JP4277736B2 - Method for treating water containing organic arsenic compound - Google Patents
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- JP4277736B2 JP4277736B2 JP2004156490A JP2004156490A JP4277736B2 JP 4277736 B2 JP4277736 B2 JP 4277736B2 JP 2004156490 A JP2004156490 A JP 2004156490A JP 2004156490 A JP2004156490 A JP 2004156490A JP 4277736 B2 JP4277736 B2 JP 4277736B2
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本発明は、ジフェニルアルシン酸のような有機ヒ素化合物を含む水の処理方法に関する。 The present invention relates to a method for treating water containing an organic arsenic compound such as diphenylarsinic acid.
ジフェニルアルシン酸は毒性を有しているためその水溶液を環境中へ廃棄する場合にはこの化合物を分解処理する必要がある。またジフェニルアルシン酸はBaeyer-Villiger反応やエポキシ化反応の触媒として合成され、触媒反応で生じる廃液はジフェニルアルシン酸含有水となる。ジフェニルアルシン酸自体は水中で安定な有機化合物であり、次亜塩素酸ナトリウム、次亜塩素酸カルシウム等の塩素系酸化剤ではほとんど分解しない。 Since diphenylarsinic acid has toxicity, it is necessary to decompose this compound when the aqueous solution is discarded into the environment. Diphenylarsinic acid is synthesized as a catalyst for the Baeyer-Villiger reaction or epoxidation reaction, and the waste liquid generated by the catalytic reaction becomes diphenylarsinic acid-containing water. Diphenylarsinic acid itself is an organic compound that is stable in water, and hardly decomposes with chlorine-based oxidizing agents such as sodium hypochlorite and calcium hypochlorite.
ジフェニルアルシン酸のような有機ヒ素化合物の分解方法として、特定の金属イオンの存在下に、該化合物に過酸化水素を反応させる方法が提案されている（特許文献１参 照）。しかし、この方法では処理後の反応液中の残留濃度が不明確である。また、処理すべき有機ヒ素化合物含有水が多量である場合、その全量を加熱するのに多大なエネルギーが必要となり、この方法は地下水汚染等の大量水の処理にはコスト高となり不向きである。
本発明の課題は、分解工程における加熱操作の排除、液体薬剤の不使用により、特許文献１の方法に比べ、より簡素な有機ヒ素化合物の分解工程を提供することである。
The subject of this invention is providing the simpler decomposition | disassembly process of an organic arsenic compound compared with the method of
本発明のもう一つの課題は、浄化指針として処理水中の有機ヒ素化合物濃度を確実に０．００１ｍｇ／Ｌ（ヒ素として）以下にすることである。 Another object of the present invention is to ensure that the concentration of the organic arsenic compound in the treated water is 0.001 mg / L (as arsenic) or less as a purification guideline.
本発明者らは、水中ダイオキシン類の分解方法として従来用いられている、対象水質に対し紫外線を照射しながらオゾンガスを吹き込む技術を有機ヒ素化合物含有水に適用したところ、同化合物を高度に分解できること、および、分解生成物である無機ヒ素化合物の除去処理が効率的に達成出来ることを見出し、本発明を完成した。 The inventors of the present invention applied a technique for blowing ozone gas while irradiating ultraviolet rays to the target water quality, which is conventionally used as a method for decomposing dioxins in water. And it discovered that the removal process of the inorganic arsenic compound which is a decomposition product can be achieved efficiently, and completed this invention.
本発明による有機ヒ素化合物含有水の処理方法は、有機ヒ素化合物含有水に対し紫外線を照射しながらオゾンガスを吹き込み、有機ヒ素化合物を無機ヒ素化合物に分解し、その後に、ポリ硫酸第二鉄と中アニオン系高分子凝集剤を加えて分解生成物である無機ヒ素化合物を静沈する操作を２回繰り返し行うことを特徴とする方法である。
In the method for treating water containing organic arsenic compound according to the present invention, ozone gas is blown into the organic arsenic compound-containing water while irradiating the organic arsenic compound-containing water to decompose the organic arsenic compound into an inorganic arsenic compound , and thereafter, polyferric sulfate and medium This is a method characterized by repeating the operation of adding an anionic polymer flocculant and allowing the inorganic arsenic compound as a decomposition product to settle down twice .
