JP2013031837A - Reducing agent for harmful element, and method for reducing harmful element - Google Patents
Reducing agent for harmful element, and method for reducing harmful element Download PDFInfo
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- 230000001603 reducing effect Effects 0.000 title claims abstract description 38
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- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 79
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- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
本発明は、排水、廃液、地下水などの水、土壌、廃棄物などの処理対象物からヒ素、６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛を除去するための有害元素低減材及び有害元素低減方法に関するものである。 The present invention relates to harmful elements for removing arsenic, hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead from water, wastewater, groundwater and other treatment objects such as soil and waste. The present invention relates to a reducing material and a method for reducing harmful elements.
近年、自然発生的要因及び／又は産業発生的要因によって発生した有害元素に起因する環境保全上の支障の除去の必要性が高まっている。このため、水質汚濁防止法では、排水中におけるヒ素（Ａｓ）の濃度が０．１ｍｇ／Ｌ以下に定められ、土壌汚染対策法では、環境省告示１３号及び４６号試験法での溶出液中におけるヒ素の濃度（土壌環境基準値（平６環庁告２５））が０．０１ｍｇ／Ｌ以下（農用地においては１５ｍｇ／Ｌ未満）に定められている。 In recent years, there has been an increasing need for removal of environmental conservation obstacles caused by harmful elements generated by natural and / or industrial factors. For this reason, in the Water Pollution Control Law, the concentration of arsenic (As) in the wastewater is set to 0.1 mg / L or less, and in the Soil Contamination Countermeasures Law, in the eluate in the Ministry of the Environment Notification Nos. 13 and 46 test methods. The concentration of arsenic (soil environmental standard value (Heisei 6 Ring Agency Notification 25)) is set to 0.01 mg / L or less (less than 15 mg / L in agricultural land).
水、土壌、廃棄物などの処理対象物からヒ素を除去する方法としては種々の方法が提案されている。例えば、特許文献１〜３には、鉄系化合物によるイオン交換反応や凝集沈殿分離を利用してヒ素を除去する方法が記載されている。特許文献４，５には、活性アルミナなどのアルミニウム化合物による化学吸着を利用してヒ素を除去する方法が記載されている。特許文献６には、第一鉄塩とＣａ（ＯＨ）２とを排水に添加してヒ素を凝集分離する方法が記載されている。特許文献７〜１１には、カルシウム源としてのカルシウムフェライトを提供する高炉徐冷スラグが記載されている。
Various methods have been proposed for removing arsenic from treatment objects such as water, soil and waste. For example, Patent Documents 1 to 3 describe a method for removing arsenic using an ion exchange reaction or agglomeration precipitation separation with an iron-based compound.
しかしながら、特許文献１〜３記載の方法では、鉄系化合物として還元性鉄粉を用いているために、処理対象物からヒ素を除去するまでに多くの時間を要する。特許文献２，３記載の方法では、鉄系化合物として硫酸第一鉄を用いているために、系に硫黄系の化合物を添加する必要があり、環境負荷の弊害が新たに発生するおそれがある。また、水酸化物としての沈殿分離では、固液分離操作が煩雑であるのに加えて、ｐＨなどの調整が必要であり、またｐＨの変動によってヒ素の補集率が大幅に変動することがある。
However, in the methods described in Patent Documents 1 to 3, since reducing iron powder is used as the iron-based compound, it takes a long time to remove arsenic from the object to be treated. In the methods described in
特許文献４，５記載の方法では、アルミニウム化合物として用いられるハイドロタルサイトや酸化アルミニウムなどの材料が高価であるのに加えて、アルミニウム摂取とアルツハイマー病との関連が指摘されるなど、安全性が十分に検証されていない。特許文献６記載の方法では、固液分離操作が煩雑であるのに加えて、ｐＨなどの調整が必要である。特許文献８記載の方法は、カルシウムフェライトと高炉水砕スラグとの混合物を用いてＣｒ（６価），Ａｓ，Ｓｅを固定化する方法であるが、これは特許文献７に記載された高炉水砕スラグによるＣｒ（６価）固定化の方法を発展させた方法であり、５〜９０％のカルシウムフェライトが必要であるため、高価である。
In the methods described in
特許文献９，１０記載の方法は、Ｓ，Ｆｅを含有する高炉徐冷スラグをヒ素低減材として用いるものであるが、Ｓの混入は新たな環境負荷の要因となりうるため好ましくない。特許文献１１記載の方法は、高炉徐冷スラグと製鋼スラグとからなるヒ素低減材であるが、Ｓを０．３％以上含有しているために、Ｓの混入が新たな環境負荷の要因となりうるため好ましくない。また、有害物質低減材を添加混合した際の水又は土壌のｐＨが７以下であることが規定されており、ｐＨが７を超えるような処理対象物には適用できない、若しくは、ｐＨを７以下に調整するための煩雑な処理が必要になる。特許文献８〜１１記載の方法では、水質検液５０ｍＬに対して１０ｇと非常に多くのヒ素低減材が必要な上に、非常に長い処理日数（実施例では２８日）が必要になる。
The methods described in
処理が求められる汚染土壌などには通常０．１μｇ／ｋｇ〜数１０００ｍｇ／ｋｇのヒ素が含まれている。このため、このような土壌に対して、同程度若しくは同程度以下の量のヒ素低減材を用いてｐＨを７以下に調整することなく、ヒ素を低減できる方法の提供が望まれている。本発明は、上記課題に鑑みてなされたものであって、その目的は、処理対象物からヒ素を簡単、迅速、且つ、安価に除去可能な有害元素低減材及び有害元素低減方法を提供することにある。 Contaminated soil or the like that is required to be treated usually contains 0.1 μg / kg to several thousand mg / kg of arsenic. For this reason, it is desired to provide a method that can reduce arsenic without adjusting the pH to 7 or less by using an arsenic reducing material of the same level or lower than that of such soil. The present invention has been made in view of the above problems, and an object thereof is to provide a harmful element reducing material and a harmful element reducing method capable of removing arsenic from an object to be treated easily, quickly and inexpensively. It is in.
