JP2007284790A - Iv族及びv族の水素化物の電解調製における最大収率を達成するための方法及び装置 - Google Patents
Iv族及びv族の水素化物の電解調製における最大収率を達成するための方法及び装置 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 150000004678 hydrides Chemical class 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 125
- 229910052785 arsenic Inorganic materials 0.000 claims description 24
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- -1 M 1 hydride Chemical class 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 150000004681 metal hydrides Chemical class 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000000203 mixture Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 36
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 35
- 239000007787 solid Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 229910000074 antimony hydride Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 229910000078 germane Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000012035 limiting reagent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000070 arsenic hydride Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000010591 solubility diagram Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
【解決手段】金属M1の水素化物ガスを電気化学セルで発生させる方法であって、電気化学セルは、金属M1を含むカソードと;金属M2を含む犠牲アノードと;金属水酸化物M3OHを含む、ある初期濃度の水性電解質溶液とを含んでなり、犠牲金属アノードは水性電解質溶液の存在下で電気化学的に酸化されて金属塩を生成し、金属M1の水素化物ガスはカソードの金属M1の還元によって生成するものであり、様々なM3OH濃度にて、M3OHが消費され酸化反応によって金属酸化物が生成したときの金属塩の溶解性プロファイル曲線を決定し;消費されたときに、金属塩が電解質溶液から析出するような濃度とならないM3OHの最大濃度を決定し;さらにM3OHの最大濃度とその最大濃度より5%低い濃度との間で、M3OHの初期濃度となる濃度を選択する工程を含む。
【選択図】図2
Description
Mo+2KOH+2H2O→6e-+K2MoO4+6H+
2As+6H2O+6e-→2AsH3+6OH-
アノード酸化反応
M2+2(n−m)OH-→M2O(n-m) (n-2m)-+ne-+(n−m)H2O(式1)
(式中、m及びnは、犠牲アノード金属M2の性質に左右される化学量論係数である。)
アルシン(水素化物)を作るカソード還元反応
As+3H2O+3e-→AsH3+3OH-(式2)
水素を作るカソード還元反応
2H2O+2e-→H2+2OH-(式3)
Claims (8)
- 金属M1の水素化物ガスを電気化学セルで発生させるための方法であって、該電気化学セルは、金属M1を含むカソードと;金属M2を含む犠牲アノードと;金属水酸化物M3OHを含む、ある初期濃度の水性電解質溶液とを含んでなり、ここで、該犠牲金属アノードは該水性電解質溶液の存在下で電気化学的に酸化されて金属塩を生成し、該金属M1の水素化物ガスは該カソードの該金属M1の還元によって生成するものであって、該方法が、
様々なM3OH濃度にて、M3OHが消費され酸化反応によって金属酸化物が生成したときの、該金属塩の溶解性プロファイル曲線を決定する工程と;
消費されたときに、金属塩が該電解質溶液から析出するような濃度とならない、M3OHの最大濃度を決定する工程と;
該M3OHの最大濃度と該M3OHの最大濃度より5%低い濃度との間で、M3OHの初期濃度となる濃度を選択する工程と
を含む、方法。 - M1が、Sb、As、Se、P、Ge、Zn、Pb、Cd及びこれらの合金からなる群から選択される、請求項1に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- 前記犠牲アノードが、水素酸化アノード、酸化還元アノード、及びHg/HgO基準電極に対して酸化電位が0.4ボルト未満である、溶解性で酸化性のイオン種からなる群から選択される、請求項1に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- 前記犠牲アノードが水素酸化アノードであり、M2が、モリブデン、タングステン、バナジウム、カドミウム、鉛、水酸化ニッケル、クロム、アンチモン、ヒ素、及びこれらの合金からなる群から選択される、請求項1に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- 前記犠牲アノードが酸化還元アノードであり、MnO2/MnO3、Fe(OH)2/Fe3O4、Ag2O/Ag2O2、及びCo(OH)3/Co(OH)2からなる群から選択される、請求項1に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- 前記金属水素化物M3OHのM3が、アルカリ及びアルカリ土類金属からなる群から選択される、請求項1に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- M3OHが、NaOH、KOH、LiOH、CsOH、NH4OH及びこれらの組み合わせからなる群から選択される、請求項6に記載の、金属M1の水素化物ガスを電気化学セルで発生させるための方法。
- KOHを約35質量%〜約39質量%含む電解質溶液と;
ヒ素を少なくとも99.0質量%含むカソードと;
モリブデンを含む少なくとも1つのアノードと;
を含む、ヒ素金属の水素化物ガスを発生するための電気化学容器。
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US79184006P | 2006-04-13 | 2006-04-13 | |
US60/791,840 | 2006-04-13 | ||
US11/687,947 US8021536B2 (en) | 2006-04-13 | 2007-03-19 | Method and apparatus for achieving maximum yield in the electrolytic preparation of group IV and V hydrides |
US11/687,947 | 2007-03-19 |
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JP2011056443A Pending JP2011137241A (ja) | 2006-04-13 | 2011-03-15 | Iv族及びv族の水素化物の電解調製における最大収率を達成するための方法及び装置 |
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KR (1) | KR100870161B1 (ja) |
CN (1) | CN101104938B (ja) |
AT (1) | ATE474075T1 (ja) |
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Cited By (3)
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JP2009149987A (ja) * | 2007-12-20 | 2009-07-09 | Air Products & Chemicals Inc | 分割電気化学セル及び安価高純度水素化物ガス製造方法 |
CN110612365A (zh) * | 2017-05-19 | 2019-12-24 | 昭和电工株式会社 | 电化学制造锗烷的方法 |
WO2022118934A1 (ja) * | 2020-12-04 | 2022-06-09 | Eneos株式会社 | 有機ハイドライド製造システム、有機ハイドライド製造システムの制御装置および有機ハイドライド製造システムの制御方法 |
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CN106207203B (zh) * | 2016-07-28 | 2018-09-14 | 华南理工大学 | 一种纳米片状Ni(OH)2催化剂及其制备方法和应用 |
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CN111979558B (zh) * | 2019-05-21 | 2023-08-01 | 紫石能源有限公司 | 电解法制备硒化氢的方法和设备 |
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KR20070101815A (ko) | 2007-10-17 |
JP4842878B2 (ja) | 2011-12-21 |
US20070240997A1 (en) | 2007-10-18 |
US20120205252A1 (en) | 2012-08-16 |
KR100870161B1 (ko) | 2008-11-24 |
EP1845172B1 (en) | 2010-07-14 |
US8591720B2 (en) | 2013-11-26 |
CN101104938A (zh) | 2008-01-16 |
US8021536B2 (en) | 2011-09-20 |
EP1845172A3 (en) | 2009-04-15 |
DE602007007684D1 (de) | 2010-08-26 |
JP2011137241A (ja) | 2011-07-14 |
CN101104938B (zh) | 2011-08-03 |
TWI363106B (en) | 2012-05-01 |
TW200738910A (en) | 2007-10-16 |
ATE474075T1 (de) | 2010-07-15 |
EP1845172A2 (en) | 2007-10-17 |
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