JP4706827B2 - Method and apparatus for treating organic halide-containing water - Google Patents
Method and apparatus for treating organic halide-containing water Download PDFInfo
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- JP4706827B2 JP4706827B2 JP2005220387A JP2005220387A JP4706827B2 JP 4706827 B2 JP4706827 B2 JP 4706827B2 JP 2005220387 A JP2005220387 A JP 2005220387A JP 2005220387 A JP2005220387 A JP 2005220387A JP 4706827 B2 JP4706827 B2 JP 4706827B2
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- 150000004820 halides Chemical class 0.000 title claims description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 64
- 239000010802 sludge Substances 0.000 claims description 56
- 238000011282 treatment Methods 0.000 claims description 50
- 239000002244 precipitate Substances 0.000 claims description 49
- -1 ferrous compound Chemical class 0.000 claims description 48
- 150000002506 iron compounds Chemical class 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 2
- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 claims 1
- 229960005191 ferric oxide Drugs 0.000 claims 1
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 claims 1
- 239000002351 wastewater Substances 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 229910000859 α-Fe Inorganic materials 0.000 description 7
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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Description
本発明は、排水等に含まれる有機ハロゲン化物を分解する処理効果と経済性に優れた処理システムに関する。より詳しくは、工程が簡単で実用性に優れ、排水等に含まれる有機ハロゲン化物を常温で分解し、排水等に含まれる有機ハロゲン化物濃度を容易に環境基準値以下に低減することができる処理システムに関する。 The present invention relates to a treatment system excellent in treatment effect and economical efficiency for decomposing organic halides contained in waste water and the like. More specifically, the process is simple, excellent in practicality, decomposes organic halides contained in wastewater etc. at room temperature, and can easily reduce the concentration of organic halides contained in wastewater etc. below the environmental standard value. About the system.
排水等に含まれる有機ハロゲン化物を除去する方法として、地下水面までピットを掘削してその底面に鉄粉層を形成し、あるいは掘削孔に圧縮空気と共に鉄粉を吹き込んで鉄粉層を形成し、該排水等を鉄粉に接触させることによって有機ハロゲン化物を分解させる処理方法が知られている（特許文献１、２）。しかし、この方法は分解に時間がかかるうえ、微細な鉄粉を必要とするため、鉄粉が排水等と共に処理槽から流出する懸念があり、また鉄粉表面の酸化や汚染により分解性能が低下する問題がある。 As a method of removing organic halides contained in drainage, etc., excavate a pit to the groundwater surface to form an iron powder layer on the bottom surface, or blow iron powder with compressed air into the excavation hole to form an iron powder layer. In addition, a treatment method for decomposing an organic halide by bringing the waste water or the like into contact with iron powder is known (Patent Documents 1 and 2). However, this method takes time to decompose and requires fine iron powder, so there is a concern that the iron powder may flow out of the treatment tank together with the drainage, etc., and the decomposition performance deteriorates due to oxidation and contamination of the iron powder surface There is a problem to do.
また、鉄粉を用いる処理方法の改良として、鉄粉と水中で弱酸性を示す還元性物質を併用して有機ハロゲン化物を無害化する処理方法が知られている（特許文献３）。この処理方法は鉄粉を単独に用いる処理方法よりも分解反応は早いが、処理時間以外は上記方法と同様の問題があり、また、弱酸性で処理するために土中の酸が金属を溶出させて排水等中から除去できない場合がある。 In addition, as an improvement of the treatment method using iron powder, a treatment method for detoxifying an organic halide by using a combination of iron powder and a reducing substance that exhibits weak acidity in water is known (Patent Document 3). Although this treatment method has a faster decomposition reaction than the treatment method using iron powder alone, it has the same problems as the above method except for the treatment time, and the acid in the soil elutes the metal to treat with weak acidity. In some cases, it cannot be removed from wastewater.
一方、銅含有鉄粉と硫酸第一鉄を併用して有機物を分解する処理方法も知られているが（特許文献４）、この方法は銅による汚染を引き起こす虞があり、また銅含有鉄粉を用いるために処理コストが高く、表面酸化に敏感なために処理効果が短期間に低下する場合がある。さらに、硫酸第一鉄から生成する水酸化鉄スラッジの含水率が高く、その処理が困難である。 On the other hand, although the processing method which decomposes | disassembles organic substance using copper containing iron powder and ferrous sulfate together is also known (patent document 4), there is a possibility that this method may cause the contamination by copper, and copper containing iron powder. Since the treatment cost is high and the surface oxidation is sensitive, the treatment effect may be reduced in a short time. Furthermore, the water content of iron hydroxide sludge produced from ferrous sulfate is high, and its treatment is difficult.