また、ヒ素以外の環境規制物質である６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛は、ヒ素と同一の処理で除去することが困難な成分であるが、これらをヒ素と同時に低減できれば、処理はより簡単、迅速、且つ、安価になりうる。そこで、本発明の他の目的は、全く同一の処理により、処理対象物からヒ素と同時に６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛を簡単、迅速、且つ、安価に除去可能な有害元素低減材及び有害元素低減方法を提供することにある。 In addition, hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead, which are environmentally restricted substances other than arsenic, are components that are difficult to remove by the same treatment as arsenic. If it can be reduced at the same time, the process can be simpler, faster and cheaper. Therefore, another object of the present invention is to provide simple, quick, and inexpensive hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead simultaneously with arsenic from an object to be treated by exactly the same treatment. It is an object of the present invention to provide a hazardous element reducing material and a method for reducing harmful elements that can be removed.
上記課題を解決し、目的を達成するために、本発明に係る有害元素低減材は、製鋼スラグを８５質量％以上含むことを特徴とする。 In order to solve the above-mentioned problems and achieve the object, the harmful element reducing material according to the present invention is characterized in that it contains 85% by mass or more of steelmaking slag.
また、本発明に係る有害元素低減材は、上記発明において、製鋼スラグは、鉄の含有率が２０質量％以上であり、カルシウムの含有率が２０質量％以上であり、且つ、ケイ素含有率が１０質量％以下である製鋼スラグであることを特徴とする。 Further, the harmful element reducing material according to the present invention is the above-described invention, wherein the steelmaking slag has an iron content of 20 mass% or more, a calcium content of 20 mass% or more, and a silicon content. It is a steelmaking slag which is 10 mass% or less.
上記課題を解決し、目的を達成するために、本発明に係る有害元素低減方法は、鉄の含有率が２０質量％以上であり、カルシウムの含有率が２０質量％以上であり、且つ、ケイ素含有率が１０質量％以下である製鋼スラグを８５質量％以上含む有害元素低減材を処理対象物に接触させることによって、該処理対象物のヒ素含有量を低減させる処理工程を含むことを特徴とする。 In order to solve the above problems and achieve the object, the method for reducing harmful elements according to the present invention has an iron content of 20 mass% or more, a calcium content of 20 mass% or more, and silicon. It includes a treatment step of reducing the arsenic content of the object to be treated by contacting the object to be treated with a harmful element reducing material containing 85% by mass or more of steelmaking slag whose content is 10% by mass or less. To do.
また、本発明に係る有害元素低減方法は、上記発明において、前記処理工程の前に、前記処理対象物に含まれる３価のヒ素を５価のヒ素に酸化させる工程を含むことを特徴とする。 In the above invention, the method for reducing harmful elements according to the present invention includes a step of oxidizing trivalent arsenic contained in the object to be treated to pentavalent arsenic before the treatment step. .
上記課題を解決し、目的を達成するために、本発明に係る有害元素低減方法は、鉄の含有率が２０質量％以上であり、カルシウムの含有率が２０質量％以上であり、且つ、ケイ素含有率が１０質量％以下である製鋼スラグを８５質量％以上含む有害元素低減材を処理対象物に接触させることによって、該処理対象物のヒ素、６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛のうちの少なくとも一つの元素の含有量を低減させる処理工程を含むことを特徴とする。 In order to solve the above problems and achieve the object, the method for reducing harmful elements according to the present invention has an iron content of 20 mass% or more, a calcium content of 20 mass% or more, and silicon. By bringing a harmful element reducing material containing 85% by mass or more of steelmaking slag having a content rate of 10% by mass or less into contact with an object to be treated, arsenic, hexavalent chromium, beryllium, nickel, copper, zinc of the object to be treated, It includes a treatment step for reducing the content of at least one element of cadmium, mercury, and lead.
