JP6239911B2 - Wastewater treatment method and treatment apparatus - Google Patents
Wastewater treatment method and treatment apparatus Download PDFInfo
- Publication number
- JP6239911B2 JP6239911B2 JP2013193790A JP2013193790A JP6239911B2 JP 6239911 B2 JP6239911 B2 JP 6239911B2 JP 2013193790 A JP2013193790 A JP 2013193790A JP 2013193790 A JP2013193790 A JP 2013193790A JP 6239911 B2 JP6239911 B2 JP 6239911B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- phosphoric acid
- waste water
- organic fluorine
- calcium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Treatment Of Biological Wastes In General (AREA)
- Water Treatment By Sorption (AREA)
Description
本発明は、有機フッ素界面活性剤含有排水から有機フッ素界面活性剤を除去する有機フッ素界面活性剤含有排水の処理方法および処理装置に関する。 The present invention relates to a method and apparatus for treating organic fluorine surfactant-containing wastewater that removes organic fluorine surfactant from organic fluorine surfactant-containing wastewater.
有機フッ素界面活性剤はその熱安定性等の特徴から工業分野等で広く使用されている。しかしながら、特にパーフルオロオクタンスルホン酸（ＰＦＯＳ）やパーフルオロオクタン酸（ＰＦＯＡ）は、その化学的な安定性等のため、生態系や環境への影響が問題となり、２０００年以降その使用が規制されてきた。米国ＥＰＡのＰＦＯＡの飲料水質基準（推奨値）は、０．４ｐｐｂ以下とされている。 Organic fluorine surfactants are widely used in industrial fields and the like due to their characteristics such as thermal stability. However, perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), in particular, have an impact on the ecosystem and environment due to their chemical stability, and their use has been regulated since 2000. I came. The drinking water quality standard (recommended value) of PFOA of the US EPA is 0.4 ppb or less.
これまで、一般的に有機フッ素界面活性剤含有排水中の有機フッ素界面活性剤を処理する方法として、微生物による分解（例えば、特許文献１参照）やマイクロバブルによる分解（例えば、特許文献２参照）、活性炭による吸着（例えば、特許文献３参照）等が提案されているが、いずれも設備が大規模であったり、ランニングコストが膨大であったりする問題があり、安価に効率よく処理できる方法が求められている。 Until now, as a method of treating the organic fluorine surfactant in the organic fluorine surfactant-containing wastewater, decomposition by microorganisms (for example, refer to Patent Document 1) or decomposition by microbubbles (for example, refer to Patent Document 2) Adsorption by activated carbon (for example, see Patent Document 3) has been proposed. However, there are problems such as large-scale equipment and enormous running costs. It has been demanded.
活性炭による吸着処理は界面活性剤を除去することは可能であるが、活性炭は有機フッ素界面活性剤に対する吸着容量が小さい。さらに原水中の他の有機物も吸着除去してしまうため、ますます吸着容量が小さくなって、頻繁に活性炭を交換する必要があり、コスト的に不利となる問題がある。 Although the adsorption treatment with activated carbon can remove the surfactant, activated carbon has a small adsorption capacity for the organic fluorine surfactant. Furthermore, since other organic substances in the raw water are also removed by adsorption, the adsorption capacity becomes smaller and the activated carbon needs to be replaced frequently, which is disadvantageous in terms of cost.
本発明の目的は、有機フッ素界面活性剤含有排水から有機フッ素界面活性剤を効率よく除去することが可能な有機フッ素界面活性剤含有排水の処理方法および処理装置を提供することにある。 The objective of this invention is providing the processing method and processing apparatus of the organic fluorine surfactant containing waste water which can remove an organic fluorine surfactant efficiently from the organic fluorine surfactant containing waste water.
本発明は、フッ化物イオンおよび有機フッ素界面活性剤を含有する排水の処理方法であって、前記排水を、リン酸のカルシウム塩と接触させる接触工程と、前記接触させた接触処理水を、活性炭で処理する活性炭処理工程と、を含み、前記接触工程において、前記リン酸のカルシウム塩を充填した充填塔に前記排水を通水する、排水の処理方法である。 The present invention relates to a method for treating waste water containing fluoride ions and an organic fluorine surfactant, wherein the waste water is brought into contact with a calcium salt of phosphoric acid, and the contact treated water thus brought into contact with activated carbon. in the activated carbon treatment step of treating, only including, in said contacting step, passed through the waste water to packed tower filled with calcium salt of phosphoric acid, a method of treating wastewater.
