JP5908372B2 - 電気分解用電極 - Google Patents
電気分解用電極 Download PDFInfo
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- JP5908372B2 JP5908372B2 JP2012182744A JP2012182744A JP5908372B2 JP 5908372 B2 JP5908372 B2 JP 5908372B2 JP 2012182744 A JP2012182744 A JP 2012182744A JP 2012182744 A JP2012182744 A JP 2012182744A JP 5908372 B2 JP5908372 B2 JP 5908372B2
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- 238000005868 electrolysis reaction Methods 0.000 title claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 164
- 229910052757 nitrogen Inorganic materials 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 229910045601 alloy Inorganic materials 0.000 claims description 58
- 239000000956 alloy Substances 0.000 claims description 58
- 239000004020 conductor Substances 0.000 claims description 16
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 12
- 239000000788 chromium alloy Substances 0.000 claims description 12
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- ZWKKPKNPCSTXGA-UHFFFAOYSA-N iron neodymium Chemical compound [Fe].[Fe].[Nd] ZWKKPKNPCSTXGA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000583 Nd alloy Inorganic materials 0.000 claims description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- IKHZKATVXPFKTI-UHFFFAOYSA-N tellanylideneiron Chemical compound [Fe].[Te] IKHZKATVXPFKTI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- 229910001215 Te alloy Inorganic materials 0.000 claims description 2
- 229910001080 W alloy Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 70
- 238000006243 chemical reaction Methods 0.000 description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 31
- 238000000034 method Methods 0.000 description 29
- 239000002184 metal Substances 0.000 description 28
- 238000006722 reduction reaction Methods 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000002516 radical scavenger Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 230000009467 reduction Effects 0.000 description 18
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000012545 processing Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- -1 nitrate and nitrite Chemical compound 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 238000010828 elution Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- YWNBJZVPFAVYHC-UHFFFAOYSA-N [Fe].[Cr].[Ni].[B] Chemical compound [Fe].[Cr].[Ni].[B] YWNBJZVPFAVYHC-UHFFFAOYSA-N 0.000 description 1
- VQYBJJWZTGPLRX-UHFFFAOYSA-N [P].[Cr].[Fe] Chemical compound [P].[Cr].[Fe] VQYBJJWZTGPLRX-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- DGDZRQOFZCNHAK-UHFFFAOYSA-N chromium iron nickel tantalum Chemical compound [Cr][Fe][Ni][Ta] DGDZRQOFZCNHAK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