本発明に係る有害元素低減材及び有害元素低減方法によれば、処理対象物からヒ素を簡単、迅速、且つ、安価に除去することができる。また、本発明に係る有害元素低減材及び有害元素低減方法によれば、全く同一の処理により、処理対象物からヒ素と同時に６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛を簡単、迅速、且つ、安価に除去することができる。 According to the harmful element reducing material and the hazardous element reducing method according to the present invention, arsenic can be easily and quickly removed from a processing target at a low cost. Further, according to the harmful element reducing material and the harmful element reducing method according to the present invention, hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead can be simultaneously treated with arsenic by the same treatment. Can be removed easily, quickly and inexpensively.
本発明の発明者らは、鋭意研究を重ねてきた結果、製鋼スラグが、Ｆｅによるイオン交換作用及び吸着作用、Ｆｅ水酸化物による凝集作用、及びＣａＯによるｐＨ調整作用を複合的に発揮することによって、ｐＨがアルカリ側で水中のヒ素及び固体から溶出するヒ素を捕集する高い能力を有することを知見した。ｐＨが酸性でもヒ素捕集効果は高くなるが、製鋼スラグそのものが処理液に溶解するため好ましくない。一方、ｐＨがアルカリ側になるほどヒ素捕集効果は高くなり、実質的にｐＨ９以上で充分な効果を発揮する。ここで、製鋼スラグとは、溶銑やスクラップなどを精錬して鋼を製造する際に同時に製造される転炉スラグ、電気炉スラグ、及びそのほか製鋼工程で製造される溶銑予備処理スラグ（溶銑を転炉に装入する前に溶銑の脱硫、脱珪などの処理をする際に生成されるスラグ。予備処理の内容に応じて生成されるスラグを脱硫スラグ、脱珪スラグなどと称する）、二次精錬スラグ（転炉などから出鋼した溶鋼に脱硫、脱ガスなどの処理をする際に生成されるスラグ）、スロッピングスラグ（転炉吹錬中に炉内から飛び出し、炉下に落下したスラグ）、鋳造スラグ（溶鋼を鋳型又は連続鋳造機に注入した後、溶鋼鍋に残留したスラグ）、及び混銑炉スラグ（混銑炉から排出されたスラグ）を意味する。より具体的には、製鋼スラグは、鉄鋼製造プロセスにおいて生成されるものであり、ＣａＯ，ＳｉＯ２，ＦｅＯ，Ｆｅ２Ｏ３，ＭｇＯ，ＭｎＯ，Ｐ２Ｏ５を主成分、Ａｌ２Ｏ３，Ｓなどを副成分として含有するものである。代表的な鉱物相としては、ダイカルシウムシリケート（β−Ｃａ２（ＳｉＯ４，ＰＯ４））、トリカルシウムシリケート（（Ｍｇ，Ｃａ，Ｍｎ，Ｆｅ）３ＳｉＯ５）、ウスタイト（ＦｅＯ）、マグネタイト（Ｍｎ，Ｆｅ）３Ｏ４）、ライム（ＣａＯ）、ダイカルシウムフェライトチタネート（Ｃａ２（Ａｌ，Ｆｅ）２Ｏ５−Ｃａ（Ｓｉ，Ｔｉ）Ｏ）などが存在する。
As a result of intensive studies, the inventors of the present invention have shown that steelmaking slag exhibits a composite action of ion exchange and adsorption by Fe, agglomeration by Fe hydroxide, and pH adjustment by CaO. It was found that the pH has a high ability to collect arsenic in water and arsenic eluted from the solid on the alkali side. Even if the pH is acidic, the arsenic collection effect is enhanced, but the steelmaking slag itself is not preferable because it dissolves in the treatment liquid. On the other hand, the arsenic trapping effect becomes higher as the pH becomes alkaline, and a sufficient effect is exhibited substantially at pH 9 or higher. Here, steelmaking slag refers to converter slag, electric furnace slag, and other hot metal pretreatment slag (smelting hot metal) produced in the steelmaking process. Slag generated when processing desulfurization, desiliconization, etc. of hot metal before charging into the furnace.Slag generated according to the pretreatment content is called desulfurization slag, desiliconization slag, etc.), secondary Refining slag (slag generated when desulfurization, degassing, etc. is performed on molten steel produced from converters), slopping slag (slag that jumps out of the furnace during converter blowing and falls under the furnace ), Casting slag (slag remaining in the molten steel pan after pouring molten steel into a mold or continuous casting machine), and kneading furnace slag (slag discharged from the kneading furnace). More specifically, steel slag is one produced in the steel manufacturing process, CaO, SiO 2, FeO, Fe 2
製鋼スラグとしては、鉄含有率が２０質量％以上、カルシウムの含有率が２０質量％以上、且つ、ケイ素含有率が１０質量％以下、好ましくは５質量％以下の転炉スラグ、脱硫スラグなどの製鋼スラグを使用するとよい。製鋼スラグによるヒ素の除去効果は、製鋼スラグに含まれるＦｅのイオン交換と吸着作用とによることから、鉄含有率が低くなるほど低下し、特許文献８〜１０に記載の高炉スラグのような鉄含有率が低いスラグではほとんど発現しない。また、特許文献１１記載の方法のように、高炉スラグに製鋼スラグを含有させた場合であっても、上記製鋼スラグの含有率が８５質量％未満である場合、さらに有害元素低減材を添加混合した後の溶液又は土壌のｐＨが９未満である場合には、ヒ素の除去効果は著しく低い。このため、製鋼スラグの含有率は８５質量％以上、低減材添加後の溶液又は土壌のｐＨは高いほどよく、特に９以上であることが望ましい。製鋼スラグを８５質量％以上含有する有害元素低減材にほぼ中性の水を添加した場合に溶液のｐＨを９以上にするのに必要な製鋼スラグの組成としては、鉄含有率が２０質量％以上、カルシウムの含有率が２０質量％以上、且つ、ケイ素含有率が１０質量％以下、好ましくは５質量％以下であることが必要であり、このような組成を有する製鋼スラグを８５質量％以上含有する有害元素低減材であれば、添加時に試薬添加などによるｐＨの調整は特に必要なく、処理対象物に対して少量の添加でもｐＨ９以上になり、迅速、且つ、効率よくヒ素を除去することができる。 