JP2015508017A - 産業廃棄物の化学的酸素要求量を電気化学的に減少させるための電極 - Google Patents
産業廃棄物の化学的酸素要求量を電気化学的に減少させるための電極 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001301 oxygen Substances 0.000 title claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 21
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 239000002440 industrial waste Substances 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000001993 wax Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000002334 glycols Chemical class 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract 3
- -1 polyethylene Polymers 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000010842 industrial wastewater Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- LDPIQRWHBLWKPR-UHFFFAOYSA-N aminoboronic acid Chemical compound NB(O)O LDPIQRWHBLWKPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 3
- 239000002518 antifoaming agent Substances 0.000 claims 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 17
- 210000004027 cell Anatomy 0.000 description 23
- 238000011282 treatment Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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Abstract
Description
酸素について38700mg/lのCOD(適当なキットを用いて分光測光法によって検出した値)を有する4リットルの鋳造工場廃液は、32°Fの平均の全硬度を有する90容積%よりもわずかに多い水道水からなり、また0.15容積%のアルキルアリールシロキサン、0.06容積%のエトキシ化ポリエチレンワックスおよび少量の下記の汚染物質を含む:
− 非イオン乳化剤および陰イオン性乳化剤
− エチレン/プロピレングリコール
− 高粘度(ISO VG 460)パラフィン系鉱油
− カルボキシルエステルをベースとする合成油
− シリコーン消泡剤
− ホウ酸アミド
− バクテリア抑制剤
− EDTA
− 典型的な鋳造工場のごみ(アルミニウム合金の塵、油脂、環境粉塵)
この鋳造工場廃液に4g/lのNaClと1g/lのFe2(SO4)3を添加し、そしてこれを、ルテニウム、イリジウムおよびチタンの酸化物の混合物で活性化した114cm2のチタン板からなるアノード、同じサイズの非活性化チタンメッシュからなるカソードおよび0.2mmの厚さのポリプロピレンメッシュからなる隔離板を有し、アノードとカソードの隙間を1mmとした電気化学セルに供給した。セルを500A/m2の電流密度で作動させ、電解液を400 l/hの一定の流量で再循環させた。CODと塩化物のレベルを監視しながら処理を行い、塩化物のレベルは後に(およそ20時間おきに)塩を添加することによって1g/lを超えるように一定に保った。130時間後に酸素について約900mg/lのCODの値に達したときに試験を停止し、それ以上減少する傾向は示さなかったが、一方、セルの電圧はそれまでにおよそ7.4Vの値で安定し、その後はわずかに増大し始めた。
実施例1の試験を、上記の塩化ナトリウムと硫酸第二鉄を添加した同じ廃液を用いて同様の電気化学セルにおいて繰り返したが、ただし、セルは二つの同じ電極で構成されていて、両者はルテニウム、イリジウムおよびチタンの酸化物の混合物で活性化した114cm2のチタン板からなっていて、一つはアノードとして作用し、一つはカソードとして作用した。電極の極性を60分毎に逆転させた。150時間後に酸素について約700mg/lのCODの値に達したときに試験を停止し、それ以上減少する傾向は示さなかった。試験の全体を通してセルの電圧は7.4Vで安定していた。