1.電気分解用電極
2.被処理水中の酸化態窒素成分の電解除去処理への適用例
3.実施例
本実施の形態に係る電気分解用電極は、その導電体の表面に合金をアモルファス状態でコーティングしてなることを特徴としている。より具体的に、この電極は、適用例として例えば、塩化物イオンを含む被処理水中の酸化態窒素成分を電気分解によって還元除去するための陰極として好適に用いることができ、その被処理水中の酸化態窒素に対して還元性能を有する合金をアモルファス状態でコーティングしてなる。
次に、本実施の形態に係る電気分解用電極を、被処理水中の酸化態窒素の電解分解による除去処理における陰極として適用した場合を例に挙げて、より詳細に説明する。
図1は、酸化態窒素の電解除去処理に用いられる電解処理装置の一例の概要を示す構成図である。図1に示すように、電解処理装置10は、酸化態窒素を含有する被処理水を収容して電気分解を行う電解槽11と、被処理水を取り込んで調整する調整槽12と、電解槽11と調整槽12との間において被処理水を循環させる循環配管13とから構成されている。
次に、上述した電解処理装置10における電解槽11にて生じる被処理水の電解処理反応について具体的に説明する。
24Cl− + 24H2O → 24ClO− + 48H+ + 48e
[反応式2]
6NO3 − + 48e + 42H2O → 6NH4 + + 60OH−
6NH4 + + 9ClO− → 3N2 + 9Cl− + 9H2O + 6H+
6NO3 − + 15Cl− + 3H2O → 3N2 + 15ClO− + 6OH−
10NH4 + + 15ClO−
→ 5N2 + 15Cl− + 15H2O + 10H+
6NO3 − + 10NH4 + → 8N2 + 18H2O + 4H+
15SO3 2− + 15ClO− → 15Cl− + 15SO4 2−
6NO3 − + 15SO3 2− + 3H2O
→ 3N2 + 15SO4 2− + 6OH−
以下、本発明の具体的な実施例について説明する。なお、下記のいずれかの実施例に本発明の範囲が限定されるものではない。
[実施例1]
実施例1では、図1に示す電解処理装置10(電解槽11は図2と同様)を用いて酸化態窒素の電解処理を行った。
実施例2では、陰極としてニッケル−クロム系合金(Ni65Cr15P16B4(at%))をアモルファス状態でコーティングした電極(アモルファス電極)を用いたこと以外は、実施例1と同様の試験を実施した。
比較例1では、陰極としてFe板(炭素鋼板)を用いたこと以外は、実施例1と同様の試験を実施した。
比較例2では、陰極としてNi板を用いたこと以外は、実施例1と同様の試験を実施した。
比較例3では、陰極としてステンレス(SUS304)板を用いたこと以外は、実施例1と同様の試験を実施した。
[実施例3]
次に、実施例3として、電解槽11に硝酸性窒素濃度20000mg/Lの被処理水を収容し、電解処理時間を20時間として電解処理を行った。なお、その他の条件は実施例1と同様にし、鉄−クロム系合金をアモルファス状態でコーティングした陰極を用いた。
[参照例1]
次に、参照例1として、陰極にFe(炭素鋼板)を用い、通電せずに上記比較例1の通電時間と同じ時間だけ同じ被処理水に浸漬させた。
[参照例2]
次に、参照例2として、陰極にプラチナ(Pt)を用い、上記実施例1と同様の試験を実施した。
Claims (3)
- 導電体の表面に、鉄−クロム系合金、鉄−ネオジム系合金、鉄−ケイ素系合金、鉄−ニッケル系合金、鉄−テルル系合金、ニッケル−クロム系合金、ニッケル−モリブデン系合金、ニッケル−タングステン系合金から選択される合金をアモルファス状態でコーティングしてなり、被処理水中の酸化態窒素成分を電気分解するために陰極として用いられることを特徴とする電気分解用電極。
- 鉄−クロム系合金、又は、ニッケル−クロム系合金をアモルファス状態でコーティングしてなることを特徴とする請求項1に記載の電気分解用電極。
- 無隔膜電解槽にて行われる電気分解に用いられることを特徴とする請求項1または2に記載の電気分解用電極。
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JP5995242B2 (ja) * | 2013-06-27 | 2016-09-21 | 住友金属鉱山エンジニアリング株式会社 | 窒素除去方法及びその装置 |
JP7279993B2 (ja) * | 2019-03-14 | 2023-05-23 | 住友金属鉱山エンジニアリング株式会社 | 酸化態窒素の処理方法 |
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US4609442A (en) * | 1985-06-24 | 1986-09-02 | The Standard Oil Company | Electrolysis of halide-containing solutions with amorphous metal alloys |
JPH0517890A (ja) * | 1991-07-10 | 1993-01-26 | Limes:Kk | 電解電極材及びその製造方法 |
JPH07268676A (ja) * | 1994-03-31 | 1995-10-17 | Toagosei Co Ltd | 水素発生用陰極材料 |
JP3738186B2 (ja) * | 2001-02-26 | 2006-01-25 | 三洋電機株式会社 | 窒素処理方法及び窒素処理システム |
JP5677752B2 (ja) * | 2010-02-25 | 2015-02-25 | 株式会社バンテック | アルカリ水電解用電極、その製造方法及び水素発生装置 |
JP5701080B2 (ja) * | 2011-01-27 | 2015-04-15 | 株式会社バンテック | アルカリ水電解用電極、その製造方法及び水素発生装置 |
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