この他に、マグネタイト−鉄複合粉末を用いる浄化方法が知られている（特許文献５）。この複合粉末は有機ハロゲン化物の分解に使用されている従来の鉄粉よりも反応性が高く活性が持続するとされているが、マグネタイト−鉄複合粉末の製造コストが高く、また、粉末表面の酸化や汚染によって処理効果が低下する問題がある。
本発明は、従来の上記問題を解決した有機ハロゲン化物含有水の処理方法を提供するものであり、有機ハロゲン化物の処理効果に優れ、しかも沈澱が圧密化されるので固液分離性が良く、かつ常温でフェライト処理が可能な経済性に優れた処理方法および処理装置を提供する。 The present invention provides a conventional method for treating organic halide-containing water that solves the above-mentioned problems, is excellent in the treatment effect of organic halides, and has good solid-liquid separation because the precipitate is consolidated. In addition, the present invention provides a processing method and a processing apparatus excellent in economic efficiency that enable ferrite processing at room temperature.
本発明は以下の構成を有する有機ハロゲン化物含有水の処理方法およびその処理装置に関する。
〔１〕有機ハロゲン化物含有水を鉄化合物に接触させて有機ハロゲン化物を分解する処理方法において、有機ハロゲン化物含有水に鉄化合物を添加する工程〔鉄化合物添加工程〕、鉄化合物を添加した上記含有水を反応槽に導いて有機ハロゲン化物を分解する工程〔分解工程〕、生成した沈澱(汚泥)を固液分離する工程〔汚泥分離工程〕、分離した汚泥の全部または一部をアルカリ性にして反応槽に返送する工程〔汚泥返送工程〕を有し、上記分解工程において、鉄化合物を添加した有機ハロゲン化物含有水とアルカリ性汚泥とを混合して、非酸化性雰囲気下、アルカリ性下で反応させ、還元性の鉄化合物沈澱を生成させて有機ハロゲン化物を分解することを特徴とする有機ハロゲン化物含有水の処理方法。
〔２〕上記[１]に記載する処理方法において、上記含有水に含まれる有機ハロゲン化物が四塩化炭素、ジクロロメタン、１,２−ジクロロエタン、１,１−ジクロロエチレン、シス−１,２−トリクロロエチレン、１,１,１−トリクロロエタン、１,１,２−トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、１,３−ジクロロプロペンの何れか一種または二種以上であり、上記有機ハロゲン化物の残留濃度を０.０１mg/L以下に低減する有機ハロゲン化物含有水の処理方法。
〔３〕上記[１]または上記[２]に記載する処理方法において、有機ハロゲン化物含有水に第一鉄化合物を添加し、該第一鉄化合物を添加した上記含有水を反応槽に導き、一方、汚泥分離工程で分離した汚泥の一部または全部をアルカリ性にして反応槽に返送し、該反応槽において、非酸化性雰囲気下、１０℃〜３０℃の温度下、ｐＨ８.５〜１１の液性下で、沈澱の２価鉄イオンと全鉄イオンの比〔Ｆｅ２＋／Ｆｅ(T)〕が０.４〜０.８であるように還元性鉄化合物沈澱を生成させる有機ハロゲン化物含有水の処理方法。
〔４〕上記[１]〜上記[３]の何れかに記載する処理方法において、鉄化合物添加工程の前に、有機ハロゲン化物含有水に鉄化合物またはアルミニウム化合物を添加し、アルカリ性下で鉄またはアルミニウムの水酸化物を沈殿させることによって、上記含有水中のケイ酸イオンないしアルミニウムイオンの少なくとも何れかを上記水酸化物と共に沈澱化し、この沈澱を濾過除去する前処理工程を設け、ケイ酸イオンないしアルミニウムイオンを除去した上記含有水を鉄化合物添加工程に導く有機ハロゲン化物含有水の処理方法。
〔５〕有機ハロゲン化物含有水に第一鉄化合物を添加する槽、第一鉄化合物を添加した上記含有水を導入する非酸化性の密閉反応槽、この密閉反応槽から抜き出したスラリーを導入する汚泥分離槽、分離した汚泥(沈殿)の一部または全部にアルカリを添加する槽、ｐＨ１１〜１３のアルカリ性にした汚泥を上記密閉反応槽に導入する管路、上記密閉反応槽において第一鉄化合物を添加した上記含有水と上記アルカリ性汚泥とを混合し、非酸化性雰囲気下、ｐＨ８.５〜１１に調整して有機ハロゲン化物を還元分解することを特徴とする有機ハロゲン化物含有水の処理装置。
〔６〕上記[５]の処理装置において、有機ハロゲン化物含有水に含まれるケイ酸ないしアルミニウムを予め沈殿化して除去する手段を、鉄化合物添加槽の前に設けた有機ハロゲン化物含有水の処理装置。
The present invention relates to a method and apparatus for treating organic halide-containing water having the following constitution.
[1] In a treatment method for decomposing an organic halide by bringing the organic halide-containing water into contact with the iron compound, a step of adding the iron compound to the organic halide-containing water [iron compound adding step], the above-described addition of the iron compound A process of decomposing organic halides by introducing the contained water into the reaction tank (decomposition process), a process of solid-liquid separation of the generated precipitate (sludge) (sludge separation process), and making all or part of the separated sludge alkaline It has a step of returning to the reaction tank (sludge return step). In the above decomposition step, the organic halide-containing water to which the iron compound is added and alkaline sludge are mixed and reacted in a non-oxidizing atmosphere and under alkaline conditions. A method for treating organic halide-containing water, comprising decomposing an organic halide by producing a reducible iron compound precipitate.
