JP2006075759A - Wastewater purifying treatment material and treatment method - Google Patents
Wastewater purifying treatment material and treatment method Download PDFInfo
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Abstract
Description
本発明は、排水に含まれる重金属の除去効果と経済性に優れた排水浄化処理材と、この処理材を用いた浄化処理方法に関する。より詳しくは、常温で使用され、使用方法が簡単であって排水に含まれる重金属の除去効果と経済性に優れた排水浄化処理材と、この処理材を用いた浄化処理方法に関する。 The present invention relates to a wastewater purification treatment material excellent in removal effect and economical efficiency of heavy metals contained in wastewater, and a purification treatment method using this treatment material. More specifically, the present invention relates to a wastewater purification treatment material that is used at room temperature, has a simple usage method, and is excellent in the removal effect and economical efficiency of heavy metals contained in wastewater, and a purification treatment method using this treatment material.
排水中の重金属を除去する手段として、キレート剤に重金属を吸着させる方法や、水酸化物や硫化物の沈澱を生成させ、この沈澱に重金属を取り込ませて共沈させる方法、排水に鉄粉を加えて重金属を沈澱させる方法などが知られている。しかし、キレート剤を用いる方法はキレート剤が高価であるため経済性に劣る、また、キレート剤は還元性がないため重金属の無害化が不十分である。さらにキレート剤が処理水中に残留する可能性がある。 As a means of removing heavy metals in the wastewater, a method of adsorbing heavy metals to the chelating agent, a method of generating precipitates of hydroxides and sulfides, taking heavy metals into the precipitates, and coprecipitation, iron powder in the wastewater In addition, methods for precipitating heavy metals are known. However, the method using a chelating agent is inferior in economic efficiency because the chelating agent is expensive, and the chelating agent is not reducible, so that detoxification of heavy metals is insufficient. In addition, chelating agents may remain in the treated water.
一方、水酸化物や硫化物の沈澱を生成させる方法は、凝集剤を必要とし、シックナーによる凝集沈降分離や、スラッジの脱水処理などの負担が大きい。また、良好な固液分離を行うために共沈剤を必要とするためにスラッジ量が増大すると云う問題がある。また、澱物の脱水性が悪いために澱物処理の負担が大きいと云う問題がある。 On the other hand, the method of generating precipitates of hydroxides and sulfides requires a flocculant and has a heavy burden such as coagulation sedimentation separation by thickener and sludge dehydration treatment. In addition, there is a problem that the amount of sludge increases because a coprecipitation agent is required to perform good solid-liquid separation. Moreover, there is a problem that the burden of starch treatment is large because the dehydrating property of starch is poor.
水酸化物沈澱を利用する他の方法として、繊維状の基材表面に金属水酸化物のゲル状沈殿物を保持させた付着材を充填した層に排水等を通じて、排水等に含まれる微粒子を吸着させる処理方法が知られている（特許文献１：特開平５−２９３３１６号公報）。この方法によれば、排水等に含まれる一部の溶存成分、例えば、カドミウム、ヒ素、水銀等の有害金属イオンや高分子凝集剤なども吸着できると説明されている。しかし、この方法では配位結合的な吸着力を利用しているため吸着力ないし吸着容量が十分ではないと云う問題がある。
本発明は、従来の排水処理方法における上記問題を解決したものであり、排水等に含まれる重金属の除去効果に優れており、かつメンテナンスが容易であって経済性に優れた排水浄化処理材とその処理方法を提供するものである。 The present invention solves the above-mentioned problems in conventional wastewater treatment methods, is excellent in the effect of removing heavy metals contained in wastewater, etc., and is easy to maintain and economical in wastewater purification treatment material The processing method is provided.