また、前記排水の処理方法において、前記リン酸のカルシウム塩が、リン酸水素カルシウム二水和物であることが好ましい。 Further, in the processing method of the preceding Sharing, ABS water, the calcium salt of the phosphoric acid is preferably calcium hydrogen phosphate dihydrate.
また、本発明は、フッ化物イオンおよび有機フッ素界面活性剤を含有する排水の処理装置であって、前記排水を、リン酸のカルシウム塩と接触させる接触手段と、前記接触させた接触処理水を、活性炭で処理する活性炭処理手段と、を備え、前記接触手段は、前記リン酸のカルシウム塩を充填した充填塔である、排水の処理装置である。 The present invention is also a waste water treatment apparatus containing fluoride ions and an organic fluorine surfactant, wherein the waste water is brought into contact with a calcium salt of phosphoric acid, and the contact treated water brought into contact with the waste water. comprises activated carbon processing means for processing with activated carbon, and said contact means, Ru packed column der packed with calcium salt of phosphoric acid, a waste water treatment apparatus.
また、前記排水の処理装置において、前記リン酸のカルシウム塩が、リン酸水素カルシウム二水和物であることが好ましい。 Further, in the processing apparatus before Sharing, ABS water, the calcium salt of the phosphoric acid is preferably calcium hydrogen phosphate dihydrate.
本発明では、有機フッ素界面活性剤含有排水を、リン酸のカルシウム塩と接触させた後に活性炭で処理することにより、有機フッ素界面活性剤含有排水から有機フッ素界面活性剤を効率よく除去することができる。 In the present invention, the organic fluorine surfactant-containing waste water can be efficiently removed from the organic fluorine surfactant-containing waste water by treating the waste water with the calcium salt of phosphoric acid and then treating with activated carbon. it can.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.
本発明の実施形態に係る排水処理装置の一例の概略を図１に示し、その構成について説明する。排水処理装置１は、接触手段としての接触装置１０と、活性炭処理手段としての活性炭処理装置１２と、を備える。
An outline of an example of a wastewater treatment apparatus according to an embodiment of the present invention is shown in FIG. The waste water treatment apparatus 1 includes a
図１の排水処理装置１において、接触装置１０の入口に原水配管１４が接続され、接触装置１０の出口と活性炭処理装置１２の入口とが接触処理水配管１６により接続され、活性炭処理装置１２の出口に処理水配管１８が接続されている。
In the waste water treatment apparatus 1 of FIG. 1, the
本実施形態に係る有機フッ素界面活性剤含有排水の処理方法および排水処理装置１の動作について説明する。 The treatment method of the organic fluorine surfactant-containing wastewater and the operation of the wastewater treatment apparatus 1 according to this embodiment will be described.
原水である有機フッ素界面活性剤含有排水は、原水配管１４を通して、リン酸のカルシウム塩が充填されたＤ充填塔等の接触装置１０に通液され、リン酸のカルシウム塩と接触される（接触工程）。
The organic fluorine surfactant-containing waste water, which is raw water, is passed through the
接触工程においてリン酸のカルシウム塩と接触された接触処理水は、接触装置１０の出口から接触処理水配管１６を通して、活性炭が充填された活性炭充填塔等の活性炭処理装置１２に通液され、活性炭で処理される（活性炭処理工程）。
The contact treated water that has been contacted with the calcium salt of phosphoric acid in the contacting step is passed through the contact treated
活性炭処理工程において活性炭処理された処理水は、活性炭処理装置１２の出口から処理水配管１８を通して、系外に排出される。
The treated water treated with activated carbon in the activated carbon treatment step is discharged from the system through the treated
本発明者らは、有機フッ素界面活性剤含有排水を、リン酸のカルシウム塩と接触させて前処理し、その後、活性炭で処理することによって、活性炭の寿命が非常に長くなることを見出した。本方法によれば、何ら特殊な装置を用いなくても、有機フッ素界面活性剤含有排水から有機フッ素界面活性剤を効率よく除去することが可能となり、低コストで有機フッ素界面活性剤含有排水の処理が可能となる。 The inventors of the present invention have found that the life of the activated carbon is greatly increased by pretreating the organic fluorine surfactant-containing wastewater with a calcium salt of phosphoric acid and then treating with the activated carbon. According to this method, it is possible to efficiently remove the organic fluorine surfactant from the organic fluorine surfactant-containing wastewater without using any special apparatus, and the organic fluorine surfactant-containing wastewater can be removed at low cost. Processing is possible.