[2] In the treatment method described in [1] above, the organic halide contained in the water is carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethylene, cis-1,2-trichloroethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene, 1,3-dichloropropene, one or more, and the residual concentration of the organic halide is 0.01 mg / L The organic halide-containing water treatment method is reduced to the following.
[3] In the treatment method described in [1] or [2] above, a ferrous compound is added to water containing organic halide, and the water containing the ferrous compound is introduced into a reaction vessel, On the other hand, part or all of the sludge separated in the sludge separation step is made alkaline and returned to the reaction tank. In the reaction tank, the pH is 8.5 to 11 at a temperature of 10 ° C. to 30 ° C. in a non-oxidizing atmosphere. Contains an organic halide that forms a reduced iron compound precipitate such that the ratio of divalent iron ions to total iron ions [Fe 2+ / Fe (T)] in the liquid state is 0.4 to 0.8. Water treatment method.
[4] In the treatment method described in any one of [1] to [3] above, before the iron compound addition step, an iron compound or an aluminum compound is added to the organic halide-containing water, and iron or By precipitating aluminum hydroxide, at least one of silicate ions or aluminum ions in the contained water is precipitated together with the hydroxide, and a pretreatment step is provided for removing the precipitate by filtration. A method for treating organic halide-containing water, wherein the above-mentioned contained water from which aluminum ions have been removed is led to an iron compound addition step.
[5] A tank for adding ferrous compound to water containing organic halide, a non-oxidizing sealed reaction tank for introducing the contained water added with ferrous compound, and a slurry extracted from the sealed reaction tank are introduced. A sludge separation tank, a tank for adding alkali to a part or all of the separated sludge (precipitation), a conduit for introducing alkaline sludge having a pH of 11 to 13 into the closed reaction tank, and a ferrous compound in the closed reaction tank An organic halide-containing water treatment apparatus characterized by mixing the above-mentioned containing water with the addition of alkaline sludge and adjusting the pH to 8.5-11 in a non-oxidizing atmosphere to reduce and decompose the organic halide. .
[6] In the treatment apparatus according to [5], the means for precipitating silicic acid or aluminum contained in the organic halide-containing water is a treatment of the organic halide-containing water provided in front of the iron compound addition tank. apparatus.
本発明の処理方法によれば、排水等に含まれる有機ハロゲン化物の濃度を環境基準値の０.０１mg/L以下に容易に低減することができる。従って、本発明の処理方法は有機ハロゲン化物を含む土壌地下水など各種の有機ハロゲン化物含有水の浄化に有効である。 According to the treatment method of the present invention, the concentration of organic halide contained in waste water or the like can be easily reduced to an environmental standard value of 0.01 mg / L or less. Therefore, the treatment method of the present invention is effective for purifying various organic halide-containing waters such as soil groundwater containing organic halides.
また、本発明の処理方法は、還元性鉄化合物沈澱の一部または全部をアルカリ化して反応槽に返送し、再び還元性鉄化合物沈殿を生成させて有機ハロゲン化物を分解することを繰り返すので、汚泥(沈澱)が還元性を維持しつつ鉄フェライト化し、汚泥が圧密化するので分離した汚泥を容易に脱水処理することができる。因みに、従来の処理方法では、水酸化鉄を主体とした汚泥であるために嵩高く、脱水処理の負担が大きい。 Further, the treatment method of the present invention repeats the step of alkalizing part or all of the reductive iron compound precipitate and returning it to the reaction vessel, again generating the reducible iron compound precipitate and decomposing the organic halide. Sludge (precipitate) turns into iron ferrite while maintaining reducibility, and the sludge is consolidated, so that the separated sludge can be easily dehydrated. Incidentally, in the conventional treatment method, since it is a sludge mainly composed of iron hydroxide, it is bulky and the burden of dehydration treatment is large.
さらに、本発明の処理方法では、沈澱を形成している鉄フェライトはマグネタイトを主体とするため磁性を帯びており、分離した沈澱を磁石に吸着させて処理することができる。このように本発明の処理方法は有機ハロゲン化物の分解効果に優れ、経済性および取扱性にも優れた処理方法である。 Furthermore, in the treatment method of the present invention, the iron ferrite forming the precipitate is magnetized because it is mainly composed of magnetite, and the separated precipitate can be adsorbed to a magnet for treatment. As described above, the treatment method of the present invention is excellent in the effect of decomposing organic halides, and is also excellent in economic efficiency and handleability.