本発明は以下の構成からなる排水浄化処理材とその処理方法に関する。
（１）繊維状物質の表面を硫化鉄によって被覆し、該硫化鉄を繊維状物質に担持させてなることを特徴とする排水浄化処理材。
（２）繊維状物質を２価鉄の塩類を含む水溶液に浸し、硫化物を添加して繊維状物質表面に硫化鉄を析出させてなる上記(1)の排水浄化処理材。
（３）繊維状物質が、石英ウール、ガラスウール、ロックウール、セラミックウール、スチールウール、またはスラグウールなどの無機繊維、あるいは有機繊維である上記(1)または上記(2)の何れかに記載する排水浄化処理材。
（４）排水を通じる容器に上記(1)〜上記(3)の何れかに記載する排水浄化処理材を充填してなる排水浄化処理材。
（５）上記(1)〜上記(4)の何れかに記載する排水浄化処理材を容器に充填し、該容器に排水を通じて上記排水浄化処理材に接触させることによって、排水に含まれる水銀、銀、カドミウム、鉛、銅、スズ、亜鉛、ニッケルの何れか１種または２種以上を除去する排水浄化処理方法。
The present invention relates to a wastewater purification treatment material having the following constitution and a treatment method thereof.
(1) A wastewater purification treatment material characterized in that the surface of a fibrous substance is coated with iron sulfide and the iron sulfide is supported on the fibrous substance.
(2) The waste water purification treatment material according to (1) above, wherein the fibrous substance is immersed in an aqueous solution containing divalent iron salts, and sulfide is added to precipitate iron sulfide on the surface of the fibrous substance.
(3) The fibrous substance is any one of the above (1) or (2), wherein the fibrous material is an inorganic fiber such as quartz wool, glass wool, rock wool, ceramic wool, steel wool, or slag wool, or an organic fiber. Wastewater purification treatment material.
(4) A wastewater purification treatment material obtained by filling a wastewater purification treatment material described in any one of (1) to (3) above into a container through which wastewater flows.
(5) Mercury contained in wastewater by filling a container with the wastewater purification treatment material described in any of (1) to (4) above and bringing the container into contact with the wastewater purification treatment material through wastewater; A wastewater purification treatment method for removing one or more of silver, cadmium, lead, copper, tin, zinc, and nickel.
〔具体的な説明〕
本発明の排水浄化材は、繊維状物質の表面を硫化鉄によって被覆し、該硫化鉄を繊維状物質に担持させてなることを特徴とする排水浄化処理材である。該排水浄化処理材は、例えば、繊維状物質を２価鉄の塩類を含む水溶液に浸し、これに硫化物を添加して繊維状物質表面に硫化鉄を析出させることによって製造することができる。あるいは２価鉄の塩類を含む水溶液に硫化物を添加して硫化鉄沈殿物をあらかじめ作成し、ここに繊維状物質を含浸させ繊維状物質に担持させることによって製造することができる。２価鉄の塩類を含む水溶液としては硫酸第一鉄水溶液などを用いることができる。また、硫化物としては硫化ナトリウムなどを用いることができる。
[Specific description]
The waste water purification material of the present invention is a waste water purification treatment material characterized in that the surface of a fibrous material is coated with iron sulfide and the iron sulfide is supported on the fibrous material. The waste water purification treatment material can be produced, for example, by immersing a fibrous material in an aqueous solution containing divalent iron salts and adding a sulfide thereto to precipitate iron sulfide on the surface of the fibrous material. Alternatively, it can be produced by adding a sulfide to an aqueous solution containing a divalent iron salt to prepare an iron sulfide precipitate in advance, impregnating the fibrous substance therein, and supporting it on the fibrous substance. As the aqueous solution containing divalent iron salts, an aqueous ferrous sulfate solution or the like can be used. Moreover, sodium sulfide etc. can be used as a sulfide.
繊維状物質としては、例えば、石英ウール、ガラスウール、ロックウール、セラミックウール、スチールウール、またはスラグウールなどの無機繊維を用いることができる。あるいは有機合成繊維を用いても良い。親水性で化学的に安定なものが好ましい。一般には直径１〜１００μmの繊維を用いることができるが、繊維状物質の太さ、密度、あるいは鉄系沈殿物と繊維状物質の重量割合などは使用環境に応じて適宜選択される。 As the fibrous material, for example, inorganic fibers such as quartz wool, glass wool, rock wool, ceramic wool, steel wool, or slag wool can be used. Alternatively, organic synthetic fibers may be used. Those that are hydrophilic and chemically stable are preferred. In general, fibers having a diameter of 1 to 100 μm can be used. However, the thickness and density of the fibrous substance, or the weight ratio of the iron-based precipitate and the fibrous substance are appropriately selected according to the use environment.