有機フッ素界面活性剤が効率よく除去されるメカニズムは必ずしも明確ではないが、前処理で接触させたリン酸のカルシウム塩から溶出するリン酸やミネラル等が影響して、活性炭が生物活性炭となり、活性炭に吸着した「原水に共存する有機物や界面活性剤」が微生物により分解され、吸着容量が大きくなって、活性炭の寿命が伸びたものと推測される。 The mechanism by which the organic fluorosurfactant is efficiently removed is not always clear, but activated carbon becomes biological activated carbon due to the influence of phosphoric acid and minerals eluted from the calcium salt of phosphoric acid contacted in the pretreatment. It is presumed that the “organic substances and surfactants coexisting in the raw water” adsorbed on the microorganisms are decomposed by microorganisms, the adsorption capacity is increased, and the life of the activated carbon is extended.
これらの微生物としては、Zoogloea sp.やBacillus sp. Pseudomonas sp.等が挙げられるが、これらに限定されない。 Examples of these microorganisms include, but are not limited to, Zoogloea sp. And Bacillus sp. Pseudomonas sp.
処理対象となる原水である有機フッ素界面活性剤含有排水に含まれる有機フッ素界面活性剤としては、例えば、炭素数２以上１２以下のパーフルオロアルキルスルホン酸、パーフルオロアルキルカルボン酸およびその塩類等が挙げられる。本実施形態に係る有機フッ素界面活性剤含有排水の処理方法および処理装置は、活性炭への吸着を特に効果的に行うことができる等の点から、特に、炭素数６〜８のパーフルオロヘキサンスルホン酸、パーフルオロヘキサン酸、パーフルオロヘプタンスルホン酸、パーフルオロヘプタン酸、パーフルオロオクタンスルホン酸、パーフルオロオクタン酸、ω−ヒドロ−パーフルオロヘプタン酸およびその塩類のうち少なくとも１つを含む有機フッ素界面活性剤含有排水の処理に好適に適用される。 Examples of the organic fluorine surfactant contained in the organic fluorine surfactant-containing waste water that is the raw water to be treated include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids and salts thereof having 2 to 12 carbon atoms. Can be mentioned. The treatment method and treatment apparatus for organic fluorine surfactant-containing wastewater according to the present embodiment are particularly suitable for perfluorohexane sulfone having 6 to 8 carbon atoms from the viewpoint that adsorption onto activated carbon can be performed particularly effectively. Organic fluorine interface comprising at least one of acids, perfluorohexanoic acid, perfluoroheptanesulfonic acid, perfluoroheptanoic acid, perfluorooctanesulfonic acid, perfluorooctanoic acid, ω-hydro-perfluoroheptanoic acid and salts thereof It is suitably applied to the treatment of activator-containing wastewater.
有機フッ素界面活性剤含有排水中の有機フッ素界面活性剤の含有量は、例えば、１０ｐｐｂ〜１０００ｐｐｂの範囲である。 The content of the organic fluorine surfactant in the organic fluorine surfactant-containing waste water is, for example, in the range of 10 ppb to 1000 ppb.
有機フッ素界面活性剤含有排水としては、例えば、フッ素化合物製造工場、フッ素製品加工工場、半導体工場の排水等が挙げられる。 Examples of the organic fluorine surfactant-containing wastewater include wastewater from a fluorine compound manufacturing factory, a fluorine product processing factory, and a semiconductor factory.
接触工程における、有機フッ素界面活性剤含有排水と、リン酸のカルシウム塩との接触方法としては、有機フッ素界面活性剤含有排水と、リン酸のカルシウム塩とを接触することができる方法であればよく、特に制限はないが、例えば、充填塔にリン酸のカルシウム塩を充填し、下降流等によって原水を通水する方法や、撹拌槽にリン酸のカルシウム塩を添加し、原水と混合して接触させる方法等が挙げられる。 In the contacting step, the contact method between the organic fluorine surfactant-containing waste water and the phosphoric acid calcium salt is any method that can contact the organic fluorine surfactant-containing waste water and the phosphoric acid calcium salt. Well, there are no particular restrictions, but for example, a method in which a packed column is filled with calcium salt of phosphoric acid and raw water is passed by descending flow, or a calcium salt of phosphoric acid is added to a stirring tank and mixed with raw water. For example.
「リン酸のカルシウム塩」としては、特に制限はないが、例えば、リン酸水素カルシウム二水和物（ＤＣＰＤ）、無水リン酸水素カルシウム、リン酸二水素カルシウム、リン酸カルシウム等が挙げられる。これらのうち、フッ素が除去できる点と、水に対する溶解度等の点から、リン酸水素カルシウム二水和物（ＤＣＰＤ）がより好ましい。 The “calcium phosphate salt” is not particularly limited, and examples thereof include calcium hydrogen phosphate dihydrate (DCPD), anhydrous calcium hydrogen phosphate, calcium dihydrogen phosphate, and calcium phosphate. Among these, calcium hydrogen phosphate dihydrate (DCPD) is more preferable from the viewpoints of removing fluorine and solubility in water.