本発明の処理方法は、有機ハロゲン化物含有水を鉄化合物に接触させて有機ハロゲン化物を分解する処理方法において、有機ハロゲン化物含有水に鉄化合物を添加する工程〔鉄化合物添加工程〕、鉄化合物を添加した上記含有水を反応槽に導いて有機ハロゲン化物を分解する工程〔分解工程〕、生成した沈澱(汚泥)を固液分離する工程〔汚泥分離工程〕、分離した汚泥の全部または一部をアルカリ性にして反応槽に返送する工程〔汚泥返送工程〕を有し、上記分解工程において、鉄化合物を添加した有機ハロゲン化物含有水とアルカリ性汚泥とを混合して、非酸化性雰囲気下、アルカリ性下で反応させ、還元性の鉄化合物沈澱を生成させて有機ハロゲン化物を分解することを特徴とする有機ハロゲン化物含有水の処理方法である。 The treatment method of the present invention comprises a step of bringing an organic halide-containing water into contact with an iron compound to decompose the organic halide, and a step of adding the iron compound to the organic halide-containing water [iron compound addition step], an iron compound Decomposing organic halides by introducing the water containing the above to the reaction tank [decomposition step], solid-liquid separation of the generated precipitate (sludge) [sludge separation step], all or part of the separated sludge And returning to the reaction tank [sludge return step], in the above decomposition step, the organic halide-containing water added with the iron compound and alkaline sludge are mixed, and the mixture is alkaline in a non-oxidizing atmosphere. The organic halide-containing water treatment method is characterized in that the organic halide is decomposed by reacting under conditions to generate a reduced iron compound precipitate.
本発明の処理方法を実施する装置構成の概略を図１に示す。図示する処理システムは、有機ハロゲン化物含有水に第一鉄化合物を添加する槽１０、第一鉄化合物を添加した上記含有水を導入する非酸化性の密閉反応槽３０、この密閉反応槽から抜き出したスラリーを導入して汚泥を分離する槽４０、分離した汚泥(沈殿)の一部または全部にアルカリを添加する槽２０、アルカリ性にした汚泥を上記密閉反応槽３０に導入する管路およびこれらの各槽を連通する管路を備えており、上記密閉反応槽３０において第一鉄化合物を添加した上記含有水とアルカリ性汚泥とを混合して有機ハロゲン化物を還元分解する処理システムである。なお、図示する処理システムにおいて、反応槽３０を２台以上直列に設置し、これらを窒素でパージした密閉構造にし、還元性雰囲気下で上記フェライト化処理を行うようにすると良い。
FIG. 1 shows an outline of an apparatus configuration for carrying out the processing method of the present invention. The illustrated processing system includes a
本発明の処理方法において、有機ハロゲン化物含有水とは、有機ハロゲン化物を含有する水を広く意味し、自然発生的または為的に生じた各種の廃水や排水、流水等を含み、例えば、工場排水や生活排水、下水、海水、河川水、沼や湖池の水、地表の溜り水、河川等の堰止域の水、地下の流水や溜り水、暗渠の水などであって、有機ハロゲン化物を含有するものを云う。なお、本発明の説明において、これらの水を含めて排水等と云う場合がある。 In the treatment method of the present invention, organic halide-containing water broadly means water containing an organic halide, and includes various types of wastewater, wastewater, running water, etc. that are generated spontaneously or intentionally. Wastewater, domestic wastewater, sewage, seawater, river water, swamp and lake pond water, surface pool water, river and other dam water, underground running water and pool water, underdrain water, etc. A substance containing a chemical compound. In the description of the present invention, these waters are sometimes referred to as drainage.
排水等に含まれる有機ハロゲン化物としては、例えば、四塩化炭素、ジクロロメタン、１,２−ジクロロエタン、１,１−ジクロロエチレン、シス−１,２−トリクロロエチレン、１,１,１−トリクロロエタン、１,１,２−トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、１,３−ジクロロプロペンの何れか一種または二種以上である。 Examples of the organic halide contained in the waste water include carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethylene, cis-1,2-trichloroethylene, 1,1,1-trichloroethane, and 1,1. , 2-trichloroethane, trichloroethylene, tetrachloroethylene, 1,3-dichloropropene, or one or more thereof.
排水等に添加する鉄化合物としては、硫酸第一鉄(FeSO4)、塩化第一鉄(FeCl2)などの第一鉄化合物が用いられる。第一鉄化合物の添加量はＦｅ2+イオン濃度４００〜６００mg/Lになる量が適当である。この鉄化合物を添加した排水等を反応槽に導入する。 Ferrous compounds such as ferrous sulfate (FeSO 4 ) and ferrous chloride (FeCl 2 ) are used as iron compounds to be added to waste water and the like. The addition amount of the ferrous compound is appropriate such that the Fe 2+ ion concentration is 400 to 600 mg / L. The waste water to which the iron compound is added is introduced into the reaction tank.