紫外線照射およびオゾンガス吹き込みの前に、凝集剤により有機ヒ素化合物含有水中の不溶性懸濁物を除去しておくことが好ましい。 Before the ultraviolet irradiation and ozone gas blowing, it is preferable to remove the insoluble suspension in the organic arsenic compound-containing water with a flocculant.
有機ヒ素化合物は例えばジフェニルアルシン酸である。 The organic arsenic compound is, for example, diphenylarsinic acid.
オゾンガスは純オゾンガスの外、オゾン含有ガスであってもよい。 The ozone gas may be ozone-containing gas in addition to pure ozone gas.
本発明によれば、分解工程における加熱操作の排除、液体薬剤の不使用により、簡素な方法で有機ヒ素化合物含有水を処理することができる。 According to the present invention, organic arsenic compound-containing water can be treated by a simple method by eliminating the heating operation in the decomposition step and not using a liquid medicine.
また、処理水中の有機ヒ素化合物濃度を確実に０．００１ｍｇ／Ｌ（ヒ素として）以下にすることができ、全ヒ素化合物濃度も飲料水基準の０．０１ｍｇ／Ｌ（ヒ素として）以下に抑えることができる。 In addition, the concentration of the organic arsenic compound in the treated water can be reliably reduced to 0.001 mg / L (as arsenic) or less, and the total arsenic compound concentration is also suppressed to 0.01 mg / L (as arsenic) or less based on drinking water. Can do.
図１は本発明方法において使用される装置の一例である。この装置は、反応塔(1)と、反応塔(1) 内に垂直に配された紫外線ランプ(2) と、反応塔(1) の塔底壁にオゾンガスを送り込むためのオゾン発生器(3) と、反応塔(1) の底部一側に被処理液を供給するための被処理液タンク(4) と、反応塔(1) の塔頂から排出されるガスを処理する活性炭塔(5) と、反応塔(1) の頂部から排出される処理液に三価鉄塩およひ疑集剤をそれぞれ供給する三価鉄塩タンク(6) およひ疑集剤タンク(7) と、処理液中の凝集物を除去するための凝集沈殿槽(8) とから主として構成されている。 FIG. 1 is an example of an apparatus used in the method of the present invention. This apparatus consists of a reaction tower (1), an ultraviolet lamp (2) arranged vertically in the reaction tower (1), and an ozone generator (3) for sending ozone gas to the bottom wall of the reaction tower (1). ), A liquid tank (4) for supplying the liquid to be treated to one side of the bottom of the reaction tower (1), and an activated carbon tower (5) for treating the gas discharged from the top of the reaction tower (1). ), And a trivalent iron salt tank (6) and a suspect agent tank (7) for supplying the trivalent iron salt and the suspected agent to the treatment liquid discharged from the top of the reaction tower (1), respectively. And a coagulation sedimentation tank (8) for removing aggregates in the treatment liquid.
被処理液は事前に凝集沈殿処理され、固形分を除去しておくことが望ましい。被処理液タンク(4) 内の被処理液は反応塔(1) の底部へ送られ、反応塔(1) 内を上昇する間に、紫外線ランプ(2) により紫外線照射され、オゾン発生器(3) から送られ液中をバブリングするオゾンガスと接触させられる。オゾンガスの最適注入率は通常１００〜３０００ｍｇ／Ｌであるが、被処理水に含まれる有機成分の量によって異なる。 It is desirable that the liquid to be treated be coagulated and precipitated in advance to remove the solid content. The liquid to be treated in the liquid tank (4) is sent to the bottom of the reaction tower (1) and irradiated with ultraviolet rays from the ultraviolet lamp (2) while rising in the reaction tower (1), and the ozone generator ( 3) Contacted with ozone gas that is sent from and bubbling in the liquid. The optimum injection rate of ozone gas is usually 100 to 3000 mg / L, but varies depending on the amount of organic components contained in the water to be treated.
