリア(CeO2)、シリカ(SiO2)、チタニア(TiO2)、アルミナ(Al2O3)を用いてそれぞれに銀粒子を担持させたNOx浄化触媒130の耐熱後浄化率を測定した結果が図8である。図8より、銀担持セリアが最も高いNOx浄化率を示していることがわかる。この結果より、本実施形態においては耐熱層135の担体としてセリアを用いた。
耐熱層135の銀粒子の平均粒径を10nm、30nm、50nm、100nm、200nmおよび300nmとしたときのそれぞれの耐熱試験前浄化率を比較したデータを図9に示す。図9において浄化促進層134における銀粒子の平均粒径は10nm〜50nmの間とした。図9より、平均粒径が50nmより小さくなるにしたがってNOx浄化率は著しく減少していくことがわかる。
耐熱層135の層厚みを10μm、20μm、30μm、40μm、50μm、60μm、70μmとしたときのそれぞれの耐熱試験前浄化率および耐熱試験後浄化率を図10に示す。図10より、耐熱層135の層厚みが30μmより小さい場合は、30μmの場合と比較して耐熱試験後浄化率が著しく低いことがわかる。
なお、本発明は上記実施形態に限定されるものではなく、本発明の技術的範囲に属する限り、以下のように変形させてもよい。
Claims (1)
- 格子状に配設されたセル壁(131)と、前記セル壁に区画された複数のセル(132)とを有する多孔質のハニカム体基材(133)の前記セル壁に、排ガスに対する浄化性能を有する触媒コート層(136)を担持してなる排ガス浄化触媒であって、
前記触媒コート層は、前記セル壁の表面に形成され、少なくとも銀担持アルミナを含む浄化促進層(134)と、
前記浄化促進層の反セル壁側の表面に形成され、銀担持セリアである耐熱層(135)を有し、
前記耐熱層における銀粒子の平均粒径は、前記浄化促進層における銀粒子の平均粒径よりも大きく、かつ、50nm以上200nm以下であり、
前記耐熱層の厚みは、30μm以上60μm以下であることを特徴とする排ガス浄化触媒。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015033040A JP6365340B2 (ja) | 2015-02-23 | 2015-02-23 | 排ガス浄化触媒 |
DE102016102524.0A DE102016102524B4 (de) | 2015-02-23 | 2016-02-15 | Abgasreinigungskatalysator |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015033040A JP6365340B2 (ja) | 2015-02-23 | 2015-02-23 | 排ガス浄化触媒 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016155053A JP2016155053A (ja) | 2016-09-01 |
JP6365340B2 true JP6365340B2 (ja) | 2018-08-01 |
Family
ID=56577377
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2015033040A Expired - Fee Related JP6365340B2 (ja) | 2015-02-23 | 2015-02-23 | 排ガス浄化触媒 |
Country Status (2)
Country | Link |
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JP (1) | JP6365340B2 (ja) |
DE (1) | DE102016102524B4 (ja) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62149343A (ja) | 1985-12-24 | 1987-07-03 | Nippon Engeruharudo Kk | 高温耐熱触媒の製造方法 |
JPS6449343A (en) | 1987-08-19 | 1989-02-23 | Fujitsu Ltd | Station condition supervising system |
JPH06319998A (ja) * | 1993-05-12 | 1994-11-22 | Riken Corp | 排ガス浄化材及び排ガス浄化方法 |
JPH11342339A (ja) * | 1998-03-31 | 1999-12-14 | Mazda Motor Corp | 排気ガス浄化用触媒 |
JP2004322022A (ja) * | 2003-04-28 | 2004-11-18 | Babcock Hitachi Kk | 排ガス浄化用触媒 |
US7678347B2 (en) * | 2005-07-15 | 2010-03-16 | Basf Catalysts Llc | High phosphorous poisoning resistant catalysts for treating automobile exhaust |
JP5000221B2 (ja) * | 2006-07-14 | 2012-08-15 | 本田技研工業株式会社 | 排ガス浄化触媒及び排ガス浄化装置 |
US8173574B2 (en) | 2006-09-20 | 2012-05-08 | Basf Corporation | Catalysts to reduce NOx in an exhaust gas stream and methods of preparation |
-
2015
- 2015-02-23 JP JP2015033040A patent/JP6365340B2/ja not_active Expired - Fee Related
-
2016
- 2016-02-15 DE DE102016102524.0A patent/DE102016102524B4/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE102016102524B4 (de) | 2020-06-25 |
DE102016102524A1 (de) | 2016-08-25 |
JP2016155053A (ja) | 2016-09-01 |
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