反応槽には、上記鉄化合物を添加した有機ハロゲン化物含有水が導入されると共に、汚泥分離工程から返送されたアルカリ性汚泥が導入される。このアルカリ性汚泥は後工程において固液分離された沈澱（汚泥）の一部または全部にアルカリを添加してｐＨ１１〜１３に調整したものである。添加するアルカリ物質としては消石灰、生石灰、水酸化ナトリウムなどを用いることができる。アルカリ性汚泥を混合することによって反応槽３０のｐＨは８.５〜１１、好ましくはｐＨ９.０〜１０に調整される。 Into the reaction tank, the organic halide-containing water added with the iron compound is introduced, and the alkaline sludge returned from the sludge separation step is introduced. This alkaline sludge is adjusted to pH 11 to 13 by adding alkali to a part or all of the precipitate (sludge) separated into solid and liquid in the subsequent step. As the alkaline substance to be added, slaked lime, quick lime, sodium hydroxide or the like can be used. By mixing the alkaline sludge, the pH of the reaction tank 30 is adjusted to 8.5 to 11, preferably pH 9.0 to 10.
反応槽において、鉄化合物を添加した有機ハロゲン化物含有水とアルカリ性返送汚泥とを混合し、非酸化性雰囲気下で反応させて、還元力を有する鉄化合物沈澱を生成させる。この鉄化合物沈澱はグリーンラストと鉄フェライトの混合物であり、還元性の沈澱である。 In the reaction tank, the organic halide-containing water to which the iron compound is added and the alkaline return sludge are mixed and reacted in a non-oxidizing atmosphere to produce an iron compound precipitate having a reducing power. This iron compound precipitate is a mixture of green last and iron ferrite and is a reductive precipitate.
グリーンラストは第一鉄と第二鉄の水酸化物が層状をなす青緑色の物質であり、層間に重金属のアニオンを取り込んだ構造を有し、例えば次式(１)によって表される。
〔ＦｅII (6-x)ＦｅIII x（ＯＨ）12〕x+〔Ａx/n・ｙＨ2Ｏ〕x- …（１）
（０.９＜ｘ＜４.２、Ｆｅ2+/全Ｆｅ＝０.３〜０.８５）。
Green last is a blue-green substance in which a hydroxide of ferrous iron and ferric iron forms a layer, and has a structure in which an anion of heavy metal is incorporated between layers, and is represented by, for example, the following formula (1).
[Fe II (6-x) Fe III x (OH) 12 ] x + [A x / n · yH 2 O] x- ... (1)
(0.9 <x <4.2, Fe 2+ / total Fe = 0.3 to 0.85).
一方、鉄フェライトはＦｅIIの鉄(III)酸塩であり、マグネタイト（ＦｅIIＦｅIII 3Ｏ4）を主体とするが、一部に重金属の鉄酸塩を含むものでもよい。 On the other hand, iron ferrites are Fe II iron (III) salt, but mainly of magnetite (Fe II Fe III 3 O 4 ), or those containing ferrate of heavy metals in a part.
排水等に含まれる有機ハロゲン化物は還元力を有する上記鉄化合物沈殿によって還元分解される。例えば、テトラクロロエチレンは次式(２)のように上記鉄化合物沈殿によって還元分解され、塩素が除去される。
２[Ｆｅ4 (II)Ｆｅ2 (III)（ＯＨ）12]2+[ＳＯ4 2-・３Ｈ2Ｏ]2-＋Ｃ2Ｃｌ4＋４ＯＨ- → ４Ｆｅ3Ｏ4＋２ＳＯ4 2-＋１８Ｈ2Ｏ＋Ｃ2Ｈ4＋２Ｃｌ2 …(２)
Organic halides contained in waste water and the like are reduced and decomposed by the iron compound precipitation having reducing power. For example, tetrachlorethylene is reductively decomposed by the iron compound precipitation as shown in the following formula (2) to remove chlorine.
2 [Fe 4 (II) Fe 2 (III) (OH) 12] 2+ [SO 4 2- · 3H 2 O] 2+ C 2 Cl 4 + 4OH - → 4Fe 3 O 4 + 2SO 4 2+ 18H 2 O + C 2 H 4 + 2Cl 2 (2)
反応槽で上記還元性鉄化合物沈澱を生成させるために、空気の流入を遮断した密閉反応槽を用い、非酸化性雰囲気下、ｐＨ８.５〜１１、好ましくはｐＨ９.０〜１０のアルカリ性下で反応させる。液温は１０℃〜３０℃程度で良く、加熱する必要はない。反応時間は一般的には１００時間〜１８０時間程度で良い。 In order to produce the reductive iron compound precipitate in the reaction vessel, a closed reaction vessel in which the inflow of air was blocked was used, and the pH was 8.5 to 11, preferably pH 9.0 to 10 in a non-oxidizing atmosphere. React. The liquid temperature may be about 10 ° C. to 30 ° C. and does not need to be heated. In general, the reaction time may be about 100 hours to 180 hours.
なお、排水等に第一鉄化合物とアルカリとを添加して鉄化合物沈澱を生成させる処理方法であっても、従来のように反応槽が密閉されておらず、非酸化性雰囲気下ではないもの、またアルカリの程度が弱いものは、上記還元力を有する沈澱が生成せず、本発明と同様の効果を得ることはできない。 In addition, even in a treatment method in which ferrous compound and alkali are added to waste water to produce an iron compound precipitate, the reaction vessel is not sealed as in the prior art and is not in a non-oxidizing atmosphere. In addition, when the alkali is weak, the precipitate having the reducing power is not generated, and the same effect as in the present invention cannot be obtained.