Steelmaking slag includes converter slag, desulfurized slag, etc. with an iron content of 20% by mass or more, a calcium content of 20% by mass or more, and a silicon content of 10% by mass or less, preferably 5% by mass or less. Steelmaking slag should be used. The removal effect of arsenic by the steelmaking slag is due to the ion exchange and adsorption action of Fe contained in the steelmaking slag, so that the lower the iron content, the lower the iron content, such as the blast furnace slag described in Patent Documents 8 to 10 It hardly appears in slag with a low rate. Moreover, even when the steelmaking slag is contained in the blast furnace slag as in the method described in Patent Document 11, if the steelmaking slag content is less than 85% by mass, a harmful element reducing material is further added and mixed. When the pH of the solution or soil after the treatment is less than 9, the arsenic removal effect is remarkably low. For this reason, the content rate of steelmaking slag is 85 mass% or more, and the pH of the solution or soil after addition of a reducing material is so high that it is desirable that it is especially 9 or more. The composition of the steelmaking slag required to bring the pH of the solution to 9 or more when adding almost neutral water to the hazardous element reducing material containing 85% by mass or more of steelmaking slag has an iron content of 20% by mass. As described above, it is necessary that the calcium content is 20% by mass or more and the silicon content is 10% by mass or less, preferably 5% by mass or less, and the steelmaking slag having such a composition is 85% by mass or more. If it is a hazardous element-reducing material, it is not particularly necessary to adjust the pH by adding a reagent at the time of addition, and even if a small amount is added to the object to be treated, the pH becomes 9 or more, and arsenic can be removed quickly and efficiently. Can do.
製鋼スラグは単独で用いても、若しくはヒ素の低減処理を円滑に行うために成形助剤を添加してもよい。処理対象物との接触表面積を増やすためには、製鋼スラグは粉砕して粉末化することが望ましいが、製鋼スラグはもともと粒径が小さいものが多いので、そのまま用いる、若しくは固液分離の際の操作性を考慮して水質を通液できるようなカラム状容器に充填する機械プレスなどの方法によって、処理に適した形状に成形するなどの手段をとることができる。水質の処理に用いる場合には、対象試料に直接本発明の製鋼スラグを添加、攪拌後、ろ過などによってスラグを取り除くことによって、水質中のヒ素は製鋼スラグと共に固相に移動し、水質中のヒ素の量を低減させることができる。粉末状の製鋼スラグをカラム状の容器に充填若しくは一定形状に成形し、これに対象の水質試料を通液することによって、水質中のヒ素を除去できる。この場合、スラグに捕集されたヒ素は酸性の溶液を通液することによってスラグから溶離するので、スラグを充填した除去カラム及び成形カラムは、水質処理に繰り返し利用することができる。 Steelmaking slag may be used alone, or a molding aid may be added to smoothly perform arsenic reduction treatment. In order to increase the surface area of contact with the object to be treated, it is desirable to pulverize and make steelmaking slag. However, steelmaking slag is originally small in particle size, so it can be used as it is or when solid-liquid separation is performed. In consideration of operability, means such as molding into a shape suitable for processing can be taken by a method such as a mechanical press that fills a column-shaped container that can pass water. When used for water quality treatment, the steelmaking slag of the present invention is added directly to the target sample, and after stirring, slag is removed by filtration or the like, so that arsenic in the water quality moves to the solid phase together with the steelmaking slag, and in the water quality The amount of arsenic can be reduced. Arsenic in the water quality can be removed by filling the steel slag in powder form into a column-shaped container or molding the powdered steel slag into a fixed shape, and passing the target water quality sample therethrough. In this case, since the arsenic collected in the slag is eluted from the slag by passing an acidic solution, the removal column and the forming column filled with the slag can be repeatedly used for water quality treatment.