リン酸水素カルシウム二水和物は、例えば特開２０１０−１７９２４１号公報に記載されているように、通常、水中のフッ素イオンを除去するために用いられるが、単独では有機フッ素界面活性剤を処理することはほとんどできない。 Calcium hydrogen phosphate dihydrate, for example, as described in JP 2010-179241, normally used to remove the water fluorine ions, organic fluorine surfactant alone It can hardly be processed.
リン酸のカルシウム塩としては、粒状等のものを用いることができる。 As a calcium salt of phosphoric acid, granular ones can be used.
リン酸のカルシウム塩としては、リン酸のカルシウム塩と粒子とを含み、リン酸のカルシウム塩が粒子に担持されている処理剤の形態として用いてもよい。リン酸のカルシウム塩が粒子に担持されている処理剤の形態として用いることによって、処理剤に有機フッ素界面活性剤含有排水を透水することで、長期にわたってリン酸のカルシウム塩が実質的に流出せず、長期にわたって透水性に優れ、処理することができる。ここで、担持とは、担体である粒子がリン酸のカルシウム塩を担ぐように支持することをいう。リン酸のカルシウム塩の体積平均粒径（レーザ回折錯乱法により測定）としては、例えば、３０〜７０μｍ程度である。 The calcium phosphate salt may include a calcium salt of phosphoric acid and particles, and may be used in the form of a treatment agent in which the calcium salt of phosphoric acid is supported on the particles. By using the calcium salt of phosphoric acid as a treatment agent supported on the particles, the calcium fluoride salt of phosphoric acid can substantially flow out over a long period of time by allowing wastewater containing an organic fluorine surfactant to flow through the treatment agent. It is excellent in water permeability over a long period of time and can be processed. Here, the term “supporting” refers to supporting the particles as a carrier so as to carry the calcium salt of phosphoric acid. The volume average particle size (measured by the laser diffraction confusion method) of the calcium salt of phosphoric acid is, for example, about 30 to 70 μm.
上記粒子としては、例えば、一般的に水の浄化等に用いられるろ過砂、ろ過砂利等が挙げられるが、これらに限定されるものではない。上記粒子のふるい分け試験（ＪＩＳ Ｚ８８０１）で求められる粒径としては、例えば、０．３〜３．０ｍｍ程度である。 Examples of the particles include, but are not limited to, filtration sand and filtration gravel that are generally used for water purification and the like. The particle size determined by the particle screening test (JIS Z8801) is, for example, about 0.3 to 3.0 mm.
上記処理剤は、粒子１００質量部に対して、リン酸のカルシウム塩が１〜１００質量部の範囲で担持されているものであることが好ましい。上記範囲に設定することによって、リン酸のカルシウム塩が粒子に効率よく担持され、より透水性、処理性に優れる処理剤となる。より好ましくは、粒子１００質量部に対して、リン酸のカルシウム塩が５〜５０質量部の範囲であり、さらに好ましくは、７〜１５質量部の範囲である。 It is preferable that the said processing agent is what the calcium salt of phosphoric acid is carry | supported in the range of 1-100 mass parts with respect to 100 mass parts of particle | grains. By setting the amount within the above range, the calcium salt of phosphoric acid is efficiently supported on the particles, and the treatment agent is more excellent in water permeability and processability. More preferably, the calcium salt of phosphoric acid is in the range of 5 to 50 parts by mass, and more preferably in the range of 7 to 15 parts by mass with respect to 100 parts by mass of the particles.
接触工程における温度は、例えば、０℃〜６０℃の範囲である。 The temperature in a contact process is the range of 0 degreeC-60 degreeC, for example.
活性炭処理工程における、活性炭による接触処理水の処理方法としては、接触処理水と活性炭とを接触することができる方法であればよく、特に制限はないが、例えば、充填塔に活性炭を充填し、下降流等によって接触処理水を通水する方法等が挙げられる。 In the activated carbon treatment step, the treatment method of the contact treated water with activated carbon may be any method that can contact the contact treated water with activated carbon, and is not particularly limited. For example, the packed tower is filled with activated carbon, For example, a method of passing contact-treated water by a downward flow or the like.