本発明の処理方法においては、グリーンラストと鉄フェライトの混合物からなる上記鉄化合物沈澱が還元力を有するように、該沈澱の２価鉄イオンと全鉄イオンの比〔Ｆｅ2+／Ｆｅ(T)〕が０.４〜０.８であるように沈澱を生成させることが好ましく、上記鉄イオン比を０.５５〜０.６５に制御するのが更に好ましい。この比が上記範囲を外れると還元力が不十分になるので好ましくない。 In the treatment method of the present invention, the ratio of divalent iron ions to total iron ions of the precipitate [Fe 2+ / Fe (T )] Is preferably 0.4 to 0.8, and the iron ion ratio is more preferably controlled to 0.55 to 0.65. If this ratio is out of the above range, the reducing power becomes insufficient.
反応槽にアルカリ性汚泥の返送を繰り返し、鉄化合物を添加した有機ハロゲン化含有水との反応を繰り返すことによって、最初は深青緑色であった沈澱はグリーンラストが酸化して鉄フェライト化することによって黒色に変化する。グリーンラストの大部分が鉄フェライトになると還元性がなくなるので、本発明の処理方法では、上記鉄化合物沈澱の２価鉄イオンと全鉄イオンの比〔Ｆｅ2+／Ｆｅ(T)〕を上記範囲内に制御して還元性沈澱を生成させる。 By repeating the return of alkaline sludge to the reaction tank and repeating the reaction with the organic halide-containing water to which the iron compound was added, the precipitate that was initially deep blue-green became black by oxidation of the green rust and iron ferrite formation. To change. Since the reducibility is lost when most of the green rust becomes iron ferrite, in the treatment method of the present invention, the ratio [Fe 2+ / Fe (T)] of the divalent iron ions to the total iron ions in the iron compound precipitate is set as described above. Control within the range to produce a reducing precipitate.
反応層において、上記還元性鉄化合物沈殿が十分に存在した状態で有機ハロゲン化物を上記還元性鉄化合物に接触させて分解するのが好ましい。そこで、還元性鉄化合物沈殿が十分に存在しない場合には、あらかじめ有機ハロゲン化物を含まない排水等を用いて上記処理工程を数回〜数十回繰り返して上記還元性鉄化合物沈殿を十分に生成させた後に、有機ハロゲン化物含有水を通水すると良い。 In the reaction layer, it is preferable to decompose the organic halide in contact with the reducing iron compound in a state where the reducing iron compound precipitate is sufficiently present. Therefore, if there is not enough reducible iron compound precipitate, repeat the above treatment process several times to several tens of times using wastewater that does not contain organic halides in advance to generate the reducible iron compound precipitate sufficiently. Then, it is preferable to pass water containing organic halide.
具体的には、例えば、トリクロロエチレンを含まない排水等に、Ｆｅ2+イオン濃度４００〜６００mg/Lになるように第一鉄化合物を添加し、この第一鉄化合物を添加した排水等に、後工程の汚泥分離工程で分離した汚泥の全部または一部にアルカリを添加してｐＨ１１〜１３にしたアルカリ性汚泥を混合し、空気の混入を遮断した密閉反応槽で、１０℃〜３０℃の温度下、ｐＨ９.０〜９.３で３０分〜２時間反応させ、生成した沈澱(汚泥)を固液分離し、再びこの汚泥の全部または一部にアルカリを添加して反応槽に返送する。このような操作によって反応槽内で所定濃度の還元性鉄化合物沈殿を生成させる。この後に、トリクロロエチレン濃度１mg/Lの有機ハロゲン化物含有水に第一鉄化合物を添加し、この第一鉄化合物を添加した有機ハロゲン化物含有水を反応槽に導入して１２０時間接触させて排水等に含まれているトリクロロエチレンを還元分解する。この処理によって沈殿を分離した排水等のトリクロロエチレン濃度を環境基準値（０.０１mg/L）以下に低減することができる。 Specifically, for example, a ferrous compound is added to wastewater that does not contain trichlorethylene so that the Fe 2+ ion concentration is 400 to 600 mg / L, and the wastewater to which this ferrous compound is added In a sealed reaction tank in which alkaline sludge having a pH of 11 to 13 is added to all or part of the sludge separated in the sludge separation step of the process and mixed to prevent air contamination, at a temperature of 10 ° C. to 30 ° C. The reaction is carried out at pH 9.0 to 9.3 for 30 minutes to 2 hours, the produced precipitate (sludge) is separated into solid and liquid, and alkali is added to all or part of this sludge and returned to the reaction vessel. By such an operation, a reducing iron compound precipitate having a predetermined concentration is generated in the reaction vessel. Thereafter, ferrous compound is added to organic halide-containing water having a trichlorethylene concentration of 1 mg / L, and the organic halide-containing water to which this ferrous compound is added is introduced into the reaction vessel and contacted for 120 hours to drain the water. The trichlorethylene contained in is reduced and decomposed. By this treatment, the concentration of trichlorethylene such as waste water from which the precipitate has been separated can be reduced below the environmental standard value (0.01 mg / L).