ヒ素の除去に利用されるヒ素の形態は特に限定されるものではないが、鉄に捕集されやすい５価のヒ素に変化させることによって、ヒ素はより効率的に製鋼スラグに捕集される。３価のヒ素から５価のヒ素への酸化は、塩素（例えば次亜塩素酸）やオゾンの添加、吹き込みなどによって容易に行うことができる。土壌や廃棄物などの処理に用いる場合には、本発明の製鋼スラグを混合して用いる方法や散布する方法、スラリー状にして注入する方法などがある。本発明の製鋼スラグの組成は、天然の岩石に近く、スラグ単体でも路盤材などの土工用材料として用いることができることから、土壌の改質方法として有用である。 Although the form of arsenic used for removal of arsenic is not particularly limited, arsenic is more efficiently collected in the steelmaking slag by changing to pentavalent arsenic that is easily collected by iron. Oxidation from trivalent arsenic to pentavalent arsenic can be easily performed by adding chlorine (for example, hypochlorous acid) or ozone, blowing in, or the like. When used for the treatment of soil, waste, etc., there are a method of mixing and using the steelmaking slag of the present invention, a method of spraying, a method of pouring in a slurry state, and the like. The composition of the steelmaking slag of the present invention is close to natural rocks, and even a slag alone can be used as an earthwork material such as a roadbed material, and thus is useful as a soil modification method.
さらに、本発明の発明者らは、上述のヒ素の捕集と全く同様の処理により、ヒ素と同時に６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛を簡単、迅速、且つ、安価に除去できることを見出した。通常、水中でオキソ酸イオンとして存在するヒ素と陽イオンとして存在するベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛とを同時に捕集できる条件を見出すことが可能な捕集材及び捕集条件は極めて少ない。しかしながら、製鋼スラグによれば、Ｆｅによるイオン交換作用及び吸着作用、Ｆｅ水酸化物による凝集作用、及びＣａＯによるｐＨ調整作用を複合的に発揮することによって、このような優れた効果が得られる。さらに、製鋼スラグによれば、含有するＦｅ（II）及び硫化物の還元作用により６価クロムを３価クロムに還元し、水酸化物として同時に捕集することができる。 Furthermore, the inventors of the present invention can easily and quickly remove hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead simultaneously with arsenic by the same treatment as the above arsenic collection. It was found that it can be removed inexpensively. Usually, a collector and a collector capable of finding conditions capable of simultaneously collecting arsenic existing as oxo acid ions in water and beryllium, nickel, copper, zinc, cadmium, mercury, and lead existing as cations. Conditions are very few. However, according to the steelmaking slag, such excellent effects can be obtained by combining the ion exchange action and adsorption action by Fe, the aggregation action by Fe hydroxide, and the pH adjustment action by CaO. Furthermore, according to the steelmaking slag, hexavalent chromium can be reduced to trivalent chromium by the reducing action of contained Fe (II) and sulfide, and simultaneously collected as hydroxide.
〔実施例１〕
実施例１では、転炉スラグ（Fe22.6%，Si4.5%，Al2.8%，Ca25.8%，As<5ppm，Se<5ppm）及び比較例としての高炉徐冷スラグ（Fe0.6%，Si15.8%，Al7.2%，Ca28.4%，As<5ppm，Se<5ppm）(ここで％は質量％を表す)を、それぞれ粉砕し２ｍｍ目のふるいにかけ、ふるいを通過したもの０．１ｇ及び０．３ｇに対してそれぞれ３価及び５価のヒ素を１μｇ／ｍｌ含む水溶液５０ｍＬを添加、攪拌、ろ過した後、ろ液中のＡｓ濃度をＩＣＰ質量分析法を用いて定量した。攪拌時間の変化に伴う３価及び５価のヒ素の残存率の変化、及びろ液の初期のｐＨをそれぞれ図１，２に示す。図１，２に示すように、転炉スラグは、高炉徐冷スラグと比較してＡｓに対して優れた捕集能力を示し、５価のＡｓにおいては、転炉スラグ０．３ｇでろ液５０ｍＬ中のＡｓが１０分で９０％以上、３０分でほぼ全量除去できることが知見された。また、３価のＡｓよりも５価のＡｓの方が効率よく除去できることが知見された。
[Example 1]
In Example 1, converter slag (Fe22.6%, Si4.5%, Al2.8%, Ca25.8%, As <5ppm, Se <5ppm) and blast furnace slow-cooled slag (Fe0.6) as a comparative example were used. %, Si15.8%, Al7.2%, Ca28.4%, As <5ppm, Se <5ppm) (where% represents mass%) were each crushed and passed through a 2mm sieve and passed through the sieve. After adding 50 mL of an aqueous solution containing 1 μg / mL of trivalent and pentavalent arsenic to 0.1 g and 0.3 g of the product, stirring and filtering, the As concentration in the filtrate was quantified using ICP mass spectrometry. did. 1 and 2 show the change in the residual ratio of trivalent and pentavalent arsenic with the change in the stirring time, and the initial pH of the filtrate, respectively. As shown in FIGS. 1 and 2, the converter slag exhibits an excellent collection capacity for As compared to the blast furnace slow-cooled slag, and for pentavalent As, the converter slag is 0.3 g and the filtrate is 50 mL. It has been found that As can be removed by 90% or more in 10 minutes and almost all in 30 minutes. It was also found that pentavalent As can be removed more efficiently than trivalent As.