活性炭としては、球状活性炭、粒状活性炭、粉末活性炭等が挙げられ、特に制限はないが、ハンドリングしやすい、圧力損失が発生しにくい等の点から、球状活性炭が好ましい。ここで、一般に、球状活性炭とは、球状に成型したもので、例えば均等係数１．４以下のもの等がある。 Examples of the activated carbon include spherical activated carbon, granular activated carbon, powdered activated carbon, and the like. Although there is no particular limitation, spherical activated carbon is preferable from the viewpoint of easy handling and less pressure loss. Here, in general, the spherical activated carbon is formed into a spherical shape, and includes, for example, one having a uniformity coefficient of 1.4 or less.
球状活性炭の市販品としては、オルビーズＱ（オルガノ株式会社製）、球状活性炭ＢＡＣ（株式会社クレハ製）等が挙げられる。粒状活性炭、粉末活性炭の市販品としては、カルゴンカーボンジャパン製ダイヤホープシリーズ等が挙げられる。 Examples of commercially available spherical activated carbon include Olby's Q (manufactured by Organo Corporation), spherical activated carbon BAC (manufactured by Kureha Corporation), and the like. Examples of commercial products of granular activated carbon and powdered activated carbon include the Diamond Hope series manufactured by Calgon Carbon Japan.
活性炭処理工程における温度は、例えば、０℃〜６０℃の範囲である。 The temperature in the activated carbon treatment step is, for example, in the range of 0 ° C to 60 ° C.
リン酸のカルシウム塩と接触させる接触工程の前段側で、原水中の懸濁物質等を除去するために砂ろ過工程等の懸濁物質除去工程を設けてもよい。 In order to remove suspended substances and the like in raw water, a suspended substance removing process such as a sand filtration process may be provided on the upstream side of the contacting process in which the calcium salt of phosphoric acid is brought into contact.
懸濁物質除去工程における処理方法としては、原水中の懸濁物質等を除去することができる方法であればよく、特に制限はないが、例えば、充填塔に砂を充填し、下降流等によって原水を通水する方法等が挙げられる。 The treatment method in the suspended matter removal step is not particularly limited as long as it is a method that can remove suspended matter in raw water, and for example, the packed tower is filled with sand and is moved downward. Examples include a method of passing raw water.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.
＜実施例１＞
図２に示す排水処理装置を用いて、有機フッ素界面活性剤含有排水の処理を行った。図２に示す排水処理装置は、接触装置１０と、活性炭処理装置１２と、を備え、接触装置１０の前段側に懸濁物質除去手段として砂ろ過装置（砂ろ過塔）２０を備える。
<Example 1>
The wastewater treatment apparatus shown in FIG. 2 was used to treat organic fluorine surfactant-containing wastewater. The wastewater treatment apparatus shown in FIG. 2 includes a
［処理条件］
原水：フッ素化学製造工程排水（パーフルオロオクタン酸（ＰＦＯＡ）含有）
原水流量：２ｍ３／ｈ
原水ＰＦＯＡ濃度：１８０〜３１０ｐｐｂ
砂ろ過塔：φ１２００ｍｍ
砂ろ過塔充填剤：砂４４０Ｌ、アンスラサイト５７０Ｌ
リン酸水素カルシウム二水和物（ＤＣＰＤ）充填塔：φ１６００ｍｍ
ＤＣＰＤ充填塔充填剤：リン酸水素カルシウム二水和物（新田ゼラチン株式会社製）含有充填剤 ４３２０Ｌ
活性炭塔：φ１２００ｍｍ
活性炭：オルガノ株式会社製、オルビーズＱ １４４０Ｌ
温度：１５〜２５℃
[Processing conditions]
Raw water: Fluorine chemical production process wastewater (containing perfluorooctanoic acid (PFOA))
Raw water flow rate: 2m 3 / h
Raw water PFOA concentration: 180-310ppb
Sand filtration tower: φ1200mm
Sand filter tower filler: Sand 440L, Anthracite 570L
Calcium hydrogen phosphate dihydrate (DCPD) packed tower: φ1600mm
DCPD packed tower filler: calcium hydrogen phosphate dihydrate (Nitta Gelatin Co., Ltd.) containing filler 4320L
Activated carbon tower: φ1200mm
Activated carbon: manufactured by Organo Corporation, Olby's Q 1440L
Temperature: 15-25 ° C