なお、有機ハロゲン化物含有水中に、有機ハロゲン化物と共に、ケイ酸イオンやアルミニウムイオンが含まれていると、これらのイオンによって上記還元性沈殿の生成が影響を受け、有機ハロゲン化物の分解効果が低下する場合がある。このような場合には、あらかじめケイ酸イオンやアルミニウムイオンを除去する工程を設けると良い。 In addition, when silicate ions and aluminum ions are contained in the organic halide-containing water together with the organic halide, the formation of the reductive precipitate is affected by these ions, and the decomposition effect of the organic halide is reduced. There is a case. In such a case, a step of removing silicate ions and aluminum ions in advance may be provided.
具体的には、有機ハロゲン化物含有水に塩化第二鉄などを添加し、アルカリ性に調整して鉄水酸化物沈殿を生成させ、上記含有水に含まれるケイ酸イオンやアルミニウムイオンをこの鉄水酸化物沈澱に取り込ませて共沈させ、この沈澱を固液分離して除去すればよい。なお、塩化第二鉄などに代えてアルミニウム化合物を添加してアルカリを加え、アルミニウム水酸化物を沈殿させても良い。この前処理によって、有機ハロゲン化物含有水のケイ酸イオンやアルミニウムイオンをあらかじめ除去した後に、鉄化合物添加、還元分解、汚泥分離、汚泥返送の上記各処理を行えば、還元性鉄化合物の沈殿生成が阻害されず、有機ハロゲン化物の分解効果を高めることができる。 Specifically, ferric chloride or the like is added to organic halide-containing water, adjusted to alkalinity to produce an iron hydroxide precipitate, and silicate ions and aluminum ions contained in the above-mentioned water are added to the iron water. The precipitate may be taken into the oxide precipitate and coprecipitated, and the precipitate may be removed by solid-liquid separation. Note that an aluminum compound may be added instead of ferric chloride and an alkali may be added to precipitate the aluminum hydroxide. By pre-removing the silicate ions and aluminum ions of the organic halide-containing water by this pretreatment, the iron compound addition, reductive decomposition, sludge separation, sludge return, and the above treatments are carried out to produce precipitates of reducing iron compounds. Is not inhibited, and the decomposition effect of the organic halide can be enhanced.
また、先に述べたように、汚泥分離槽において分離された汚泥の全部または一部はアルカリ性にして反応槽に返送されるが、反応槽に返送されない汚泥はフィルタープレスなどによって脱水し、水分は系外に排水される。一方、濾渣は還元力が残存しており、しかもこの濾渣は透水性が良いので、必要に応じ、図２に示すように、この濾渣に汚染度の高くない別系統の排水等を通水し、濾渣に残存する還元力を利用して排水等の汚染を分解し、排水等から除去することができる。 As described above, all or a part of the sludge separated in the sludge separation tank is made alkaline and returned to the reaction tank, but the sludge not returned to the reaction tank is dehydrated by a filter press or the like, Drained outside the system. On the other hand, the filter residue has a reducing power, and this filter residue has good water permeability. Therefore, as shown in FIG. By using the reducing power remaining in the filter residue, it is possible to decompose the wastewater and the like and remove it from the wastewater.
以下、本発明の実施例を比較例と共に示す。
〔実施例１〕
図１に示す本発明の処理フローに従い、あらかじめ還元性鉄化合物沈殿を十分に生成させるため、トリクロロエチレンを含まない排水等２Ｌを添加槽１０に導入し、硫酸第一鉄をＦｅ(II)として６００mg/Ｌになるように添加した。一方、固液分離した沈澱に消石灰を添加してｐＨ１１に調整し、このアルカリ性沈澱を２００ｇ/Ｌの濃度で反応槽に戻し、硫酸第一鉄を添加した排水等と混合し、嫌気性雰囲気下、ｐＨ９.０、液温２０℃で３０分〜２時間反応させた。次いで、反応槽から抜き出したスラリーをシックナーで２０時間静置して沈澱を分離した。この沈澱に消石灰を加えてアルカリ性にしたものを反応槽に戻してさらに還元性鉄化合物沈殿を生成させた。この沈澱の生成分離を３０回繰り返し、、トリクロロエチレンの分解に必要な濃度の還元性沈殿を生成させた。この後に、トリクロロエチレン濃度１mg/Lの排水等２Ｌを上記処理系に導入し、鉄化合物の添加、還元性沈殿の生成、汚泥の分離、汚泥のアルカリ化、アルカリ性汚泥の返送の各処理を繰り返し行った。なお、反応槽での処理時間は１２０時間、繰り返し回数３０回とした。この結果、沈殿を分離した排水等のトリクロロエチレン濃度は０.０１mg/Ｌ以下であった。
Examples of the present invention are shown below together with comparative examples.