本発明の排水浄化処理材は、例えば、排水を通じるカラム等の容器に該処理材を充填して使用することができる。本発明の排水浄化処理材をカラム等に充填したものは、繊維状物質を用いているので、球状の担体やブロック状の担体に比べて表面積が大きく、空隙率が高いので、繊維状物質と硫化鉄微粒子が相互に絡み合った状態になり、繊維状物質の表面に硫化鉄が安定に保持される。従って、カラム等に排水を通じた場合、硫化鉄が繊維状物質から脱落して流出する割合が少なく、安定な処理効果を得ることができる。 The waste water purification treatment material of the present invention can be used, for example, by filling the treatment material in a container such as a column through which waste water passes. Since the waste water purification treatment material of the present invention packed in a column or the like uses a fibrous material, it has a larger surface area and a higher porosity than a spherical carrier or a block-like carrier. The iron sulfide fine particles are intertwined with each other, and iron sulfide is stably held on the surface of the fibrous material. Therefore, when drainage is passed through a column or the like, the ratio of iron sulfide falling off from the fibrous material and flowing out is small, and a stable treatment effect can be obtained.
上記排水浄化処理材に排水を接触することによって、排水に含まれる水銀、銀、カドミウム、鉛、銅、スズ、亜鉛、ニッケルなどが繊維状物質表面の硫化鉄と反応して硫化物となり、澱物化して排水から除去される。具体的には、例えば、排水に含まれるカドミウムイオンは次式のように硫化鉄と反応して硫化物沈澱になる。
ＦｅＳ＋Ｃｄ2+ → ＣｄＳ＋Ｆｅ2+
By contacting the wastewater with the wastewater purification treatment material, mercury, silver, cadmium, lead, copper, tin, zinc, nickel, etc. contained in the wastewater react with iron sulfide on the surface of the fibrous material to form sulfides. It is materialized and removed from the waste water. Specifically, for example, cadmium ions contained in the waste water react with iron sulfide to form a sulfide precipitate as shown in the following formula.
FeS + Cd 2+ → CdS + Fe 2+
水銀、銀、鉛、銅、スズ、亜鉛、ニッケルなどのように硫化鉄(ＦｅＳ)よりも溶解度積の低い硫化物を形成する金属イオンはカドミウムと同様に繊維表面の硫化鉄と置換反応して硫化物沈澱となる。 Metal ions that form sulfides with a lower solubility product than iron sulfide (FeS), such as mercury, silver, lead, copper, tin, zinc, and nickel, react with iron sulfide on the fiber surface in the same manner as cadmium. Sulfide precipitation occurs.
上記排水浄化処理材に排水を繰り返し通液し、あるいは連続的に通液することによって処理効果が低下してきたら、該排水浄化処理材をカラム等から取り出して新しい排水浄化処理材に交換すれば良い。 If the treatment effect is reduced by repeatedly or continuously passing wastewater through the wastewater purification treatment material, the wastewater purification treatment material may be removed from the column or the like and replaced with a new wastewater purification treatment material. .
本発明の排水浄化処理材は、排水に含まれる重金属を硫化物沈澱として取り込むので、重金属を効果的に排水から除去することができる。また、本発明の排水浄化処理材を使用する場合には加熱する必要がなく、さらに、繊維状物質と一体に取り出して除去することができるので取り扱が容易であり、澱物の後処理の負担が少なく、経済性および取扱性に優れる。 Since the wastewater purification treatment material of the present invention takes in heavy metals contained in wastewater as sulfide precipitates, heavy metals can be effectively removed from wastewater. In addition, when using the wastewater purification treatment material of the present invention, it is not necessary to heat, and furthermore, since it can be taken out and removed integrally with the fibrous material, it is easy to handle, and the post-treatment of starch There is little burden and it is excellent in economy and handling.