実施例2の試験を、同じ廃液であるがしかし硫酸第二鉄を外部添加しない廃液を用いて同様の電気化学セルにおいて繰り返したが、ただし、二つの電極は両者とも、ルテニウム、イリジウムおよびチタンの酸化物の混合物で活性化した114cm2のチタン板から得て、この板の上端に機械的に留めることによって固定した広い網目の柔らかい鉄のネットを有していた。電極の極性を60分毎に逆転させた。4時間後に試験を停止し、その後、活性化したチタン板から鉄のネットを取りはずし、そして廃液をろ過工程に供した。次いで、電気化学処理を再開し、7.3Vのセル電圧でさらに63時間延長し、その結果、酸素について140mg/lの残留CODを検出し、全体の処理が200時間に達したときには酸素についてさらに21mg/lまで低下した。
実施例1の試験を、同じ廃液を用いて同様の電気化学セルにおいて、硫酸第二鉄を外部添加せずに繰り返した。110時間後にセル電圧が初期の7.35Vから8Vの値に達したときに試験を停止し、このとき残留CODは酸素について900mg/lよりもわずかに高かった。
Claims (14)
- 廃水の化学的酸素要求量を減少させるのに適した電極であって、
a)永久要素、および
b)永久要素と向き合うように配置されていて、永久要素に分離可能に取り付けられているとともに電気的に接触している犠牲要素、
を有していて、前記永久要素は貴金属またはその酸化物を含む触媒被覆を備えたバルブ金属からなる支持体からなり、前記犠牲要素は元素状の鉄を含む、前記電極。 - 前記犠牲要素は前記永久要素に留められた金属のメッシュまたはワイヤからなる、請求項1に記載の電極。
- 前記犠牲要素は前記永久要素と同一の広がりを有している、請求項1または2に記載の電極。
- 前記触媒被覆はルテニウムおよび/またはイリジウムの酸化物とチタンおよび/またはタンタルの酸化物との混合物を含む、請求項1から3のいずれかに記載の電極。
- 工業廃水の化学的酸素要求量を減少させるための電気化学的システムであって、アノードとして機能する請求項1から4のいずれかに記載の電極とカソードとして機能するバルブ金属または鋼からなる電極を含む電解槽を有する、前記電気化学的システム。
- 工業廃水の化学的酸素要求量を減少させるための電気化学的システムであって、請求項1から4のいずれかに記載の一対の電極を含む電解槽を有し、電極の各々はアノードおよびカソードとして交互に分極化される、前記電気化学的システム。
- 水流に関して前記電解槽に接続された沈降ユニットおよび/またはろ過ユニットを含む、請求項5または6に記載のシステム。
- 前記電解槽の下流に逆浸透ユニットを有する、請求項5から7のいずれかに記載のシステム。
- 油性の化合物、グリコールまたはワックスを含む廃水の化学的酸素要求量を減少させるための方法であって、三価の鉄の存在下でアノードで塩素を発生させることによって廃水を電気分解する工程を含む、前記方法。
- 以下の連続工程:
a)塩化物イオンの濃度が1〜10g/lに達するまで、廃水に塩を選択的に添加する工程;
b)請求項5または6に記載の電気化学的システムの前記電解槽において廃水の最初の電気分解を行い、それにより前記永久要素の表面上で塩素を発生させ、そして前記犠牲要素を部分的に溶解させる工程;
c)前記電極の前記犠牲要素をはずした後、電気化学的システムの前記電解槽において廃水の二次の電気分解を行う工程;
を含む、請求項9に記載の方法。 - 以下の連続工程:
a)塩化物イオンの濃度が1〜10g/lに達するまで、廃水に塩を選択的に添加する工程;
b)請求項7に記載の電気化学的システムの前記電解槽において廃水の最初の電気分解を行い、それにより前記永久要素の表面上で塩素を発生させ、そして前記犠牲要素を部分的に溶解させる工程;
c)前記最初の電気分解から出る廃水の最初の浄化を前記沈降ユニットおよび/またはろ過ユニットにおいて行う工程;
d)前記電極の前記犠牲要素をはずした後、電気化学的システムの前記電解槽において廃水の二次の電気分解を行う工程;
を含む、請求項9に記載の方法。 - 以下の連続工程:
a)塩化物イオンの濃度が1〜10g/lに達するまで、廃水に塩を選択的に添加する工程;
b)請求項8に記載の電気化学的システムの前記電解槽において廃水の最初の電気分解を行い、それにより前記永久要素の表面上で塩素を発生させ、そして前記犠牲要素を部分的に溶解させる工程;
c)前記最初の電気分解から出る廃水の最初の浄化を前記沈降ユニットおよび/またはろ過ユニットにおいて行う工程;
d)前記電極の前記犠牲要素をはずした後、電気化学的システムの前記電解槽において廃水の二次の電気分解を行う工程;
e)前記二次の電気分解から出る廃水の最終的な浄化を前記逆浸透ユニットにおいて行う工程;
を含む、請求項9に記載の方法。 - 前記廃水は鋳造工場の残液である、請求項9から12のいずれかに記載の方法。
- 前記廃水はシロキサン、ポリエチレンワックス、グリコール、鉱油、合成油、シリコーン消泡剤、非シリコーン消泡剤、界面活性剤、EDTAおよびホウ酸アミドからなる群から選択される一つ以上の成分を含む、請求項9から13のいずれかに記載の方法。
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