[Example 1]
In accordance with the treatment flow of the present invention shown in FIG. 1, 2 L of waste water or the like not containing trichloroethylene is introduced into the
〔比較例１〕
トリクロロエチレン１mg/Ｌを含む排水等２Ｌに、還元用鉄粉（平均粒径１００μm）を５０ｇ添加し、嫌気性環境下、ｐＨ９.０で１２０時間分解反応を進めた。生成した沈殿を除去した排水等に含まれるトリクロロエチレンの残留濃度は０.１mg/Ｌであった。
[Comparative Example 1]
50 g of iron powder for reduction (average particle size 100 μm) was added to 2 L of waste water containing 1 mg / L of trichlorethylene, and the decomposition reaction was advanced for 120 hours at pH 9.0 in an anaerobic environment. The residual concentration of trichlorethylene contained in the waste water from which the generated precipitate was removed was 0.1 mg / L.
１０−鉄化合物添加槽、２０−アルカリ添加槽、３０−反応槽、４０−固液分離槽。 10-iron compound addition tank, 20-alkali addition tank, 30-reaction tank, 40-solid-liquid separation tank.
Claims (6)
In the treatment method of decomposing an organic halide by bringing the organic halide-containing water into contact with the iron compound, a step of adding the iron compound to the organic halide-containing water [iron compound addition step], the above-mentioned water containing the iron compound added thereto Step of decomposing organic halide by introducing into reaction tank (decomposition step), step of solid-liquid separation of generated precipitate (sludge) (sludge separation step), making all or part of the separated sludge alkaline, It has a return process (sludge return process), and in the above decomposition process, the organic halide-containing water added with iron compound and alkaline sludge are mixed and reacted in a non-oxidizing atmosphere and under alkaline conditions. A method for treating organic halide-containing water, comprising decomposing an organic halide by forming an iron compound precipitate.
The treatment method according to claim 1, wherein the organic halide contained in the water contains carbon tetrachloride, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethylene, cis-1,2-trichloroethylene, 1,1,1. Any one or more of 1-trichloroethane, 1,1,2-trichloroethane, trichlorethylene, tetrachloroethylene, and 1,3-dichloropropene, and reduce the residual concentration of the organic halide to 0.01 mg / L or less. A method for treating organic halide-containing water.
The treatment method according to claim 1 or 2, wherein a ferrous compound is added to the organic halide-containing water, and the water containing the ferrous compound is introduced into a reaction vessel, while being separated in a sludge separation step. A part or all of the sludge was made alkaline and returned to the reaction tank, where it was precipitated in a non-oxidizing atmosphere at a temperature of 10 ° C. to 30 ° C. and a liquid of pH 8.5-11. A method for treating organic halide-containing water, wherein a reduced iron compound precipitate is produced such that the ratio [Fe 2+ / Fe (T)] of divalent iron ions to total iron ions is 0.4 to 0.8.
The treatment method according to any one of claims 1 to 3, wherein an iron compound or an aluminum compound is added to the organic halide-containing water before the iron compound addition step to precipitate iron or aluminum hydroxide under alkalinity. By containing the silicate ions or aluminum ions in the contained water, the precipitating step for precipitating together with the hydroxide and precipitating the precipitates by filtration is provided, and the silicate ions or aluminum ions are removed. A method for treating water containing an organic halide that leads water to an iron compound addition step.
A tank for adding ferrous compound to water containing organic halide, a non-oxidizing sealed reaction tank for introducing the above-mentioned water containing ferrous compound, and a sludge separation tank for introducing slurry extracted from this sealed reaction tank , A tank for adding alkali to a part or all of the separated sludge (precipitation), a pipe for introducing alkaline sludge having a pH of 11 to 13 to the sealed reaction tank, and a ferrous compound in the sealed reaction tank. An organic halide-containing water treatment apparatus comprising: mixing the above-mentioned water and the above alkaline sludge , adjusting the pH to 8.5 to 11 in a non-oxidizing atmosphere to reduce and decompose the organic halide.
6. The treatment apparatus according to claim 5, wherein means for precipitating and removing silicic acid or aluminum contained in the organic halide-containing water is provided in front of the iron compound addition tank.
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| JP2003080074A (en) * | 2001-07-04 | 2003-03-18 | Kawasaki Steel Corp | Iron powder for dehalogenation decomposition of organic halogen compound and method for cleaning soil, water and/or gas |
| JP2003340465A (en) * | 2002-05-30 | 2003-12-02 | Ngk Insulators Ltd | Method for cleaning waste water, groundwater or soil leachate |
| JP2004243222A (en) * | 2003-02-13 | 2004-09-02 | Sumitomo Metal Ind Ltd | Water cleaning agent, cleaning method, and metal recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003080074A (en) * | 2001-07-04 | 2003-03-18 | Kawasaki Steel Corp | Iron powder for dehalogenation decomposition of organic halogen compound and method for cleaning soil, water and/or gas |
| JP2003340465A (en) * | 2002-05-30 | 2003-12-02 | Ngk Insulators Ltd | Method for cleaning waste water, groundwater or soil leachate |
| JP2004243222A (en) * | 2003-02-13 | 2004-09-02 | Sumitomo Metal Ind Ltd | Water cleaning agent, cleaning method, and metal recovery method |
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