〔実施例２〕
実施例２では、始めに、褐色森林土と基材との混合土壌からなる汚染土壌認証標準物質（日本分析化学会製JSAC0462(As：71.5±2.9mg/kg)，JSAC0464(As：271.1±9.0mg/kg)）０．５ｇに対して、スラグ類を表１に示すように混合した。スラグ類は粉砕し２ｍｍ目のふるいを通過したものを用いた。次に、この混合物に対して環境庁告示４６号試験法に基づく溶出試験を行い抽出液中のＡｓの濃度を測定することによってＡｓの溶出量を測定した。ここで、各スラグの組成は、転炉スラグ（Fe22.6%，Si4.5%，Al2.8%，Ca25.8%，As<5ppm，Se<5ppm）、脱硫スラグ（Fe29.9%，Si2.8%，Al2.1%，Ca27.8%，As<5ppm，Se<5ppm）、高炉徐冷スラグ（Fe0.6%，Si15.8%，Al7.2%，Ca28.4%，As<5ppm，Se<5ppm）である(ここで％は質量％を表す)。測定結果を以下の表１に示す。表１に示すように、汚染土壌認証標準物質に転炉スラグ又は脱硫スラグを添加した本発明例１〜８では、転炉スラグ又は脱硫スラグがＡｓを捕集するため、比較例１〜５と比較して、抽出液中のＡｓの濃度が低く、Ａｓ溶出量の顕著な抑制効果が認められた。このことから、汚染土壌認証標準物質に転炉スラグ又は脱硫スラグを添加することによって、処理対象物のＡｓ含有量の低減およびＡｓの溶出が抑制できることが知見された。
[Example 2]
In Example 2, first, a contaminated soil certified reference material (JSAC0462 (As: 71.5 ± 2.9 mg / kg), JSAC0464 (As: 271.1 ± 9.0, manufactured by Analytical Chemical Society of Japan) consisting of a mixed soil of brown forest soil and a base material is used. mg / kg)) 0.5 g was mixed with slag as shown in Table 1. The slag used was crushed and passed through a 2 mm sieve. Next, an elution test based on the Environmental Agency Notification No. 46 test method was performed on this mixture, and the As elution amount was measured by measuring the concentration of As in the extract. Here, the composition of each slag is the converter slag (Fe22.6%, Si4.5%, Al2.8%, Ca25.8%, As <5ppm, Se <5ppm), desulfurization slag (Fe29.9%, Si2.8%, Al2.1%, Ca27.8%, As <5ppm, Se <5ppm), Blast furnace annealing slag (Fe0.6%, Si15.8%, Al7.2%, Ca28.4%, As <5 ppm, Se <5 ppm) (where% represents mass%). The measurement results are shown in Table 1 below. As shown in Table 1, in Examples 1-8 of the present invention in which converter slag or desulfurization slag was added to the contaminated soil certified reference material, converter slag or desulfurization slag collects As, so Comparative Examples 1-5 and In comparison, the concentration of As in the extract was low, and a remarkable suppression effect on the As elution amount was observed. From this, it has been found that by adding converter slag or desulfurization slag to the contaminated soil certified reference material, it is possible to reduce the As content of the processing object and to suppress the elution of As.