なお、リン酸水素カルシウム二水和物含有充填剤およびリン酸水素カルシウム二水和物（ＤＣＰＤ）充填塔は、以下のようにして作製した。傾胴型重力式ミキサ（容量１１０Ｌ）に、急速ろ過用砂（トーケミ製、「日本水道協会規格 ＪＷＷＡ Ａ１０３−１：２００４規格品、有効径：０．６ｍｍ、均等係数：１．５以下、最大径２．８ｍｍ以下、最小径０．３ｍｍ以上」）およびリン酸水素カルシウム二水和物（ＤＣＰＤ）の粉末（平均粒径：５４μｍ）の合計１００質量部当たり、急速ろ過用砂を９０質量部、ＤＣＰＤを１０質量部の割合で投入し、３分間混合を行った。ガラス製カラム筐体に、上記混合により得られた急速ろ過用砂とＤＣＰＤとの混合物およびガラスウールを充填して、ＤＣＰＤ充填塔とした。 In addition, the calcium hydrogen phosphate dihydrate-containing filler and the calcium hydrogen phosphate dihydrate (DCPD) packed tower were prepared as follows. Tilting cylinder type gravity mixer (capacity 110L), sand for rapid filtration (made by Tochemi, “Japan Waterworks Association Standard JWWA A103-1: 2004 standard product, effective diameter: 0.6 mm, uniformity coefficient: 1.5 or less, maximum 90 parts by mass of sand for rapid filtration per 100 parts by mass of powder (average particle size: 54 μm) of 2.8 mm or less diameter and minimum diameter of 0.3 mm or more ”) and calcium hydrogen phosphate dihydrate (DCPD) powder (average particle size: 54 μm) DCPD was added at a rate of 10 parts by mass and mixed for 3 minutes. A glass column housing was filled with a mixture of sand for rapid filtration obtained by the above mixing and DCPD and glass wool to obtain a DCPD packed tower.
処理結果を図４に示す。また、通水１０００時間後の、各塔出口の水質分析結果を表１に示す。なお、表１に示す水質分析のうち、有機フッ素界面活性剤の分析は、ＡＢＳＣＩＥＸ（エービーサイエックス）社製ＬＣ−ＭＳ／ＭＳシステムを用いて行った。その他の成分は、イオンクロマト等の一般的な方法で行った。 The processing results are shown in FIG. Table 1 shows the results of water quality analysis at the exit of each tower after 1000 hours of water flow. In addition, among the water quality analysis shown in Table 1, the analysis of the organic fluorine surfactant was performed using an LC-MS / MS system manufactured by ABSCIEX. Other components were performed by a general method such as ion chromatography.
＜比較例１＞
図３に示す排水処理装置を用いた以外は、実施例１と同様にして、有機フッ素界面活性剤含有排水の処理を行った。図３に示す排水処理装置は、活性炭処理装置３２を備え、活性炭処理装置３２の前段側に懸濁物質除去手段として砂ろ過装置（砂ろ過塔）３０を備える。処理結果を図４に示す。
<Comparative Example 1>
Exhaust water containing an organic fluorine surfactant was treated in the same manner as in Example 1 except that the waste water treatment apparatus shown in FIG. 3 was used. The waste water treatment apparatus shown in FIG. 3 includes an activated
＜実施例２＞
図２に示す排水処理装置を用いて、有機フッ素界面活性剤含有排水の処理を行った。
<Example 2>
The wastewater treatment apparatus shown in FIG. 2 was used to treat organic fluorine surfactant-containing wastewater.
［処理条件］
原水：フッ素化学製造工程排水（ω−ヒドロ−パーフルオロヘプタン酸含有）
原水流量：２ｍ３／ｈ
原水パーフルオロヘプタン酸濃度：５６０〜８００ｐｐｂ
[Processing conditions]
Raw water: Fluorine chemical production process wastewater (ω-hydro-perfluoroheptanoic acid included)
Raw water flow rate: 2m 3 / h
Raw water perfluoroheptanoic acid concentration: 560-800 ppb
その他の条件は実施例１と同様である。処理結果を図５に示す。また、通水１０００時間後の、各塔出口の水質分析結果を表２に示す。 Other conditions are the same as in the first embodiment. The processing result is shown in FIG. Table 2 shows the results of water quality analysis at the outlet of each tower after 1000 hours of water flow.
＜比較例２＞
図３に示す排水処理装置を用いた以外は、実施例２と同様にして、有機フッ素界面活性剤含有排水の処理を行った。処理結果を図５に示す。
<Comparative example 2>
Exhaust water containing an organic fluorine surfactant was treated in the same manner as in Example 2 except that the waste water treatment apparatus shown in FIG. 3 was used. The processing result is shown in FIG.
＜実施例３＞
図２に示す排水処理装置を用いて、有機フッ素界面活性剤含有排水の処理を行った。
<Example 3>
The wastewater treatment apparatus shown in FIG. 2 was used to treat organic fluorine surfactant-containing wastewater.
