JP2017177060A - 排ガス浄化触媒 - Google Patents
排ガス浄化触媒 Download PDFInfo
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- JP2017177060A JP2017177060A JP2016072063A JP2016072063A JP2017177060A JP 2017177060 A JP2017177060 A JP 2017177060A JP 2016072063 A JP2016072063 A JP 2016072063A JP 2016072063 A JP2016072063 A JP 2016072063A JP 2017177060 A JP2017177060 A JP 2017177060A
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- Prior art keywords
- exhaust gas
- catalyst
- carrier
- zeolite
- denitration
- 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.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 239000007789 gas Substances 0.000 claims abstract description 91
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 81
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 53
- 239000010457 zeolite Substances 0.000 claims abstract description 53
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims abstract description 31
- 238000002485 combustion reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910018512 Al—OH Inorganic materials 0.000 claims abstract description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- -1 inorganic acid salts Chemical class 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100029133 DNA damage-induced apoptosis suppressor protein Human genes 0.000 description 1
- 101000918646 Homo sapiens DNA damage-induced apoptosis suppressor protein Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- BQPMXCYIQRRYMJ-UHFFFAOYSA-N bismuth;trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BQPMXCYIQRRYMJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- 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
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
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- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
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- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- 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)
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- 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
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- General Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
本発明による排ガス浄化触媒は、燃焼排ガス中の窒素酸化物と接触してこれを窒素に還元することができればいかなる形態を有していてもよく、例えば、粒状、ペレット状、ハニカム状、波状小片、板状等の形態が挙げられるが、適用する反応器やガス流通条件により任意に選定することができる。
以下に、本発明による排ガス処理触媒について具体的に実施例を用いて説明し、併せて、実施例との比較のための比較例を示すが、本発明は、実施例に示すものに限定されるものではない。
本発明により排ガス処理触媒は、Al−OHに関して特定の性質を有する担体が用いられていることを特徴とする。下記実施例1〜4の排ガス処理触媒の担体として、FER型ゼオライトに由来し、かつ、フーリエ変換赤外分光装置(FT−IR)で測定されるAl−OHスペクトルのピーク面積(A)を、測定担体重量(W)で除した値(S)が1500〜3500であるゼオライトを用いた。
(実施例1)
値(S)が1528である、FER型ゼオライト(東ソー製)を使用した。
値(S)が1766であるFER型ゼオライト(東ソー製)を担体とする触媒を調製した。そのための調製手順は、ゼオライトを替えた以外は実施例1と同様とした。
値(S)が2323であるFER型ゼオライト(東ソー製)を担体とする触媒を調製した。そのための手順は、ゼオライトを替えた以外は実施例1と同様とした。
値(S)が3265であるFER型ゼオライト(東ソー製)を担体とする触媒を調製した。そのための手順は、ゼオライトを替えた以外は実施例1と同様とした。
値(S)が1242であるFER型ゼオライト(東ソー製)を担体とする触媒を調製した。そのための手順は、ゼオライトを替えた以外は実施例1と同様とした。
上記の実施例1〜4および比較例1の各触媒について触媒性能試験を行った。上記の実施例1〜4および比較例1の各触媒についてプレス成形を行い、その後に成形物を粉砕し、メッシュサイズ26から16に整粒した。
=(NOxin−NOxout)/NOxin×100…(1)
により算出した。
2 波板状の基材
3 平板状の基材
4 ケーシング
Claims (3)
- 燃焼排ガス中の窒素酸化物を窒素に還元して除去する燃焼排ガス浄化方法に用いられ、該燃焼排ガスには、該窒素酸化物を還元するための還元剤としてアルコールが添加される、排ガス浄化触媒であって、
該触媒は、担体と該担体に担持される脱硝触媒金属とからなり、該担体は、フーリエ変換赤外分光装置(FT−IR)で測定されるAl−OHスペクトルのピーク面積(A)を、測定担体重量(W)で除した値(S)が1500〜3500であるゼオライトであることを特徴とする排ガス浄化触媒。 - 前記ゼオライトは、FER型構造を有する、請求項1に記載の排ガス浄化触媒。
- 前記脱硝触媒金属は、Biである、請求項1または2に記載の排ガス浄化触媒。
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JP2016072063A JP6886776B2 (ja) | 2016-03-31 | 2016-03-31 | 排ガス浄化触媒 |
US16/089,886 US20190083964A1 (en) | 2016-03-31 | 2017-02-28 | Exhaust gas purification catalyst |
KR1020187025652A KR20180132623A (ko) | 2016-03-31 | 2017-02-28 | 배기가스 정화촉매 |
PCT/JP2017/007597 WO2017169450A1 (ja) | 2016-03-31 | 2017-02-28 | 排ガス浄化触媒 |
EP17773995.0A EP3437736A4 (en) | 2016-03-31 | 2017-02-28 | CATALYST FOR EXHAUST GAS PURIFICATION |
CN201780021500.5A CN109070067A (zh) | 2016-03-31 | 2017-02-28 | 废气净化催化剂 |
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JP2023501862A (ja) * | 2019-12-13 | 2023-01-20 | 南▲開▼大学 | 脱硝触媒および該触媒を用いた脱硝方法 |
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EP4194091A1 (en) * | 2020-08-04 | 2023-06-14 | Mitsubishi Heavy Industries, Ltd. | Denitration catalyst and method for purifying exhaust gas |
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JP2016027935A (ja) * | 2012-12-03 | 2016-02-25 | 日立造船株式会社 | 燃焼排ガス浄化用触媒およびこの触媒を用いる脱硝浄化方法 |
JP6205153B2 (ja) * | 2013-03-29 | 2017-09-27 | 日立造船株式会社 | 排ガス浄化システムにおける脱硝触媒のオンサイト再生方法 |
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CN106132540B (zh) * | 2014-03-27 | 2020-03-17 | 日立造船株式会社 | 蜂窝结构体、及使用该蜂窝结构体的废气净化用催化剂、以及废气净化用催化剂的制备方法 |
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