〔実施例３〕
実施例３では、実施例１，２で使用したものと同じ転炉スラグ（Fe22.6%，Si4.5%，Al2.8%，Ca25.8%，As<5ppm，Se<5ppm）及び脱硫スラグ（Fe29.9%，Si2.8%，Al2.1%，Ca27.8%，As<5ppm，Se<5ppm）(ここで％は質量％を表す)を、実施例１，２と同様に粉砕して２ｍｍ目のふるいにかけ、ふるいを通過したもの０．１ｇ及び０．３ｇに対してそれぞれ、５価のヒ素及び６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛をそれぞれ１μｇ／ｍＬずつ含む水溶液５０ｍＬを添加、３０分間攪拌、ろ過した後、ろ液中のヒ素、６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛の濃度をＩＣＰ質量分析法を用いて定量した。ろ液中の各元素の濃度より、転炉スラグ及び脱硫スラグに捕集されなかった各元素の残存率を図３に示す。図３に示すように、転炉スラグ及び脱硫スラグは、ヒ素と同様、６価クロム、ベリリウム、ニッケル、銅、亜鉛、カドミウム、水銀、及び鉛に対しても優れた捕集能力を示した。また、６価クロムについては、転炉スラグの添加に伴いろ液５０ｍＬ中の６価クロムが３０％程度残存、ニッケルについては、転炉スラグ０．１ｇの添加に伴いろ液５０ｍＬ中のニッケルが１４％残存、カドミウムについては、転炉スラグ０．１ｇの添加に伴いろ液５０ｍＬ中のカドミウムが２８％残存した以外は、３０分でほぼ全量除去できることができた。
Example 3
In Example 3, the same converter slag (Fe22.6%, Si4.5%, Al2.8%, Ca25.8%, As <5ppm, Se <5ppm) and desulfurization used in Examples 1 and 2 were used. Slag (Fe29.9%, Si2.8%, Al2.1%, Ca27.8%, As <5ppm, Se <5ppm) (where% represents mass%) is the same as in Examples 1 and 2. After pulverizing and passing through a 2 mm sieve, 0.1 g and 0.3 g passed through the sieve, pentavalent arsenic and hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead, respectively. After adding 50 mL of an aqueous solution containing 1 μg / mL each, stirring and filtering for 30 minutes, the concentration of arsenic, hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead in the filtrate was determined by ICP mass spectrometry. Was quantified. FIG. 3 shows the residual rate of each element not collected in the converter slag and desulfurization slag, based on the concentration of each element in the filtrate. As shown in FIG. 3, the converter slag and the desulfurization slag showed excellent collection ability for hexavalent chromium, beryllium, nickel, copper, zinc, cadmium, mercury, and lead as well as arsenic. For hexavalent chromium, approximately 30% of hexavalent chromium remains in 50 mL of filtrate with addition of converter slag, and for nickel, nickel in 50 mL of filtrate increases with addition of 0.1 g of converter slag. As for 14% remaining cadmium, almost all of the cadmium could be removed in 30 minutes except that 28% of cadmium in 50 mL of the filtrate remained with the addition of 0.1 g of converter slag.
〔実施例４〕
実施例４では、褐色森林土と基材との混合土壌からなる汚染土壌認証標準物質（日本分析化学会製JSAC0466(As：1093±32mg/kg、Cr：1483±23mg/kg、Cd：1199±19mg/kg、Hg：113.5±5.6mg/kg、Pb：1214±2.6mg/kg)）０．５ｇに対して、実施例１〜３で使用した転炉スラグ（Fe22.6%，Si4.5%，Al2.8%，Ca25.8%，As<5ppm，Se<5ppm）及び脱硫スラグ（Fe29.9%，Si2.8%，Al2.1%，Ca27.8%，As<5ppm，Se<5ppm）(ここで％は質量％を表す)を実施例１〜３と同様に粉砕し、２ｍｍ目のふるいを通過したもの０．１ｇ及び０．５ｇを添加、混合した。次に、この混合物に対して環境庁告示４６号試験法に基づく溶出試験を行い抽出液中のヒ素、６価クロム、カドミウム、水銀、及び鉛の濃度をＩＣＰ質量分析法で測定することによってヒ素、６価クロム、カドミウム、水銀、及び鉛の溶出量を測定した。測定結果を以下の表２に示す。比較例として汚染土壌認証標準物質にスラグを添加せずに溶出試験を実施した結果を表２に併せて示す。ヒ素に関しては捕集率もあわせて示した。表２に示すように、汚染土壌認証標準物質に転炉スラグ又は脱硫スラグを添加した本発明例９〜１２では、転炉スラグ又は脱硫スラグがＡｓを捕集し、さらに、６価クロム、カドミウム、水銀、及び鉛の抽出液中の濃度がすべて０．００１ｍｇ／Ｌ未満になり、スラグ添加のない場合に比べて溶出量の顕著な抑制効果が認められた。このことから、汚染土壌認証標準物質に転炉スラグ又は脱硫スラグを添加することによって、処理対象物のヒ素、６価クロム、カドミウム、水銀、及び鉛の含有量の低減と、ヒ素、６価クロム、カドミウム、水銀、及び鉛の溶出とが抑制できることが知見された。
Example 4
In Example 4, a contaminated soil certified reference material consisting of a mixed soil of brown forest soil and a base material (JSAC0466 (As: 1093 ± 32 mg / kg, Cr: 1483 ± 23 mg / kg, Cd: 1199 ±, manufactured by Japan Analytical Chemical Society) 19 mg / kg, Hg: 113.5 ± 5.6 mg / kg, Pb: 1214 ± 2.6 mg / kg)) 0.5 g) converter slag (Fe 22.6%, Si4.5 used in Examples 1 to 3) %, Al2.8%, Ca25.8%, As <5ppm, Se <5ppm) and desulfurized slag (Fe29.9%, Si2.8%, Al2.1%, Ca27.8%, As <5ppm, Se < 5 ppm) (where% represents mass%) was pulverized in the same manner as in Examples 1 to 3, and 0.1 g and 0.5 g that passed through a 2 mm sieve were added and mixed. Next, this mixture was subjected to a dissolution test based on the Environmental Agency Notification No. 46 test method, and the concentrations of arsenic, hexavalent chromium, cadmium, mercury, and lead in the extract were measured by ICP mass spectrometry. The amount of elution of hexavalent chromium, cadmium, mercury, and lead was measured. The measurement results are shown in Table 2 below. As a comparative example, Table 2 also shows the results of conducting a dissolution test without adding slag to contaminated soil certified reference materials. For arsenic, the collection rate is also shown. As shown in Table 2, in Examples 9-12 of the present invention in which converter slag or desulfurization slag was added to the contaminated soil certified reference material, the converter slag or desulfurization slag collected As, and hexavalent chromium and cadmium. The concentrations of mercury, lead, and lead in the extract were all less than 0.001 mg / L, and a remarkable suppression effect of the elution amount was observed compared to the case where no slag was added. Therefore, by adding converter slag or desulfurization slag to the certified reference material for contaminated soil, the content of arsenic, hexavalent chromium, cadmium, mercury and lead in the processing object can be reduced, and arsenic and hexavalent chromium. It was found that elution of cadmium, mercury, and lead can be suppressed.