反応塔(1) 内でジフェニルアルシン酸は紫外線照射およびオゾンガス吹き込みにより無機ヒ素、主に五価の酸化ヒ素（ヒ酸）に分解される。反応塔(1) から排出された処理水に三価の鉄塩であるポリ硫酸第二鉄を三価鉄塩タンク(6) から加えることにより、ヒ酸は不溶性のヒ酸鉄を形成する。次いで処理水に疑集剤タンク(7) から高分子疑集剤を加え、その後凝集沈殿槽(8) において不溶性のヒ酸鉄を処理水から除去する。ヒ酸は三価の酸化ヒ素（亜ヒ酸）に比べ三価の鉄イオンと容易に反応するため、本方法は三価の酸化ヒ素を含む一般のヒ素含有排水の処理に比べ高度に無機ヒ素の除去を行うことができる。反応塔(1) の塔頂から排出されるガスは活性炭塔(5) で処理される。 In the reaction tower (1), diphenylarsinic acid is decomposed into inorganic arsenic, mainly pentavalent arsenic oxide (arsenic acid) by ultraviolet irradiation and ozone gas blowing. Arsenic acid forms insoluble iron arsenate by adding ferric sulfate, which is a trivalent iron salt, to the treated water discharged from the reaction tower (1) from the trivalent iron salt tank (6). Next, the polymer suspect agent is added to the treated water from the suspect agent tank (7), and then insoluble iron arsenate is removed from the treated water in the coagulation sedimentation tank (8). Since arsenic reacts more easily with trivalent iron ions than trivalent arsenic oxide (arsenous acid), this method is highly inorganic arsenic compared to the treatment of general arsenic-containing wastewater containing trivalent arsenic oxide. Can be removed. The gas discharged from the top of the reaction tower (1) is treated in the activated carbon tower (5).
つぎに、本発明を具体的に説明するために、本発明の実施例を挙げる。 Next, in order to describe the present invention specifically, examples of the present invention will be given.
実施例１
ジフェニルアルシン酸を含む地下水を対象試料とし、これにポリ硫酸第二鉄３００ｍｇ／Ｌを加え、５Ｎ−ＮａＯＨによりｐＨを７に調整した。その後この試料に中アニオン系高分子凝集剤を加えて撹件し、静沈した。静沈後の上澄み液中のジフェニルアルシン酸濃度は２１ｍｇ／Ｌ（ヒ素として）であった。
Example 1
Groundwater containing diphenylarsinic acid was used as a target sample, 300 mg / L of polyferric sulfate was added thereto, and the pH was adjusted to 7 with 5N NaOH. Thereafter, a medium anionic polymer flocculant was added to the sample and the mixture was stirred and allowed to settle. The concentration of diphenylarsinic acid in the supernatant after static precipitation was 21 mg / L (as arsenic).
その後、上澄み液を紫外線ランプおよびオゾン発生器を備えた反応塔に入れ、紫外線ランプを点灯し、直にオゾン供給を２ｇ／ｈの速度で開始した。オゾン供給開始から１時間後、２時間後および４時間後における反応液中ジフェニルアルシン酸および全ヒ素の濃度を測定した。なおジフェニルアルシン酸はＬＣ−ＭＳ／ＭＳ法、全ヒ素はＩＣＰ／ＭＳ法により厳密に測定した。 Thereafter, the supernatant liquid was put into a reaction tower equipped with an ultraviolet lamp and an ozone generator, the ultraviolet lamp was turned on, and ozone supply was immediately started at a rate of 2 g / h. The concentrations of diphenylarsinic acid and total arsenic in the reaction solution were measured 1 hour, 2 hours and 4 hours after the start of ozone supply. Diphenylarsinic acid was strictly measured by LC-MS / MS method, and total arsenic was measured by ICP / MS method.
その結果、１時間、２時間および４時間反応後の反応液中ジフェニルアルシン酸濃度はそれぞれ０．００５４ｍｇ／Ｌ、０．０００７ｍｇ／Ｌ、０．００００３ｍｇ／Ｌまで減少し、ジフェニルアルシン酸は非常に低濃度まで分解できることがわかった。 As a result, the concentrations of diphenylarsinic acid in the reaction solution after the reaction for 1 hour, 2 hours and 4 hours were decreased to 0.0054 mg / L, 0.0007 mg / L and 0.00003 mg / L, respectively, and diphenylarsinic acid had a very low concentration. It was found that it can be decomposed.
実施例１の結果を表１に示す。
実施例２
紫外線照射とオゾン供給による２時間処理後、処理水にポリ硫酸第二鉄を３４０ｍｇ／Ｌ加え、ＮａＯＨによりｐＨを７に調整し、次いで処理水に中アニオン系高分子凝集剤を加えて撹拌し、静沈し、上澄み水中の全ヒ素濃度を測定した。次いで上澄み水に対し再度同量のポリ硫酸第二鉄、５Ｎ−ＮａＯＮおよび中アニオン系高分子凝集剤を加え、全体を撹拌し、静沈し、上記と同じように上澄み水中のヒ素濃度を測定した。
Example 2
After 2 hours of treatment with UV irradiation and ozone supply, add 340 mg / L of polyferric sulfate to the treated water, adjust the pH to 7 with NaOH, then add the medium anionic polymer flocculant to the treated water and stir. The total arsenic concentration in the supernatant water was measured. Next, add the same amount of ferric sulfate, 5N-NaON and medium anionic polymer flocculant to the supernatant water again, stir the whole, settle down, and measure the arsenic concentration in the supernatant water as above. did.
その結果、２９ｍｇ／Ｌという高濃度ヒ素含有水に対し、上記条件の処理１回で０．０２９ｍｇ／Ｌにまでヒ素濃度を減少させ、さらにもう一回上記条件の処理を行うと０．００６０ｍｇ／Ｌという極低濃度に全ヒ素濃度を低減することができた。 As a result, when the arsenic concentration was reduced to 0.029 mg / L in one treatment of the above conditions with respect to high concentration arsenic-containing water of 29 mg / L, and the treatment under the above conditions was performed once more, 0.0060 mg / L The total arsenic concentration could be reduced to an extremely low concentration of L.
この結果により、試料中に含まれるジフェニルアルシン酸以外の構造不明のヒ素化含物も紫外線照射とオゾン供給による処理により三価の鉄イオンと反応し易い無機ヒ素化合物に変換していることが証明された。 This result proves that arsenic inclusions of unknown structure other than diphenylarsinic acid contained in the sample have also been converted into inorganic arsenic compounds that react easily with trivalent iron ions by treatment with ultraviolet irradiation and ozone supply. It was.
実施例２の結果を表２に示す。
(1) 反応塔
(2) 紫外線ランプ
(3) オゾン発生器
(4) 被処理液タンク
(5) 活性炭塔
(6) 三価鉄塩タンク
(7) 疑集剤タンク
(8) 凝集沈殿槽
(1) Reaction tower
(2) UV lamp
(3) Ozone generator
(4) Liquid tank to be treated
(5) Activated carbon tower
(6) Trivalent iron salt tank
(7) Suspect agent tank
(8) Coagulation sedimentation tank
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| JP2004156490A JP4277736B2 (en) | 2004-05-26 | 2004-05-26 | Method for treating water containing organic arsenic compound |
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| JP4277736B2 true JP4277736B2 (en) | 2009-06-10 |
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| KR100734900B1 (en) * | 2004-10-18 | 2007-07-03 | 가부시끼가이샤 아스텍 | The treatment method for organoarsenic contained water |
| US8148134B2 (en) | 2006-09-01 | 2012-04-03 | Kowa Company, Ltd. | Microorganism capable of degrading diphenylarsinic acid |
| JP4697188B2 (en) * | 2007-05-30 | 2011-06-08 | 日立造船株式会社 | Method for treating water containing organic arsenic compound |
| CN101898855B (en) * | 2010-07-16 | 2012-02-29 | 华东理工大学 | Integrated ex-situ repair system for underground water polluted by volatile organic compound |
| JP5749521B2 (en) * | 2011-03-01 | 2015-07-15 | エア・ウォーター株式会社 | Waste water treatment apparatus and method |
| CN107055678A (en) * | 2017-04-26 | 2017-08-18 | 陕西朗正环保科技有限公司 | A kind of triphase catalytic oxidation sewage water treatment method and reactor |
| CN111298770B (en) * | 2019-12-18 | 2022-07-05 | 沈阳化工大学 | Method for simultaneously purifying organic arsenic and inorganic arsenic composite polluted wastewater |
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| JPH09225482A (en) * | 1996-02-20 | 1997-09-02 | Ebara Corp | Treatment of hardly decomposable organic material-containing waste water |
| JP2001158622A (en) * | 1999-11-30 | 2001-06-12 | Jgc Corp | Method of treating organoarsenic compound |
| JP4598415B2 (en) * | 2004-02-27 | 2010-12-15 | オルガノ株式会社 | Organic arsenic compound processing method |
| JP2005279409A (en) * | 2004-03-29 | 2005-10-13 | Kubota Corp | Treatment method of organometallic compound-containing waste water |
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