繊維状物質として金属製錬の副産物であるスラグウールを用いることによって安価で環境負荷の低い排水処理が可能である。また、本発明の排水浄化処理材は中性〜弱アルカリ性下で使用することができ、ｐＨの調整が容易であり、単一充填層内で重金属の無害化と濃縮分離を達成することができる。例えば、重金属濃度が低い汚染排水を処理する場合、従来は塩化鉄などの共沈剤を用いるために大量のスラッジ量が発生し、シックナーなどの固液分離手段を必要とするが、本発明の浄化処理材によれば、従来のような固液分離手段を必要とせず、排水中の重金属は澱物となって繊維状物質に沈着するので、これを一体に取り出すことによってそのまま排水と分離することができ、後処理が格段に容易である。 By using slag wool, which is a by-product of metal smelting, as a fibrous material, wastewater treatment with low cost and low environmental impact is possible. Moreover, the waste water purification treatment material of the present invention can be used under neutral to weak alkalinity, pH can be easily adjusted, and heavy metals can be rendered harmless and concentrated and separated in a single packed bed. . For example, when treating contaminated wastewater with a low concentration of heavy metals, conventionally, a large amount of sludge is generated due to the use of a coprecipitation agent such as iron chloride, and a solid-liquid separation means such as a thickener is required. According to the purification treatment material, conventional solid-liquid separation means is not required, and the heavy metal in the wastewater becomes starch and deposits on the fibrous material. And post-processing is much easier.
〔実施例〕
硫酸第一鉄水溶液（５mM ＦｅＳＯ4・７Ｈ2Ｏ）１０００mLに、スラグ繊維２０ｇを浸漬し、十分に攪拌して繊維をなじませる。この溶液に硫化ソーダ１.７ｇを滴下し、攪拌しながら硫化鉄を生成させ、スラグ繊維表面をこの硫化鉄によって被覆した。硫化鉄によって被覆したスラグ繊維を回収して、カラム（直径５cm×高さ７cm）に均一に充填した。このカラムの上部から排水を液線流速６０mm/minで内部に通液して流下させた。流下前の排水に含まれる重金属濃度と、流下後の重金属濃度を表１に示した。
〔Example〕
20 g of slag fiber is immersed in 1000 mL of ferrous sulfate aqueous solution (5 mM FeSO 4 .7H 2 O), and the mixture is thoroughly agitated to allow the fiber to become familiar. To this solution, 1.7 g of sodium sulfide was added dropwise to produce iron sulfide while stirring, and the surface of the slag fiber was covered with this iron sulfide. Slag fibers coated with iron sulfide were collected and uniformly packed in a column (diameter 5 cm × height 7 cm). Waste water was allowed to flow through the top of the column at a liquid flow rate of 60 mm / min. Table 1 shows the heavy metal concentration contained in the wastewater before flowing down and the heavy metal concentration after flowing down.
表１に示すように、本発明の排水浄化処理剤を通過した排水の重金属イオンは大幅に低減されており、この処理効果は流下量５００mLと２０００mLのいずれにおいても大きな違いはなく、排水の処理流量が増えても安定に重金属を除去できる。
As shown in Table 1, the amount of heavy metal ions in the wastewater that passed through the wastewater purification treatment agent of the present invention is greatly reduced, and this treatment effect is not significantly different between the flow-down amounts of 500 mL and 2000 mL. Even if the flow rate increases, heavy metals can be removed stably.
Claims (5)
A wastewater purification treatment material comprising a fibrous substance having a surface coated with iron sulfide and the iron sulfide being supported on the fibrous substance.
The wastewater purification treatment material according to claim 1, wherein the fibrous material is immersed in an aqueous solution containing divalent iron salts, and sulfide is added to precipitate iron sulfide on the surface of the fibrous material.
The wastewater purification treatment material according to any one of claims 1 and 2, wherein the fibrous substance is an inorganic fiber such as quartz wool, glass wool, rock wool, ceramic wool, steel wool, or slag wool, or an organic fiber. .
A wastewater purification treatment material obtained by filling a wastewater purification treatment material according to any one of claims 1 to 3 into a container through which wastewater flows.
Mercury, silver, cadmium, lead contained in wastewater by filling the wastewater purification treatment material according to any one of claims 1 to 4 into a container and bringing the container into contact with the wastewater purification treatment material through drainage. Waste water purification treatment method for removing any one or more of copper, tin, zinc and nickel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019063710A (en) * | 2017-09-29 | 2019-04-25 | Ｄｏｗａテクノロジー株式会社 | Treatment method and treatment apparatus of liquid to be treated |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019063710A (en) * | 2017-09-29 | 2019-04-25 | Ｄｏｗａテクノロジー株式会社 | Treatment method and treatment apparatus of liquid to be treated |
| JP7008456B2 (en) | 2017-09-29 | 2022-01-25 | Ｄｏｗａテクノロジー株式会社 | Treatment method and treatment equipment for the liquid to be treated |
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