〔実施例５〕
実施例５では、実施例１で使用したものと同じ転炉スラグ（転炉スラグＡと称する：Fe22.6%，Si4.5%，Al2.8%，Ca25.8%，As<5ppm，Se<5ppm）及び組成の異なる２種の転炉スラグ（転炉スラグＢと称する：Fe13.3%，Si18.8%，Al1.9%，Ca23.6%，As<5ppm，Se<5ppm及び転炉スラグＣと称する：Fe21.3%，Si9.8%，Al2.8%，Ca24.6%，As<5ppm，Se<5ppm）(ここで％は質量％を表す)をそれぞれ粉砕し２ｍｍ目のふるいにかけ、ふるいを通過したもの０．１ｇ及び０．３ｇに対してそれぞれ５価のヒ素を１ｍｇ／Ｌ含む水溶液５０ｍＬを添加、３０分間攪拌、ろ過した後、ろ液中のＡｓ濃度をＩＣＰ質量分析法を用いて定量した。定量結果を表３に示す。表３に示すように、転炉スラグＡでは８５％を超える高いＡｓ捕集率が得られている。これに対して、Ｆｅの含有率が２０質量％未満、ケイ素含有率が１０質量％超えの転炉スラグＢを用いた場合には、Ａｓ捕集率は２０％未満と著しく低い。また、Ｆｅの含有率は２０質量％以上、ケイ素含有率５〜１０質量％の転炉スラグＣを用いた場合には、Ａｓ捕集率は６０％前後であり、スラグＢよりも高いＡｓ捕集率が得られたものの、ケイ素含有率が５質量％未満のスラグＡの場合に比べて捕集率は低い。以上のことから、同じ転炉スラグであっても、本発明に係る成分組成を満たすことが高効率なＡｓ捕集には不可欠であることが知見された。
Example 5
In Example 5, the same converter slag as used in Example 1 (referred to as converter slag A: Fe22.6%, Si4.5%, Al2.8%, Ca25.8%, As <5ppm, Se <5ppm) and two types of converter slag with different compositions (referred to as converter slag B: Fe13.3%, Si18.8%, Al1.9%, Ca23.6%, As <5ppm, Se <5ppm and Furnace slag C: Fe21.3%, Si9.8%, Al2.8%, Ca24.6%, As <5ppm, Se <5ppm) (where% represents mass%) After adding 50 mL of an aqueous solution containing 1 mg / L of pentavalent arsenic to 0.1 g and 0.3 g of each passed through the sieve, stirring and filtering for 30 minutes, the As concentration in the filtrate was determined by ICP Quantification was performed using mass spectrometry. The quantitative results are shown in Table 3. As shown in Table 3, the converter slag A has a high As collection rate exceeding 85%. On the other hand, when the converter slag B having a Fe content of less than 20% by mass and a silicon content of more than 10% by mass is used, the As collection rate is significantly lower than 20%. Further, when the converter slag C having a Fe content of 20% by mass or more and a silicon content of 5 to 10% by mass is used, the As collection rate is around 60%, and the As collection rate is higher than the slag B. Although the collection rate was obtained, the collection rate is low compared to the case of slag A having a silicon content of less than 5% by mass. From the above, it was found that even for the same converter slag, satisfying the component composition according to the present invention is essential for highly efficient As collection.
以上、本発明者によってなされた発明を適用した実施の形態について説明したが、本実施形態による本発明の開示の一部をなす記述及び図面により本発明は限定されることはない。すなわち、本実施形態に基づいて当業者などによりなされる他の実施の形態、実施例及び運用技術などは全て本発明の範疇に含まれる。 Although the embodiment to which the invention made by the present inventor is applied has been described above, the present invention is not limited by the description and the drawings that form a part of the disclosure of the present invention according to this embodiment. That is, other embodiments, examples, operational techniques, and the like made by those skilled in the art based on the present embodiment are all included in the scope of the present invention.
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