［処理条件］
原水：フッ素化学製造工程排水（パーフルオロヘキサン酸含有）
原水流量：２ｍ３／ｈ
原水パーフルオロヘキサン酸濃度：７〜１５ｐｐｂ
[Processing conditions]
Raw water: Fluorine chemical manufacturing process wastewater (containing perfluorohexanoic acid)
Raw water flow rate: 2m 3 / h
Raw water perfluorohexanoic acid concentration: 7-15ppb
その他の条件は実施例１と同様である。処理結果を図６に示す。また、通水１０００時間後の、各塔出口の水質分析結果を表３に示す。 Other conditions are the same as in the first embodiment. The processing result is shown in FIG. Table 3 shows the results of water quality analysis at the outlet of each tower after 1000 hours of water flow.
＜比較例３＞
図３に示す排水処理装置を用いた以外は、実施例３と同様にして、有機フッ素界面活性剤含有排水の処理を行った。処理結果を図６に示す。
<Comparative Example 3>
Exhaust water containing an organic fluorine surfactant was treated in the same manner as in Example 3 except that the waste water treatment apparatus shown in FIG. 3 was used. The processing result is shown in FIG.
このように、有機フッ素界面活性剤含有排水を、リン酸のカルシウム塩と接触させた後に活性炭で処理することにより、有機フッ素界面活性剤含有排水から有機フッ素界面活性剤を効率よく除去することができた。 In this way, the organic fluorine surfactant-containing wastewater can be efficiently removed from the organic fluorine surfactant-containing wastewater by treating the wastewater containing the organic fluorine surfactant with the calcium salt of phosphoric acid and then treating with activated carbon. did it.
１ 排水処理装置、１０ 接触装置、１２，３２ 活性炭処理装置、１４ 原水配管、１６ 接触処理水配管、１８ 処理水配管、２０，３０ 砂ろ過装置。 DESCRIPTION OF SYMBOLS 1 Waste water treatment apparatus, 10 Contact apparatus, 12, 32 Activated carbon treatment apparatus, 14 Raw water piping, 16 Contact treated water piping, 18 Treated water piping, 20, 30 Sand filtration apparatus.
Claims (4)
前記排水を、リン酸のカルシウム塩と接触させる接触工程と、
前記接触させた接触処理水を、活性炭で処理する活性炭処理工程と、
を含み、
前記接触工程において、前記リン酸のカルシウム塩を充填した充填塔に前記排水を通水することを特徴とする排水の処理方法。 A wastewater treatment method containing fluoride ions and an organic fluorine surfactant,
Contacting the waste water with a calcium salt of phosphoric acid;
An activated carbon treatment step of treating the contact treated water with the activated carbon,
Only including,
In the contacting step, the waste water is passed through a packed tower filled with the calcium salt of phosphoric acid .
前記リン酸のカルシウム塩が、リン酸水素カルシウム二水和物であることを特徴とする排水の処理方法。 A wastewater treatment method according to claim 1,
The method for treating waste water, wherein the calcium salt of phosphoric acid is calcium hydrogen phosphate dihydrate.
前記排水を、リン酸のカルシウム塩と接触させる接触手段と、
前記接触させた接触処理水を、活性炭で処理する活性炭処理手段と、
を備え、
前記接触手段は、前記リン酸のカルシウム塩を充填した充填塔であることを特徴とする排水の処理装置。 A wastewater treatment apparatus containing fluoride ions and an organic fluorine surfactant,
Contact means for contacting the waste water with a calcium salt of phosphoric acid;
Activated carbon treatment means for treating the contact treated water with the activated carbon,
Equipped with a,
It said contact means, wastewater treatment device according to claim packed column der Rukoto packed with calcium salts of the phosphoric acid.
前記リン酸のカルシウム塩が、リン酸水素カルシウム二水和物であることを特徴とする排水の処理装置。 A wastewater treatment apparatus according to claim 3 ,
An apparatus for treating waste water, wherein the calcium salt of phosphoric acid is calcium hydrogen phosphate dihydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013193790A JP6239911B2 (en) | 2013-09-19 | 2013-09-19 | Wastewater treatment method and treatment apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013193790A JP6239911B2 (en) | 2013-09-19 | 2013-09-19 | Wastewater treatment method and treatment apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015058398A JP2015058398A (en) | 2015-03-30 |
| JP6239911B2 true JP6239911B2 (en) | 2017-11-29 |
Family
ID=52816363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013193790A Active JP6239911B2 (en) | 2013-09-19 | 2013-09-19 | Wastewater treatment method and treatment apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6239911B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7824914B2 (en) * | 2023-08-10 | 2026-03-05 | 野村マイクロ・サイエンス株式会社 | Pure water production method and production equipment, pure water production method and pure water production system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02191543A (en) * | 1989-01-19 | 1990-07-27 | Agency Of Ind Science & Technol | Method for removing fluoride ion |
| JP2000202445A (en) * | 1999-01-13 | 2000-07-25 | Kurita Water Ind Ltd | Method of treating recovered water from semiconductor manufacturing process containing fluoride ions |
| JP4132436B2 (en) * | 1999-07-09 | 2008-08-13 | アタカ大機株式会社 | Method and apparatus for treating volatile organochlorine compounds |
| JP3969185B2 (en) * | 2002-05-24 | 2007-09-05 | 栗田工業株式会社 | Pure water production equipment |
| JP4821173B2 (en) * | 2005-05-20 | 2011-11-24 | 日本錬水株式会社 | Treatment method for waste water containing fluoride ions |
| JP4703370B2 (en) * | 2005-11-02 | 2011-06-15 | オルガノ株式会社 | Nitrogen-containing wastewater treatment method |
| JP3974929B1 (en) * | 2006-06-07 | 2007-09-12 | シャープ株式会社 | Waste water treatment method and waste water treatment equipment |
-
2013
- 2013-09-19 JP JP2013193790A patent/JP6239911B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015058398A (en) | 2015-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yao et al. | Effective adsorption/electrocatalytic degradation of perchlorate using Pd/Pt supported on N-doped activated carbon fiber cathode | |
| Zhang et al. | Sorption characteristics and mechanisms of ammonium by coal by-products: slag, honeycomb-cinder and coal gangue | |
| CN105849038B (en) | The refining methd of the production method and aqueous hydrogen peroxide solution of anion exchanger and cation exchange column mixture and mixed bed | |
| TWI540103B (en) | Method for removing boron from a boron-containing wastewater | |
| EP2792645B1 (en) | Process for removing fluorides from water | |
| JPH1085743A (en) | Method and apparatus for treating water containing boron | |
| CN110330164A (en) | A kind of method of alkalinity high fluorine Sewage treatment fluorine resource and sodium resource with high salt | |
| Stanley et al. | Biosorption of copper (II) from chemical mechanical planarization wastewaters | |
| Li et al. | Biosorption of copper ion by natural and modified wheat straw in fixed-bed column | |
| Li et al. | A combined precipitation-adsorption method for harmless treatment of glyphosate mother liquor | |
| WO2013136677A1 (en) | Ammoniacal nitrogen and phosphorus recovery agent and method for producing same | |
| Wei et al. | Co-removal of phosphorus and nitrogen with commercial 201× 7 anion exchange resin during tertiary treatment of WWTP effluent and phosphate recovery | |
| JP6239911B2 (en) | Wastewater treatment method and treatment apparatus | |
| Kołodyńska | Cu (II), Zn (II), Ni (II), and Cd (II) complexes with HEDP removal from industrial effluents on different ion exchangers | |
| Ding et al. | Adsorptive removal of gallic acid from aqueous solution onto magnetic ion exchange resin | |
| Gil et al. | Removal of tetrachloroethylene from aqueous solutions by adsorption on clay minerals | |
| Tinas et al. | Preparation of Fe $ _ {3} $ O $ _ {4} $@ montmorillonite composite as an effective sorbent for the removal of lead and cadmium from wastewater samples | |
| Konga et al. | Studies o n removal of Cu2+ from effluent water by using rice husk | |
| JP5311227B2 (en) | Anion exchanger, its pretreatment method and regeneration method, and purification method and purification apparatus of alkaline aqueous solution | |
| WO2008069136A1 (en) | Method for purifying chemical added with chelating agent | |
| Cao et al. | ZnO/PUF composites with a large capacity for phosphate adsorption: adsorption behavior and mechanism studies | |
| Ahmari et al. | Removal of Cu (II) from aqueous solution using dried activated sludge and dried activated nano-sludge: adsorption on a fixed bed column | |
| JP4956905B2 (en) | Method and apparatus for treating fluorine-containing water containing TOC component | |
| Pal et al. | Effective removal of brilliant green dye from aqueous solution by adsorption onto biopolymer supported silver nanoparticles beads | |
| Senthil Kumar et al. | Kinetics and adsorption equilibrium in the system aqueous solution of copper ions—granulated activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160616 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170322 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170328 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170529 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170613 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170814 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171017 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171102 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6239911 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |