JP2007125536A - Immobilizing agent and method for harmful component - Google Patents

Immobilizing agent and method for harmful component Download PDF

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JP2007125536A
JP2007125536A JP2006020029A JP2006020029A JP2007125536A JP 2007125536 A JP2007125536 A JP 2007125536A JP 2006020029 A JP2006020029 A JP 2006020029A JP 2006020029 A JP2006020029 A JP 2006020029A JP 2007125536 A JP2007125536 A JP 2007125536A
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JP4827541B2 (en
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Yoshiyuki Jinno
善行 神野
Toshio Ashitani
俊夫 蘆谷
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an immobilizing agent for a harmful component capable of simply eluting no harmful component even if an immobilized material after an aqueous solution and/or a sludgy material containing the harmful component such as a heavy metal and arsenic is in contact with an acidic liquid such as an acid resin, and an inexpensive immobilizing method for the aqueous solution and/or the sludgy material containing the harmful component such as the heavy metal and arsenic using this immobilizing agent. <P>SOLUTION: The immobilizing agent comprises a silica material, and a magnesium or strontium compound. Also the immobilizing method for the harmful component comprises a pre-treatment of the aqueous solution and/or the sludgy material containing the harmful component in response to the harmful component and then a load of the silica material, wherein the immobilizing agent for the harmful component including the magnesium or strontium compound so that the pH of the aqueous solution and/or the sludgy material containing the harmful component is in the range of 4 to 12, or loading this immobilizing agent and next a pH adjusting agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、有害成分の固定化薬剤および固定化方法に関するものである。詳しくは、排水、廃液等の水溶液および／または汚泥、ケーキ等の泥状物に含有する重金属や砒素等の有害成分を固定化する薬剤、およびこの固定化薬剤を用いて有害成分を含有する水溶液および／または泥状物中の有害成分を固定化する方法に関するものである。   The present invention relates to an immobilizing agent for harmful components and an immobilizing method. Specifically, an aqueous solution such as drainage and waste liquid and / or a chemical that immobilizes harmful components such as heavy metals and arsenic contained in sludge and sludge such as cake, and an aqueous solution that contains harmful components using this immobilized chemical And / or a method for immobilizing harmful components in mud.

砒素等を含有する廃棄物の固定化方法として、鉄塩またはアルミニウム塩に水酸化カルシウムを添加して行う方法（例えば、非特許文献１参照。）、または脱アルカリシリカを添加して行う方法（例えば、特許文献１参照。）のような化学処理による方法が知られている。   As a method for immobilizing waste containing arsenic or the like, a method in which calcium hydroxide is added to an iron salt or an aluminum salt (for example, see Non-Patent Document 1), or a method in which dealkalized silica is added ( For example, a method by chemical treatment as in Patent Document 1 is known.

しかしながら、これらの化学処理法では、固定化処理物中への有害成分の固定化が不十分であるため、固定化処理物が酸性雨等に接触してｐＨが低下したり、酸化還元作用を受けて元素の価数が変化したりすると、一旦は固定化された有害成分が雨水や地下水に溶出するため、重金属や砒素等の有害成分を含有する浸出水の漏出を完全に防止することは困難である。化学処理後の固定化処理物にセメントを添加して固化するセメント固化法は有害成分の溶出を防止する有力な方法であるが、化学処理と固化処理の二段処理であるためおよびセメント固化処理物の発生量が多いため、処理費が高くなるという欠点がある。   However, in these chemical treatment methods, the immobilization of harmful components in the immobilization treatment product is insufficient, so that the immobilization treatment product comes into contact with acid rain or the like to lower the pH, or the redox action. If the valence of the element changes, the harmful components once immobilized will elute into the rainwater and groundwater, so it is not possible to completely prevent leakage of leachate containing harmful components such as heavy metals and arsenic. Have difficulty. The cement solidification method, in which cement is added to the solidified product after chemical treatment and solidified, is a powerful method to prevent the elution of harmful components, but it is a two-stage treatment of chemical treatment and solidification treatment, and cement solidification treatment. There is a disadvantage that the processing cost becomes high because of the large amount of generated matter.

また、アロフェンまたは火山灰と水酸化カルシウムとを原材料に用いた重金属の吸着作用を有する汚水の浄化材および浄化方法（例えば、特許文献２参照。）も知られている。   In addition, a sewage purifying material and a purifying method (for example, see Patent Document 2) having an action of adsorbing heavy metals using allophane or volcanic ash and calcium hydroxide as raw materials are also known.

しかし、吸着作用を有する浄化材のみでは、排水基準（平成１６年５月環境省令第１６号）を達成することが困難で、固定化処理物の管理が必要であった。
日本鉱業会誌 １９７３年 第８９巻、１１月号（第１０２０号）、１０１〜１０６頁 特開２０００−２０４５４２号公報 特開平５−１３７９０５号公報 However, it was difficult to achieve the wastewater standard (Ministry of the Environment Ordinance No. 16 in May 2004) only with the purification material having an adsorption action, and it was necessary to manage the immobilization treatment.
Journal of the Japan Mining Association, 1973, 89, November (No. 1020), 101-106 JP 2000-204542 A JP-A-5-137905

本発明の目的は、重金属や砒素等の有害成分を含有する水溶液および／または泥状物を固定化して得られる固定化処理物が、酸性雨等の酸性液体に接触しても有害成分が簡単に溶出しないようにすることが可能な有害成分の固定化薬剤、およびこの固定化薬剤を用いた重金属や砒素等の有害成分を含有する水溶液および／または泥状物中の有害成分を容易に固定化する方法を提供することである。   The object of the present invention is to make it easy even if an immobilized treatment product obtained by immobilizing an aqueous solution and / or mud containing a harmful component such as heavy metal or arsenic comes into contact with an acidic liquid such as acid rain. Fixing of harmful components that can be prevented from eluting in water, and easily fixing harmful components in aqueous solutions and / or mud containing harmful components such as heavy metals and arsenic using this fixing agent Is to provide a way to

すなわち本発明の有害成分の固定化薬剤は、シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなることを特徴とし、有害成分を含有する水溶液および／または泥状物中の有害成分の固定化方法は、有害成分を含有する水溶液および／または泥状物に、有害成分に応じた前処理を行った後、有害成分を含有する水溶液および／または泥状物のｐＨが４〜１２の範囲になるように、シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなる有害成分の固定化薬剤を添加すること、またはこの固定化薬剤を添加し、次いでｐＨ調整剤を添加することを特徴とする。
なお、固定化とは、有害成分を捕捉し、有害成分の溶出を抑制することであり、これによって有害成分は無害化される。 That is, the harmful component immobilization agent of the present invention is characterized by comprising a silica material and a magnesium compound or a strontium compound, and the method for immobilizing a harmful component in an aqueous solution and / or mud containing the harmful component includes: The aqueous solution and / or mud containing the harmful component is pretreated according to the harmful component, and then the pH of the aqueous solution and / or the mud containing the harmful component is in the range of 4 to 12. In addition, it is characterized by adding an immobilizing agent of a harmful component comprising a silica material and a magnesium compound or a strontium compound, or adding this immobilizing agent and then adding a pH adjuster.
The immobilization means capturing harmful components and suppressing the elution of harmful components, thereby detoxifying the harmful components.

本発明の有害成分の固定化薬剤を使用して、重金属や砒素等の有害成分を含有する水溶液および／または泥状物を固定化して得られる固定化処理物は、酸性雨等の酸性液体に接触しても有害成分が簡単に溶出しない。本発明の有害成分の固定化薬剤を構成する材料は容易に安価に入手できる材料であり、取り扱いも容易で実用的である。   An immobilized treatment product obtained by immobilizing an aqueous solution and / or mud containing a harmful component such as heavy metal and arsenic using the harmful component immobilization agent of the present invention is converted into an acidic liquid such as acid rain. Hazardous components do not elute easily when contacted. The material constituting the harmful component-immobilized drug of the present invention is a material that can be easily obtained at low cost, and is easy to handle and practical.

以下、本発明を詳細に説明する。
本発明の重金属や砒素等の有害成分の固定化薬剤は、シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなる。 Hereinafter, the present invention will be described in detail.
The agent for immobilizing harmful components such as heavy metals and arsenic of the present invention comprises a silica material and a magnesium compound or a strontium compound.

固定化薬剤の構成成分の一つであるシリカ材料としては、火山灰などの火山噴出物、ガラスカレット、ガラス研磨スラッジ、シリカ質堆積物（けいそう土など）、粘土鉱物（ベントナイト、はくとう土など）、珪砂、石炭灰、シリカゲルおよびシリカヒュームなどが挙げられ、好ましくは火山噴出物、ガラスカレット、珪砂が使用される。これらは単独または組み合わせて使用される。   Silica materials that are one of the components of immobilization agents include volcanic eruptions such as volcanic ash, glass cullet, glass polishing sludge, siliceous deposits (such as diatomaceous earth), and clay minerals (bentonite, clay) Etc.), silica sand, coal ash, silica gel, silica fume and the like, and volcanic ejecta, glass cullet, and silica sand are preferably used. These are used alone or in combination.

このシリカ材料は、珪素（Ｓｉ）成分の含有量がシリカ（ＳｉＯ２）換算で５０〜９９．９重量％、好ましくは６０〜９０重量％、より好ましくは７０〜８５重量％のものである。ここで、シリカ換算の含有量とは、このシリカ材料中のＳｉ成分の全てがＳｉＯ2を形成しているとしたときの当該シリカ材料中のＳｉＯ2の含有量を意味する。
また、その平均粒子径は、通常０．１〜４００μｍ、好ましくは１〜１００μｍ、より好ましくは２〜２０μｍであり、その比表面積は、１００〜５，０００，０００ｃｍ２／ｇ、好ましくは５００〜５００,０００ｃｍ２／ｇ、より好ましくは１,０００〜１００,０００ｃｍ２／ｇである。０．１μｍ未満では取り扱い難くなり、また４００μｍを越えると反応性が低下し、好ましくない。 This silica material has a silicon (Si) component content of 50 to 99.9 wt%, preferably 60 to 90 wt%, more preferably 70 to 85 wt% in terms of silica (SiO 2 ). Here, the content of silica in terms means the content of SiO 2 of the silica material when all the Si component of the silica material is to be formed a SiO 2.
Moreover, the average particle diameter is 0.1-400 micrometers normally, Preferably it is 1-100 micrometers, More preferably, it is 2-20 micrometers, The specific surface area is 100-5,000,000 cm < 2 > / g, Preferably it is 500-. 500,000 cm 2 / g, more preferably 1,000 to 100,000 cm 2 / g. If it is less than 0.1 μm, handling becomes difficult, and if it exceeds 400 μm, the reactivity is lowered, which is not preferable.

このシリカ材料は、そのまま、乾燥および／または分級された加工品（市販品）、更には高温加熱発泡された加工品（市販品）等を用いることができる。   As this silica material, a dried and / or classified processed product (commercial product), a processed product subjected to high temperature heating foaming (commercial product), and the like can be used as they are.

固定化薬剤の構成成分のもう一つは、マグネシウム化合物またはストロンチウム化合物である。
マグネシウム化合物としては、マグネシウムの水酸化物、酸化物または炭酸塩等であり、具体的には、水酸化マグネシウム（Ｍｇ(ＯＨ)２）、酸化マグネシウム（ＭｇＯ）、炭酸マグネシウム（ＭｇＣＯ３）等であり、好ましくは水酸化マグネシウム、酸化マグネシウムが使用される。これらは単独または組み合わせて使用される。
マグネシウム化合物の平均粒子径は、通常０．１〜２００μｍ、好ましくは１〜１００μｍ、より好ましくは２〜２０μｍである。０．１μｍ未満では取り扱い難くなり、また２００μｍを越えると反応性が低下し、好ましくない。 Another component of the immobilized drug is a magnesium compound or a strontium compound.
Examples of the magnesium compound include magnesium hydroxide, oxide, carbonate, and the like. Specifically, magnesium hydroxide (Mg (OH) 2 ), magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), and the like. Yes, preferably magnesium hydroxide or magnesium oxide is used. These are used alone or in combination.
The average particle size of the magnesium compound is usually 0.1 to 200 μm, preferably 1 to 100 μm, more preferably 2 to 20 μm. If it is less than 0.1 μm, handling becomes difficult, and if it exceeds 200 μm, the reactivity is lowered, which is not preferable.

ストロンチウム化合物としては、ストロンチウムの水酸化物、酸化物または炭酸塩等であり、具体的には、水酸化ストロンチウム（Ｓｒ(ＯＨ)２）、酸化ストロンチウム（ＳｒＯ）、炭酸ストロンチウム（ＳｒＣＯ３）等であり、好ましくは炭酸ストロンチウムが使用される。これらは単独または組み合わせて使用される。
ストロンチウム化合物の平均粒子径は、通常０．１〜２００μｍ、好ましくは１〜１００μｍ、より好ましくは２〜２０μｍである。０．１μｍ未満では取り扱い難くなり、また２００μｍを越えると反応性が低下し、好ましくない。 Examples of the strontium compound include strontium hydroxide, oxide or carbonate, and specifically, strontium hydroxide (Sr (OH) 2 ), strontium oxide (SrO), strontium carbonate (SrCO 3 ), and the like. Yes, preferably strontium carbonate is used. These are used alone or in combination.
The average particle diameter of the strontium compound is usually 0.1 to 200 μm, preferably 1 to 100 μm, more preferably 2 to 20 μm. If it is less than 0.1 μm, handling becomes difficult, and if it exceeds 200 μm, the reactivity is lowered, which is not preferable.

固定化薬剤がシリカ材料とマグネシウム化合物とからなる場合、シリカ材料とマグネシウム化合物の割合を、シリカ材料中の珪素成分をシリカ換算した重量とマグネシウム化合物中に含有されるマグネシウム原子の重量との比（ＳｉＯ２：Ｍｇ）で表すと、通常１００：５〜１,０００であり、好ましくは１００：１０〜８００、より好ましくは１００：１５〜４００、更に好ましくは１００：２０〜２００である。
固定化薬剤がシリカ材料とストロンチウム化合物とからなる場合、シリカ材料とストロンチウム化合物の割合を、シリカ材料中の珪素成分をシリカ換算した重量とストロンチウム化合物中に含有されるストロンチウム原子の重量との比（ＳｉＯ２：Ｓｒ）で表すと、通常１００：２０〜１,５００であり、好ましくは１００：３０〜１，０００、より好ましくは１００：４０〜５００、更に好ましくは１００：５０〜２００である。
これらの組成範囲から外れると、固定化性能が低下し、好ましくない。 When the immobilization agent is composed of a silica material and a magnesium compound, the ratio of the silica material and the magnesium compound is determined by the ratio of the weight of the silicon component in the silica material converted to silica and the weight of the magnesium atom contained in the magnesium compound ( When expressed in terms of (SiO 2 : Mg), it is usually 100: 5 to 1,000, preferably 100: 10 to 800, more preferably 100: 15 to 400, and still more preferably 100: 20 to 200.
When the immobilization agent is composed of a silica material and a strontium compound, the ratio of the silica material and the strontium compound is determined by the ratio of the weight of the silicon component in the silica material converted to silica and the weight of the strontium atom contained in the strontium compound ( When expressed by SiO 2 : Sr), it is usually 100: 20 to 1,500, preferably 100: 30 to 1,000, more preferably 100: 40 to 500, and still more preferably 100: 50 to 200.
If it is out of these composition ranges, the immobilization performance is lowered, which is not preferable.

該固定化薬剤においては、カルシウム化合物は固定化性能を低下させるので、固定化薬剤、それを構成するシリカ材料、マグネシウム化合物、ストロンチウム化合物のそれぞれについて、カルシウム化合物の含有量がＣａＯ換算で好ましくは１０重量％以下、より好ましくは５重量％以下、更に好ましくは１重量％以下のものを使用するのが好ましい。   In the immobilization agent, the calcium compound decreases the immobilization performance. Therefore, the content of the calcium compound is preferably 10 in terms of CaO for each of the immobilization agent, the silica material constituting the immobilization agent, the magnesium compound, and the strontium compound. It is preferable to use those not more than wt%, more preferably not more than 5 wt%, still more preferably not more than 1 wt%.

この固定化薬剤は、粉末状または水スラリー状で使用される。取り扱い易さから、好ましくは水スラリー状で使用される。
水スラリー中の固定化薬剤含有量は、添加とｐＨ調整のし易さから、通常５〜５０重量％、好ましくは１０〜３０重量％とする。
この水スラリーは、通常、アルカリ性であり、例えば、５０重量％の火山灰（丸中白土（株）製、シルトＦ）と５０重量％の水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）とからなる固定化薬剤（ＳｉＯ２：Ｍｇ＝１００：５７）を２０重量％含有する水スラリーのｐＨは９〜１１である。 This immobilization drug is used in the form of powder or water slurry. In view of ease of handling, it is preferably used in the form of a water slurry.
The content of the immobilized drug in the water slurry is usually 5 to 50% by weight, preferably 10 to 30% by weight, because of easy addition and pH adjustment.
This water slurry is usually alkaline. For example, 50% by weight of volcanic ash (manufactured by Marunaka Shirato Co., Ltd., Silt F) and 50% by weight of magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg ( The pH of the water slurry containing 20% by weight of an immobilizing agent (SiO 2 : Mg = 100: 57) consisting of (OH) 2 purity: 95% by weight or more) is 9-11.

本発明の固定化方法は、有害成分を含有する水溶液および／または泥状物に、有害成分に応じた前処理を行った後、有害成分を含有する水溶液および／または泥状物のｐＨが４〜１２の範囲になるように、シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなる有害成分の固定化薬剤を添加すること、またはこの固定化薬剤を添加し、次いでｐＨ調整剤を添加することを特徴とし、このことによって水溶液および／または泥状物中の有害成分を容易に固定化するものである。   In the immobilization method of the present invention, an aqueous solution and / or mud containing a harmful component is pretreated according to the harmful component, and then the pH of the aqueous solution and / or the mud containing the harmful component is 4. Adding an immobilizing agent of a harmful component consisting of a silica material and a magnesium compound or a strontium compound, or adding this immobilizing agent, and then adding a pH adjusting agent so as to be in the range of ˜12. It is characterized by the fact that it can easily fix harmful components in aqueous solution and / or mud.

本発明の処理対象とする水溶液としては、有害成分を含有する排水、廃液、地下水、河川水等が挙げられ、例えば、工場排水や鉱山廃液、土壌を洗浄した排水がある。また泥状物としては、有害成分を含有する廃液処理によって発生したケーキ、建設汚泥、下水汚泥、鉱さい、燃殻、土壌等が挙げられる。
有害成分としては、砒素、水銀、クロム、セレン、カドミウム、鉛、アンチモン、亜鉛、銅、マンガン、コバルト、ニッケル、モリブデン、スズ、燐などの元素またはこれらの化合物が挙げられるが、これらに限定されるものではない。 Examples of the aqueous solution to be treated according to the present invention include wastewater containing harmful components, waste liquid, groundwater, river water, and the like. Examples include factory wastewater, mine wastewater, and wastewater from which soil has been washed. Examples of the muddy material include cakes, construction sludge, sewage sludge, slag, fuel shells, soil and the like generated by waste liquid treatment containing harmful components.
Hazardous components include, but are not limited to, elements such as arsenic, mercury, chromium, selenium, cadmium, lead, antimony, zinc, copper, manganese, cobalt, nickel, molybdenum, tin, phosphorus, or compounds thereof. It is not something.

本発明の方法において、重金属や砒素等の有害成分を含有する水溶液および／または泥状物に前記固定化薬剤を添加する前に、有害成分を固定化し易い形態にしたり、より毒性の少ない形態にして取り扱いを容易にしたりするために、有害成分に応じた前処理を行う。
前処理としては、有害成分に応じて、酸化剤、還元剤、共沈剤からなる群より選ばれた少なくとも一種の薬剤を、有害成分を含有する水溶液および／または泥状物に添加し、ｐＨを１〜４に調整する方法などが挙げられる。 In the method of the present invention, before adding the immobilizing agent to an aqueous solution and / or mud containing a harmful component such as heavy metal or arsenic, the harmful component can be easily fixed or less toxic. In order to facilitate handling, pre-treatment according to harmful components is performed.
As pretreatment, at least one agent selected from the group consisting of an oxidizing agent, a reducing agent, and a coprecipitation agent is added to an aqueous solution and / or mud containing the harmful component according to the harmful component, and the pH is increased. The method of adjusting to 1-4 is mentioned.

前記酸化剤としては、例えば、次亜塩素酸塩、第二鉄塩、第二銅塩、マンガン化合物等が挙げられ、なかでも次亜塩素酸ナトリウム、硫酸第二鉄、塩化第二鉄、硫酸第二銅、塩化第二銅、二酸化マンガンが好ましい。酸化剤の添加量は、有害成分を含有する水溶液および／または泥状物中に含有される還元態の有害成分を酸化態にするのに必要な化学量論量以上であり、例えば、第二鉄塩を使用して亜砒酸を砒酸塩にする時、第二鉄塩の量は、亜砒酸を基準に２モル倍以上である。
通常、水溶液および／または泥状物中の有害成分が、第一鉄塩のような溶解度の高いもの、亜砒酸塩のような共沈し難いもの、または亜砒酸塩のような有害ガスを発生し易いものであるとき、前記の酸化剤を添加し、これらを酸化することによって、各々、第二鉄塩のような難溶性のもの、砒酸塩のような共沈し易いもの、または有害ガスを発生し難いものにすることができる。 Examples of the oxidizing agent include hypochlorite, ferric salt, cupric salt, manganese compounds, etc., among them sodium hypochlorite, ferric sulfate, ferric chloride, sulfuric acid. Cupric, cupric chloride and manganese dioxide are preferred. The addition amount of the oxidizing agent is not less than the stoichiometric amount necessary for converting the reduced harmful component contained in the aqueous solution and / or the sludge containing the harmful component into the oxidized state, for example, the second When iron salt is used to convert arsenous acid to arsenate, the amount of ferric salt is 2 moles or more based on arsenous acid.
Usually, harmful components in aqueous solution and / or mud are likely to generate highly soluble substances such as ferrous salts, difficult to co-precipitate such as arsenite, or harmful gases such as arsenite. When these are added, the above oxidizing agents are added, and these are oxidized to generate insoluble substances such as ferric salts, coprecipitates such as arsenates, or harmful gases, respectively. Can be difficult.

前記還元剤としては、例えば、チオ硫酸塩、第一鉄塩、第一銅塩、亜硝酸塩、亜硫酸塩、硫黄化合物等が挙げられ、なかでもチオ硫酸ナトリウム、硫酸第一鉄、塩化第一鉄、硫酸第一銅、塩化第一銅、亜硝酸ナトリウム、亜硫酸ナトリウム、硫化鉄が好ましい。還元剤の添加量は、有害成分を含有する水溶液および／または泥状物中に含有される酸化態の有害成分を還元態にするのに必要な化学量論量以上であり、例えば、第一鉄塩を使用して６価クロムを３価クロムにする時、第一鉄塩の量は、６価クロムを基準に３モル倍以上である。
通常、水溶液および／または泥状物中の有害成分が、６価クロムや６価セレンのような溶解度の高いものであるとき、前記の還元剤を添加し、これらを還元することによって、３価クロムや４価セレンのような難溶性のものにすることができる。 Examples of the reducing agent include thiosulfate, ferrous salt, cuprous salt, nitrite, sulfite, sulfur compound, and the like. Among them, sodium thiosulfate, ferrous sulfate, ferrous chloride Cuprous sulfate, cuprous chloride, sodium nitrite, sodium sulfite and iron sulfide are preferred. The amount of the reducing agent added is equal to or more than the stoichiometric amount necessary for converting the oxidized harmful component contained in the aqueous solution and / or sludge containing the harmful component into the reduced state. When hexavalent chromium is converted to trivalent chromium using an iron salt, the amount of ferrous salt is 3 moles or more based on hexavalent chromium.
Usually, when a harmful component in an aqueous solution and / or a muddy substance is a highly soluble substance such as hexavalent chromium or hexavalent selenium, the above-mentioned reducing agent is added, and these are reduced to reduce trivalent. It can be made insoluble such as chromium and tetravalent selenium.

前記共沈剤としては、例えば、第二鉄塩、アルミニウム塩、第二銅塩、亜鉛塩、マグネシウム塩、カルシウム塩、金属リン酸塩等が挙げられ、なかでも硫酸第二鉄、塩化第二鉄、硫酸アルミニウム、第一リン酸塩（例えば、第一リン酸カルシウム、第一リン酸ナトリウム、第一リン酸カリウム、第一リン酸マグネシウムなど）が好ましい。共沈剤の添加量は、有害成分を含有する水溶液および／または泥状物中に含有される有害成分を基準に、通常２モル倍以上である。   Examples of the coprecipitation agent include ferric salt, aluminum salt, cupric salt, zinc salt, magnesium salt, calcium salt, metal phosphate and the like, among others, ferric sulfate, ferric chloride. Iron, aluminum sulfate, and primary phosphate (for example, primary calcium phosphate, primary sodium phosphate, primary potassium phosphate, primary magnesium phosphate, etc.) are preferred. The addition amount of the coprecipitation agent is usually 2 mol times or more based on the harmful components contained in the aqueous solution and / or mud containing the harmful components.

前記前処理においては、酸化剤、還元剤、共沈剤からなる群より選ばれた少なくとも一種の薬剤を、有害成分に応じて、有害成分を含有する水溶液および／または泥状物に添加し、ｐＨを１〜４の範囲に調整する。
使用する薬剤またはその量によって、薬剤を添加した水溶液および／または泥状物のｐＨは１〜４の範囲になる場合もあるし、範囲外になる場合もある。ｐＨを１〜４の範囲内にするため、または範囲内でｐＨを変更する場合に、酸またはアルカリであるｐＨ調整剤を添加してｐＨを調整する。すなわち、前処理において、必要によりｐＨ調整剤を添加してｐＨを調整する。 In the pretreatment, at least one agent selected from the group consisting of an oxidizing agent, a reducing agent, and a coprecipitation agent is added to an aqueous solution and / or a mud containing the harmful component, depending on the harmful component, Adjust the pH to the range of 1-4.
Depending on the drug used or its amount, the pH of the aqueous solution and / or mud containing the drug may be in the range of 1 to 4, or may be outside the range. In order to make pH into the range of 1-4, or when changing pH within the range, pH adjuster which is an acid or an alkali is added and pH is adjusted. That is, in the pretreatment, if necessary, a pH adjuster is added to adjust the pH.

この場合のｐＨ調整剤としては、硫酸、塩酸、燐酸、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウムおよび硫酸鉄等の酸性硫酸塩等が挙げられる。これらは水溶液または水スラリーで添加される。
また、酸化カルシウム、水酸化カルシウム及び炭酸カルシウム等のカルシウム化合物は、この場合、固定化性能を低下させるので好ましくない。 Examples of the pH adjuster in this case include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and iron sulfate sulfate. These are added as aqueous solutions or water slurries.
In this case, calcium compounds such as calcium oxide, calcium hydroxide and calcium carbonate are not preferable because they deteriorate the fixing performance.

前処理を行った後、有害成分を含有する水溶液および／または泥状物に、水溶液および／または泥状物のｐＨが４〜１２の範囲になるように前記固定化薬剤を添加し、または前記固定化薬剤を添加し、次いでｐＨ調整剤を添加し、有害成分を固定化する。
前処理を行った後、固定化薬剤を添加する際に、固定化薬剤の構成成分であるシリカ材料と、マグネシウム化合物またはストロンチウム化合物とを別々に添加しても良い。 After the pretreatment, the immobilized agent is added to the aqueous solution and / or mud containing the harmful component so that the pH of the aqueous solution and / or the mud is in the range of 4 to 12, or An immobilizing agent is added, and then a pH adjuster is added to immobilize harmful components.
After the pretreatment, when the immobilizing agent is added, the silica material that is a component of the immobilizing agent and the magnesium compound or the strontium compound may be added separately.

前記したとおり、本発明の固定化薬剤は、通常、アルカリ性を呈しており、この固定化薬剤を、前処理して得た水溶液および／または泥状物に、ｐＨが４〜１２の範囲になるように添加する。本発明の固定化薬剤を添加した後に目的とするｐＨの範囲にならない時には、固定化薬剤を添加し、次いでｐＨ調整剤を添加する。
ｐＨが４〜１２の範囲内で有害成分のそれぞれにとって最適なｐＨ範囲が存在し、そのｐＨとなるように添加するのが好ましい。例えば、下記するように、有害成分が砒素の場合にはｐＨ５〜９、有害成分が６価クロムの場合にはｐＨ７〜９とするのが好ましい。
また、ｐＨが最適ｐＨから外れたり、ｐＨ４〜１２の範囲内でｐＨを変更したりする場合等、必要によりｐＨ調整剤を添加して行う。
ｐＨ調整剤としては、硫酸、塩酸、燐酸、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、酸化カルシウム、水酸化カルシウム、炭酸カルシウムおよび硫酸鉄等の酸性硫酸塩等が挙げられる。これらは水溶液または水スラリーで添加される。
固定化薬剤の添加で目的とするｐＨの範囲にならない時には、ｐＨ調整剤として、通常、上記ｐＨ調整剤のうちのアルカリ化合物である水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、酸化カルシウム、水酸化カルシウムまたは炭酸カルシウムが添加される。
ｐＨ調整剤として、酸化カルシウム、水酸化カルシウムまたは炭酸カルシウムを使用する場合は、前記固定化薬剤を添加した後に添加する。固定化薬剤の添加よりも前に添加することは、固定化性能が低下するので好ましくない。 As described above, the immobilized drug of the present invention is usually alkaline, and the pH is in the range of 4 to 12 in an aqueous solution and / or mud obtained by pretreating this immobilized drug. Add as follows. When the target pH is not reached after the immobilizing agent of the present invention is added, the immobilizing agent is added, and then the pH adjusting agent is added.
There is an optimum pH range for each of the harmful components within the pH range of 4 to 12, and it is preferable to add such a pH. For example, as described below, when the harmful component is arsenic, the pH is preferably 5 to 9, and when the harmful component is hexavalent chromium, the pH is preferably 7 to 9.
In addition, when the pH deviates from the optimum pH or when the pH is changed within the range of pH 4 to 12, a pH adjusting agent is added as necessary.
pH adjusters include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium oxide, calcium hydroxide, calcium carbonate, and iron sulfate. Examples include salts. These are added as aqueous solutions or water slurries.
When the target pH range is not reached by addition of the immobilizing agent, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, carbonic acid, which is an alkali compound of the above pH adjusters, is usually used as the pH adjuster. Potassium, potassium bicarbonate, calcium oxide, calcium hydroxide or calcium carbonate is added.
When calcium oxide, calcium hydroxide or calcium carbonate is used as a pH adjuster, it is added after the immobilizing agent is added. Addition before the addition of the immobilizing agent is not preferable because immobilization performance is deteriorated.

前処理と固定化の具体的な例について説明する。
（１）砒素含有廃液の場合
前処理として砒素含有廃液に硫酸第二鉄水溶液を添加してｐＨを１．５〜２．５にし、次にこの廃液のｐＨが５〜９になるように、前記固定化薬剤を添加する。このことにより、有害成分である砒素と酸化／共沈剤である硫酸第二鉄と固定化薬剤とが反応して、水に不溶性のもの（シリカ化合物など）が生成し、有害成分が固定化される。
（２）６価クロム含有廃液の場合
前処理として６価クロム含有廃液に硫酸第一鉄と硫酸第二鉄の混合水溶液を添加し、さらに硫酸を添加してｐＨを２〜２．５にし、次にこの廃液のｐＨが７〜９になるように前記固定化薬剤を添加する。このことにより、有害成分である６価クロムと還元／共沈剤である混合硫酸鉄（硫酸第一鉄と硫酸第二鉄）と固定化薬剤とが反応して、水に不溶性のもの（シリカ化合物など）が生成し、有害成分が固定化される。
（３）鉛含有廃液の場合
前処理として鉛含有廃液に硫酸第一鉄と硫酸第二鉄の混合水溶液を添加し、さらに第一リン酸マグネシウムの水スラリーを添加する。必要に応じて硫酸を添加し、ｐＨを２〜３にする。次にこの廃液のｐＨが５〜７になるように前記固定化薬剤を添加し、次いでこの廃液のｐＨが９〜１０になるように水酸化カルシウムを添加する。このことにより、有害成分である鉛と還元／共沈剤である混合硫酸鉄（硫酸第一鉄と硫酸第二鉄）と共沈剤である第一リン酸マグネシウムと固定化薬剤とが反応して、水に不溶性のもの（シリカ化合物など）が生成し、有害成分が固定化される。 A specific example of preprocessing and immobilization will be described.
(1) In the case of arsenic-containing waste liquid As a pretreatment, an aqueous ferric sulfate solution is added to the arsenic-containing waste liquid to adjust the pH to 1.5 to 2.5, and then the pH of this waste liquid is adjusted to 5 to 9, Add the immobilized drug. As a result, arsenic, which is a harmful component, ferric sulfate, which is an oxidizing / co-precipitating agent, and an immobilizing agent react with each other to produce water-insoluble substances (such as silica compounds), and the harmful component is immobilized. Is done.
(2) In the case of hexavalent chromium-containing waste liquid As a pretreatment, a mixed aqueous solution of ferrous sulfate and ferric sulfate is added to the hexavalent chromium-containing waste liquid, and sulfuric acid is further added to adjust the pH to 2 to 2.5. Next, the immobilizing agent is added so that the pH of the waste liquid becomes 7-9. As a result, hexavalent chromium which is a harmful component, mixed iron sulfate (ferrous sulfate and ferric sulfate) which is a reducing / coprecipitation agent reacts with the immobilizing agent, and is insoluble in water (silica). Compound, etc.) are generated, and harmful components are immobilized.
(3) In the case of lead-containing waste liquid As a pretreatment, a mixed aqueous solution of ferrous sulfate and ferric sulfate is added to the lead-containing waste liquid, and an aqueous slurry of magnesium phosphate is further added. Sulfuric acid is added as necessary to bring the pH to 2-3. Next, the immobilizing agent is added so that the pH of the waste liquid becomes 5 to 7, and then calcium hydroxide is added so that the pH of the waste liquid becomes 9 to 10. As a result, lead, which is a harmful component, mixed iron sulfate (ferrous sulfate and ferric sulfate) which is a reducing / coprecipitation agent, magnesium phosphate which is a coprecipitation agent, and the immobilized agent react with each other. As a result, water-insoluble substances (such as silica compounds) are generated, and harmful components are immobilized.

本発明の固定化方法では、シアン化水素（ＨＣＮ）、アルシン（ＡｓＨ３）等の発生が予想される場合、前処理の際に酸化還元電位を調整することによって、これらのガス等の発生を抑制するのが好ましい。 In the immobilization method of the present invention, when generation of hydrogen cyanide (HCN), arsine (AsH 3 ) or the like is expected, the generation of these gases or the like is suppressed by adjusting the oxidation-reduction potential during the pretreatment. Is preferred.

具体的には、例えば下記の（１）〜（６）の方法が挙げられる。
（１）シアン化合物と砒素を含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、ｐＨ１０以上の条件下で次亜塩素酸ナトリウム水溶液等の次亜塩素酸塩の水溶液を酸化還元電位が３００〜３５０ｍＶになるまで添加し、０〜１０分間保持し、次いでｐＨを７〜８に調整し、次亜塩素酸ナトリウム水溶液等の次亜塩素酸塩の水溶液を酸化還元電位が６００〜６５０ｍＶになるまで添加し、０〜３０分間保持し、シアン化合物を事前に酸化分解し有害なシアン化水素の発生を抑制した後、硫酸第二鉄水溶液等の第二鉄塩の水溶液を、Ｆｅ３＋／Ａｓモル比が２倍以上、好ましくは５倍以上、より好ましくは１０倍以上となる量を添加し、砒素の固定化処理中の有害なアルシンの発生を抑制する。 Specific examples include the following methods (1) to (6).
(1) In the case of an aqueous solution and / or mud containing cyanide and arsenic, an aqueous solution of hypochlorite, such as an aqueous sodium hypochlorite solution, under the condition of pH 10 or higher. Until the oxidation-reduction potential reaches 300 to 350 mV, hold for 0 to 10 minutes, then adjust the pH to 7 to 8, and add an aqueous solution of hypochlorite such as an aqueous sodium hypochlorite solution to the oxidation-reduction potential. Is added until it reaches 600 to 650 mV, and held for 0 to 30 minutes. After the cyanide is oxidatively decomposed in advance to prevent generation of harmful hydrogen cyanide, an aqueous solution of a ferric salt such as an aqueous ferric sulfate solution is added. The amount of Fe 3+ / As molar ratio is 2 times or more, preferably 5 times or more, more preferably 10 times or more, to suppress generation of harmful arsine during the arsenic immobilization treatment.

（２）ｐＨ１０において酸化還元電位（以下、換算酸化還元電位という）が３００ｍＶ未満で、砒素を含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、アルカリ条件下で次亜塩素酸ナトリウム水溶液等の次亜塩素酸塩の水溶液を換算酸化還元電位が３００〜５００ｍＶになるまで添加した後、硫酸第二鉄水溶液等の第二鉄塩の水溶液を、Ｆｅ３＋／Ａｓモル比が２倍以上、好ましくは５倍以上、より好ましくは１０倍以上となる量を添加し、砒素の固定化処理中の有害なアルシンの発生を抑制する。 (2) In the case of an aqueous solution and / or mud containing arsenic having a redox potential (hereinafter referred to as a reduced redox potential) of less than 300 mV at pH 10, the aqueous solution and / or the mud are subjected to the following under alkaline conditions. After adding an aqueous solution of hypochlorite such as an aqueous solution of sodium chlorite until the reduced redox potential becomes 300 to 500 mV, an aqueous solution of ferric salt such as an aqueous solution of ferric sulfate is added to Fe 3+ / As mol. Addition of an amount that makes the ratio 2 times or more, preferably 5 times or more, more preferably 10 times or more, suppresses the generation of harmful arsine during the arsenic immobilization treatment.

（３）換算酸化還元電位が３００〜８００ｍＶで、砒素を含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、硫酸第二鉄水溶液等の第二鉄塩の水溶液を、Ｆｅ３＋／Ａｓモル比が２倍以上、好ましくは５倍以上、より好ましくは１０倍以上となる量を添加し、砒素の固定化処理中の有害なアルシンの発生を抑制する。なお、この場合、既にアルシンが発生し難い状態になっているので、敢えて次亜塩素酸塩の水溶液等を添加して酸化還元電位を調整しなくても良い。 (3) In the case of an aqueous solution and / or mud containing an arsenic having an equivalent oxidation-reduction potential of 300 to 800 mV, an aqueous solution of a ferric salt such as a ferric sulfate aqueous solution is added to the aqueous solution and / or the mud. , Fe 3+ / As molar ratio is added 2 times or more, preferably 5 times or more, more preferably 10 times or more to suppress generation of harmful arsine during arsenic immobilization treatment. In this case, since arsine is already hardly generated, it is not necessary to adjust the redox potential by adding a hypochlorite aqueous solution or the like.

（４）換算酸化還元電位が８００ｍＶを越え、砒素を含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、アルカリ条件下でチオ硫酸ナトリウム水溶液等のチオ硫酸塩の水溶液を換算酸化還元電位が５００〜８００ｍＶになるまで添加した後、硫酸第二鉄水溶液等の第二鉄塩の水溶液を、Ｆｅ３＋／Ａｓモル比が２倍以上、好ましくは５倍以上、より好ましくは１０倍以上となる量を添加し、砒素の固定化処理中の有害なアルシンの発生を抑制する。なお、このように換算酸化還元電位が８００ｍＶを越える場合、水溶液および／または泥状物中に次亜塩素酸ナトリウム水溶液等の次亜塩素酸塩が含有している可能性がある為、同時に固定化処理中の有害な塩素の発生を抑制している。 (4) In the case of an aqueous solution and / or mud containing an arsenic whose converted oxidation-reduction potential exceeds 800 mV, an aqueous solution of thiosulfate such as an aqueous sodium thiosulfate solution is used in the aqueous solution and / or mud under alkaline conditions. Is added until the converted oxidation-reduction potential reaches 500 to 800 mV, and then an aqueous solution of ferric salt such as ferric sulfate aqueous solution has an Fe 3+ / As molar ratio of 2 times or more, preferably 5 times or more, more preferably Is added in an amount of 10 times or more to suppress the generation of harmful arsine during the arsenic immobilization process. In addition, when the converted oxidation-reduction potential exceeds 800 mV, hypochlorite such as sodium hypochlorite aqueous solution may be contained in the aqueous solution and / or the sludge, so that it is fixed at the same time. The generation of harmful chlorine during chemical treatment is suppressed.

（５）換算酸化還元電位が５０ｍＶ未満で、セレンを含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、アルカリ条件下で硫酸第ニ鉄水溶液等の第ニ鉄塩の水溶液を、Ｆｅ3＋／Ｓｅモル比が４倍以上となる量、かつ換算酸化還元電位が５０〜２５０ｍＶになるまで添加し、セレンの固定化処理中の有害なセレン化水素の発生を抑制する。 (5) In the case of an aqueous solution and / or mud containing a selenium having a reduced redox potential of less than 50 mV, a ferric salt such as a ferric sulfate aqueous solution under alkaline conditions in the aqueous solution and / or mud Is added until the Fe 3+ / Se molar ratio is 4 times or more and the reduced oxidation-reduction potential is 50 to 250 mV to suppress generation of harmful hydrogen selenide during the selenium immobilization treatment. .

(６)換算酸化還元電位が２５０ｍＶを越え、セレンを含有する水溶液および／または泥状物の場合、水溶液および／または泥状物に、アルカリ条件下で硫酸第一鉄水溶液等の第一鉄塩の水溶液を、Ｆｅ2＋／Ｓｅモル比が２倍以上となる量、かつ換算酸化還元電位が５０〜２５０ｍＶになるまで添加し、セレンの固定化処理中の有害なセレン化水素の発生を抑制する。 (6) In the case of an aqueous solution and / or mud containing an equivalent oxidation-reduction potential exceeding 250 mV and containing selenium, a ferrous salt such as an aqueous ferrous sulfate solution is used in the aqueous solution and / or mud under alkaline conditions. Is added until the Fe 2+ / Se molar ratio is doubled or more and the reduced oxidation-reduction potential is 50 to 250 mV, thereby suppressing generation of harmful hydrogen selenide during the selenium immobilization treatment. .

本発明の固定化方法は、キレート剤、吸着剤（活性アルミナ、活性炭など）または凝集剤等を用いる処理方法を施した水溶液および／または泥状物に適用しても良いし、また本発明の固定化方法を施した水溶液および／または泥状物に対してキレート剤、吸着剤（活性アルミナ、活性炭など）または凝集剤等を用いる処理方法を適用しても良い。   The immobilization method of the present invention may be applied to an aqueous solution and / or mud that has been subjected to a treatment method using a chelating agent, an adsorbent (active alumina, activated carbon, etc.) or a flocculant. A treatment method using a chelating agent, an adsorbent (active alumina, activated carbon, etc.), a flocculant, or the like may be applied to the aqueous solution and / or the sludge subjected to the immobilization method.

本発明では、有害ガスが発生する可能性があることから、固定化に使用する反応槽、攪拌装置、送液装置、水溶液および／または泥状物と接する部分等は、ガラス（強化ガラス、耐熱ガラスなど）、ガラス繊維、繊維強化プラスチック、セラミック、または耐酸モルタル等の材料からなるものが好ましい。また同様の理由から、金属粉粒子を含有する水溶液を処理する場合、事前に水溶液中の金属微粒子を濾過または沈降分離等により除去した後、処理することが好ましい。   In the present invention, since harmful gas may be generated, the reaction tank, the stirring device, the liquid feeding device, the portion in contact with the aqueous solution and / or the muddy material, etc. used for immobilization are made of glass (tempered glass, heat resistant Glass, etc.), glass fiber, fiber reinforced plastic, ceramic, or acid resistant mortar is preferred. For the same reason, when treating an aqueous solution containing metal powder particles, it is preferable to treat the metal fine particles in the aqueous solution in advance after removing them by filtration or sedimentation separation.

本発明では、有害成分を含有する水溶液および／または泥状物を固定化して得られる固定化処理物を放置熟成することによって、有害成分の溶出抑制効果が高くなる。水溶液処理の場合、固定化後の固定化処理物と上澄み液を固液分離し熟成することが好ましい。熟成時間は長いほど溶出抑制効果が強化されるため、固定化処理物を２０時間以上放置、熟成することが好ましい。熟成は、例えば、静置条件下、０〜４０℃の空気中で行われる。
また熟成が完了するまでは、固定化処理物を酸性液体に接触させるのは好ましくない。 In the present invention, the effect of suppressing the elution of harmful components is enhanced by leaving and aging an immobilized treatment product obtained by immobilizing an aqueous solution and / or mud containing a harmful component. In the case of an aqueous solution treatment, it is preferable to solidify the immobilization treatment product and the supernatant after immobilization and ripen. The longer the aging time is, the stronger the elution suppressing effect is. Therefore, it is preferable that the immobilization product is left for aging for 20 hours or more. Aging is performed, for example, in air at 0 to 40 ° C. under stationary conditions.
In addition, it is not preferable to bring the immobilized treatment product into contact with the acidic liquid until ripening is completed.

本発明の前記固定化薬剤に代えて、水酸化カルシウム、水酸化マグネシウム等を用いる固定化では、有害成分の固定化が不十分であるため、固定化後の固定化処理物が酸性雨等に接触してｐＨが低下したりすると、一旦は固定化された有害成分が液中に溶出する。この場合、液中に溶出する有害成分が排水基準（例えば、砒素の場合、０．１ｍｇ／ｌ以下）を達成することができない。従って、固定化処理物を埋立て処分した場合、浸出水の恒久対策が必要となる。
溶出の有無は、固定化処理物を酸性水溶液を用いて洗浄し、液中に溶出する有害成分（砒素など）を定量すること（酸洗浄溶出試験）により調べることができる。
例えば、砒素の排水基準は０．１ｍｇ／ｌ以下であるが、固定化条件の変動、固定化処理物の処分環境の変動等もあるので、実用的には、この酸洗浄溶出試験で約０．０５ｍｇ/ｌ以下を奏する固定化方法が好ましく採用される。 In the immobilization using calcium hydroxide, magnesium hydroxide or the like instead of the immobilization agent of the present invention, the immobilization of harmful components is insufficient. When the pH decreases due to contact, the harmful components once immobilized are eluted in the liquid. In this case, the harmful component eluted in the liquid cannot achieve the waste water standard (for example, 0.1 mg / l or less in the case of arsenic). Therefore, when the immobilization treatment is disposed of in landfill, permanent measures for leachate are required.
The presence or absence of elution can be examined by washing the immobilized product with an acidic aqueous solution and quantifying harmful components (such as arsenic) eluted in the solution (acid washing elution test).
For example, the drainage standard for arsenic is 0.1 mg / l or less, but there are also fluctuations in immobilization conditions, changes in the disposal environment of the immobilization treatment, etc. An immobilization method of 0.05 mg / l or less is preferably employed.

本発明においては、有害成分の固定化薬剤の原料として、日本全国に分布する火山灰などの火山噴出物および粘土鉱物などの有効利用や、ガラスカレットおよびガラス研磨スラッジなどの廃棄物利用を図ることができ、マグネシウム化合物を含め、容易に安価に入手できる材料を用いて、重金属や砒素等の有害成分を含有する水溶液および／または泥状物中の有害成分を容易に固定化することができ、固定化処理物が酸性雨等の酸性液体と接触しても有害成分の漏洩を防止することが可能である。   In the present invention, it is possible to effectively use volcanic eruptions such as volcanic ash and clay minerals distributed throughout Japan, as well as wastes such as glass cullet and glass polishing sludge, as raw materials for harmful component immobilization agents. It is possible to fix and easily fix harmful components in aqueous solutions and / or mud containing toxic components such as heavy metals and arsenic using materials that can be easily obtained at low cost, including magnesium compounds. Leakage of harmful components can be prevented even when the chemical treatment product comes into contact with an acidic liquid such as acid rain.

以下、本発明を実施例で詳細に説明するが、本発明はこれらに限定されるものではない。
なお、成分濃度や物性の測定は次の方法で行った。
（１）砒素濃度：ＪＩＳ Ｋ ０１０２ ６１．２水素化物発生原子吸光法 備考３に基づいて行った。
（２）鉛濃度：濃度が高い場合はＪＩＳ Ｋ ０１０２ ５４．２フレーム原子吸光法に基づき、濃度が低い場合はＪＩＳ Ｋ ０１０２ ６５．１．３電気加熱原子吸光法に基づいて行った。
（３）燐濃度：ＪＩＳ Ｋ ０１０２ ４６．３．１またはＪＩＳ Ｋ ０１０２ ４６．３．３の前処理を行った後にＪＩＳ Ｋ ０１０２ ４６．１．１モリブデン青・アスコルビン酸還元吸光光度法に基づいて行った。
（４）平均粒子径：マイクロトラック粒度分布測定装置９３２０ＨＲＡ（Ｘ−１００）（日機装（株）製）を用いて求めた。
（５）比表面積：流動法ＢＥＴ一点法比表面積測定装置ＭＯＮＯＳＯＲＢ（ユアサアイオニクス（株）製）を用いて求めた。
（６）結晶性：Ｘ線回折装置ＲＡＤ−ＲＢ ＲＵ−２００（（株）リガク製）を用いて求めた。
（７）アルシン濃度：ガス検知器（新コスモス電機（株）製：商品名“ＸＤ−３０３ＡＨ”）を用いて測定した。
（８）ｐＨ：ハンディータイプｐＨメーター（堀場（株）製：商品名“Ｄ−２２”、ｐＨ電極９６２１−１０Ｄ付き）を用いて測定した。
（９）酸化還元電位：ポータブルＯＲＰ計（東亜ディーケーケー（株）製：商品名“ＲＭ−２０Ｐ”、複合センサーＰＳＴ−２７３９Ｃ付き）を用いて測定し、水素電極基準値で表した。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
The component concentration and physical properties were measured by the following method.
(1) Arsenic concentration: Measured based on JIS K 0102 61.2 Hydride generation atomic absorption method Remark 3.
(2) Lead concentration: When the concentration was high, it was based on JIS K 0102 54.2 flame atomic absorption method, and when the concentration was low, it was based on JIS K 0102 65.1.3.
(3) Phosphorus concentration: after pretreatment of JIS K 0102 46.3.1 or JIS K 0102 463.3, based on JIS K 0102 46.1.1 Molybdenum Blue / Ascorbic Acid Reduction Spectrophotometry went.
(4) Average particle diameter: It was determined using a Microtrac particle size distribution analyzer 9320HRA (X-100) (manufactured by Nikkiso Co., Ltd.).
(5) Specific surface area: It was determined using a flow method BET single point method specific surface area measuring device MONOSORB (manufactured by Yuasa Ionics Co., Ltd.).
(6) Crystallinity: It was determined using an X-ray diffractometer RAD-RB RU-200 (manufactured by Rigaku Corporation).
(7) Arsine concentration: measured using a gas detector (manufactured by Shin Cosmos Electric Co., Ltd .: trade name “XD-303AH”).
(8) pH: Measured using a handy type pH meter (manufactured by Horiba, Ltd .: trade name “D-22”, with pH electrode 9621-10D).
(9) Oxidation-reduction potential: Measured using a portable ORP meter (manufactured by Toa DKK Co., Ltd .: trade name “RM-20P”, with combined sensor PST-2739C), and expressed as a hydrogen electrode reference value.

実施例１
（有害成分の固定化薬剤の調製）
シリカ材料として火山灰のシルトＦ（丸中白土（株）製）を用いた。
該シルトＦは、Ｓｉ、Ａｌ、Ｆｅ、Ｃａ、Ｍｇ、ＫおよびＮａ成分のそれぞれを、ＳｉＯ２に換算して７１．１重量％、Ａｌ２Ｏ３に換算して１２〜１４重量％、Ｆｅ２Ｏ３に換算して１〜２重量％、ＣａＯに換算して１．２重量％、ＭｇＯに換算して０．０５〜０．１２重量％、Ｋ２Ｏに換算して１．５〜３．５重量％、Ｎａ２Ｏに換算して１．８〜３．２重量％含有し、更に鉛を０．６ｐｐｍ以下、砒素を０．０５ｐｐｍ以下、リンを２０ｐｐｍ以下、水分を２．２重量％含有し、平均粒子径が８．１μｍ、比表面積が１６９，０００ｃｍ２／ｇで非晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該水酸化マグネシウムは、Ｍｇ原子を４０．５重量％（Ｍｇ(ＯＨ)２に換算すると９７．１重量％）、Ｃａ成分をＣａＯに換算して０．２９重量％、水分を０．５３重量％含有し、平均粒子径が４．２μｍのものである。
該シルトＦ５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％の火山灰と５０重量％の水酸化マグネシウムとからなる固定化薬剤Ａ（ＳｉＯ２：Ｍｇ＝１００：５７）を調製した。 Example 1
(Preparation of immobilized drug for harmful components)
Volcanic ash silt F (manufactured by Marunaka Shirato Co., Ltd.) was used as the silica material.
The silt F is, Si, Al, Fe, Ca, Mg, respectively K and Na component, 71.1 wt% in terms of SiO 2, 12 to 14 wt% in terms of Al 2 O 3, Fe 1 to 2% by weight in terms of 2 O 3 , 1.2% by weight in terms of CaO, 0.05 to 0.12% in terms of MgO, 1.5 to 5% in terms of K 2 O 3.5% by weight, converted to Na 2 O, 1.8 to 3.2% by weight, lead 0.6 ppm or less, arsenic 0.05 ppm or less, phosphorus 20 ppm or less, moisture 2.2 It is contained by weight%, has an average particle diameter of 8.1 μm, a specific surface area of 169,000 cm 2 / g, and is amorphous.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
The magnesium hydroxide has 40.5 wt% Mg atoms (97.1 wt% converted to Mg (OH) 2 ), 0.29 wt% Ca component converted to CaO, and 0.53 wt% water. The average particle diameter is 4.2 μm.
50 parts by weight of Silt F and 50 parts by weight of magnesium hydroxide are mixed to prepare an immobilizing agent A (SiO 2 : Mg = 100: 57) composed of 50% by weight of volcanic ash and 50% by weight of magnesium hydroxide. did.

（砒素含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４３０ｍｇ／ｌ、ｐＨ９．９８、酸化還元電位＋４０８ｍＶ（換算酸化還元電位：＋４０７ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が９．３倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．７５であった。 (Immobilization of waste liquid containing arsenic)
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid with an As concentration of 430 mg / l, pH 9.98, oxidation-reduction potential +408 mV (converted oxidation-reduction potential: +407 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 9.3 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.75.

次に、前処理した砒素含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように前記固定化薬剤Ａを添加した。具体的には、固定化薬剤Ａ２０ｇと水８０ｇを混合して得られた水スラリーを９６．０ｇ（固定化薬剤Ａとして１９．２０ｇ）添加し、更に１５分間反応させた。固定化薬剤Ａ添加後の砒素含有廃液のｐＨは６．１７であった。固定化薬剤Ａ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９３時間保持して熟成し、含水率４０重量％の固定化処理物３５ｇを得た。濾液の砒素濃度は０．０１ｍｇ／ｌ未満であった。   Next, the immobilizing agent A was added to the pretreated arsenic-containing waste liquid while stirring in a room temperature atmosphere so that the pH of the waste liquid was about 6. Specifically, 96.0 g of water slurry obtained by mixing 20 g of immobilized drug A and 80 g of water (19.20 g as immobilized drug A) was added, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilized drug A was 6.17. After the reaction of adding the immobilized drug A, stirring is stopped, and then the resulting cake (immobilized product) is allowed to stand for 30 minutes to settle, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 93 hours in air at room temperature to obtain 35 g of immobilization treatment product having a water content of 40% by weight. The arsenic concentration of the filtrate was less than 0.01 mg / l.

（酸洗浄溶出試験１）
次に、得られた含水率４０重量％の固定化処理物２０ｇをフッ素樹脂製撹拌羽根を備えたガラス製容器に入れ、次いでｐＨ２．５に調整した塩酸溶液を固定化処理物の３０倍量を加えてスラリー化した後、室温雰囲気で攪拌しながら、スラリーのｐＨが常に２．５〜２．６となるように０．５ｍｏｌ／ｌ塩酸溶液でｐＨ調整しながら、６時間攪拌した。次に、このスラリーを粒子保持能力１．０μｍのガラス繊維製濾紙で濾過し、この濾液の砒素濃度を測定した。濾液の砒素濃度は０．０２ｍｇ／ｌであった。 (Acid washing dissolution test 1)
Next, 20 g of the obtained immobilization treatment product having a water content of 40% by weight is put into a glass container equipped with a fluororesin stirring blade, and then the hydrochloric acid solution adjusted to pH 2.5 is 30 times the immobilization treatment product. Then, the mixture was stirred at room temperature for 6 hours while adjusting the pH with a 0.5 mol / l hydrochloric acid solution so that the pH of the slurry was always 2.5 to 2.6. Next, the slurry was filtered through a glass fiber filter paper having a particle holding capacity of 1.0 μm, and the arsenic concentration of the filtrate was measured. The arsenic concentration of the filtrate was 0.02 mg / l.

（アルシン発生濃度）
上記の各工程におけるアルシン発生濃度を測定した。この結果を表１に示す。
また、このときの廃液のｐＨおよび酸化還元電位をあわせて表１に示す。 (Arsine concentration)
The arsine generation concentration in each of the above steps was measured. The results are shown in Table 1.
In addition, the pH and oxidation-reduction potential of the waste liquid at this time are shown in Table 1.

Figure 2007125536
Figure 2007125536

実施例２
（有害成分の固定化薬剤の調製）
シリカ材料として火山灰の前記シルトＦ（丸中白土（株）製）を用いた。
ストロンチウム化合物として炭酸ストロンチウム（和光純薬工業（株）製、ＳｒＣＯ３純度：９５重量％以上）を用いた。
該炭酸ストロンチウムは、Ｓｒ原子を５６．７重量％（ＳｒＣＯ３に換算すると９５．５重量％）、Ｃａ成分をＣａＯに換算して０．０９重量％、水分を０．１重量％含有し、平均粒子径が３．３μｍのものである。
該シルトＦ５０重量部と、該炭酸ストロンチウム５０重量部を混合し、５０重量％の火山灰と５０重量％の炭酸ストロンチウムとからなる固定化薬剤Ｂ（ＳｉＯ２：Ｓｒ＝１００：８０）を調製した。 Example 2
(Preparation of immobilized drug for harmful components)
The silt F of volcanic ash (manufactured by Marunaka Shirato Co., Ltd.) was used as the silica material.
As the strontium compound, strontium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., SrCO 3 purity: 95% by weight or more) was used.
The strontium carbonate contains 56.7% by weight of Sr atoms (95.5% by weight when converted to SrCO 3 ), 0.09% by weight when converted to CaO, and 0.1% by weight of water, The average particle size is 3.3 μm.
50 parts by weight of the silt F and 50 parts by weight of the strontium carbonate were mixed to prepare an immobilizing agent B (SiO 2 : Sr = 100: 80) composed of 50% by weight of volcanic ash and 50% by weight of strontium carbonate.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｂを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３７０ｍｇ／ｌ、ｐＨ９．８０、酸化還元電位＋４０７ｍＶ（換算酸化還元電位：＋３９５ｍＶ）の砒素含有廃液１Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．３４）を用いて調製した４１重量％水溶液を２６．０ｇ（Ｆｅ３＋／Ａｓモル比が１０．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８１であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｂ３０ｇと水１２０ｇを混合して得られた水スラリーを１３４．３ｇ（固定化薬剤Ｂとして２６．８６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｂを添加後の砒素含有廃液のｐＨは５．９７であった。固定化薬剤Ｂ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約１Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に６５時間保持して熟成し、含水率１９重量％の固定化処理物４３ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率１９重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug B was used.
In a glass container equipped with a fluororesin stirring blade, 1 L of an arsenic-containing waste liquid having an As concentration of 370 mg / l, pH 9.80, oxidation-reduction potential +407 mV (converted oxidation-reduction potential: +395 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.34) was 26.0 g (Fe 3+ / As molar ratio was 10.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.81.
Next, 134.3 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilizing agent B and 120 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 26.86 g) was added as chemical agent B, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing agent B was 5.97. After the reaction of immobilizing the chemical B, the stirring is stopped, and then the resulting cake (immobilized product) is allowed to stand for 30 minutes to settle, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 1 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 65 hours, and 43 g of immobilization treatment product having a water content of 19% by weight was obtained. The arsenic concentration of the filtrate at this time is shown in Table 2.
In addition, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 19% by weight. The results are shown in Table 2.

実施例３
（有害成分の固定化薬剤の調製）
シリカ材料としてガラスカレットを用いた。
該ガラスカレットは、Ｓｉ成分をＳｉＯ２に換算して６７．２重量％、Ｃａ成分をＣａＯに換算して９．８重量％、水分を１．１重量％含有し、平均粒子径が１１１μｍ、比表面積が３，９００ｃｍ２／ｇで非晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該ガラスカレット５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％のガラスカレットと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｃ（ＳｉＯ２：Ｍｇ＝１００：６０）を調製した。 Example 3
(Preparation of immobilized drug for harmful components)
Glass cullet was used as the silica material.
The glass cullet, 67.2 wt% in terms of Si component in SiO 2, 9.8 wt% in terms of Ca component in CaO, water contained 1.1 weight%, average particle diameter 111Myuemu, The specific surface area is 3,900 cm 2 / g and is amorphous.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the glass cullet and 50 parts by weight of magnesium hydroxide are mixed, and an immobilizing agent C (SiO 2 : Mg = 100: 60) comprising 50% by weight of glass cullet and 50% by weight of magnesium hydroxide. Was prepared.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｃを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３８０ｍｇ／ｌ、ｐＨ９．９５、酸化還元電位＋３７５ｍＶ（換算酸化還元電位：＋３７２ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．５倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８２であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｃ３０ｇと水１２０ｇを混合して得られた水スラリーを９３．４ｇ（固定化薬剤Ｃとして１８．６８ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｃを添加後の砒素含有廃液のｐＨは６．０３であった。固定化薬剤Ｃ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９４時間保持して熟成し、含水率１３重量％の固定化処理物２５ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率１３重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug C was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of arsenic-containing waste liquid with an As concentration of 380 mg / l, pH 9.95, oxidation-reduction potential +375 mV (equivalent oxidation-reduction potential: +372 mV) was added and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 10.5 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.82.
Next, 93.4 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilized chemical C and 120 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. (18.68 g) was added as chemical agent C, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent C was 6.03. After the reaction of adding the immobilizing agent C, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 94 hours in air at room temperature to obtain 25 g of immobilization treatment product having a water content of 13% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 for 20 g of the obtained immobilized processed product having a water content of 13% by weight. The results are shown in Table 2.

実施例４
（有害成分の固定化薬剤の調製）
シリカ材料として、けいそう土（和光純薬工業（株）製）を用いた。
該けいそう土は、Ｓｉ成分をＳｉＯ２に換算して７１．９重量％、Ｃａ成分をＣａＯに換算して１．０重量％、水分を５．２重量％含有し、平均粒子径が１４．７μｍ、比表面積が４００，０００ｃｍ２／ｇで非晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該けいそう土５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％のけいそう土と５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｄ（ＳｉＯ２：Ｍｇ＝１００：５６）を調製した。 Example 4
(Preparation of immobilized drug for harmful components)
As a silica material, diatomaceous earth (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
The diatomaceous earth is 71.9 wt% in terms of Si component in SiO 2, 1.0 wt% in terms of Ca component in CaO, water contained 5.2 weight%, average particle size 14 0.7 μm, specific surface area is 400,000 cm 2 / g and amorphous.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the diatomaceous earth and 50 parts by weight of the magnesium hydroxide are mixed, and an immobilizing agent D (SiO 2 : Mg = 100: 100% consisting of 50% by weight of diatomaceous earth and 50% by weight of magnesium hydroxide). 56) was prepared.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｄを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４５０ｍｇ／ｌ、ｐＨ１０．０２、酸化還元電位＋３９９ｍＶ（換算酸化還元電位：＋４００ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が８．９倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８０であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｄ３０ｇと水１２０ｇを混合して得られた水スラリーを９２．５ｇ（固定化薬剤Ｄとして１８．５０ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｄを添加後の砒素含有廃液のｐＨは６．２３であった。固定化薬剤Ｄ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率３４重量％の固定化処理物３２ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３４重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug D was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 450 mg / l, a pH of 10.02, an oxidation-reduction potential of +399 mV (converted oxidation-reduction potential: +400 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 8.9 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.80.
Next, 92.5 g of water slurry obtained by mixing 30 g of immobilized drug D and 120 g of water so that the pH of the waste liquid is about 6 while stirring the pretreated arsenic-containing waste liquid in a room temperature atmosphere (fixed) 18.50 g) was added as chemical agent D, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug D was 6.23. After the reaction of adding the immobilizing agent D, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Next, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 89 hours, to obtain 32 g of immobilization treatment product having a moisture content of 34% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a moisture content of 34% by weight. The results are shown in Table 2.

実施例５
（有害成分の固定化薬剤の調製）
シリカ材料としてベントナイト（和光純薬工業（株）製）を用いた。
該ベントナイトは、Ｓｉ成分をＳｉＯ２に換算して５９．５重量％、Ｃａ成分をＣａＯに換算して２．９重量％、水分を６．７重量％含有し、平均粒子径が７．６μｍ、比表面積が３５８，０００ｃｍ２／ｇで結晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該ベントナイト５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％のベントナイトと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｅ（ＳｉＯ２：Ｍｇ＝１００：６８）を調製した。 Example 5
(Preparation of immobilized drug for harmful components)
Bentonite (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the silica material.
The bentonite, 59.5 wt% in terms of Si component in SiO 2, 2.9 wt% in terms of Ca component in CaO, moisture contained 6.7 wt%, average particle diameter of 7.6μm The specific surface area is 358,000 cm 2 / g and crystalline.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the bentonite and 50 parts by weight of the magnesium hydroxide are mixed to prepare an immobilizing agent E (SiO 2 : Mg = 100: 68) composed of 50% by weight of bentonite and 50% by weight of magnesium hydroxide. did.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｅを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３８０ｍｇ／ｌ、ｐＨ９．６３、酸化還元電位＋４１４ｍＶ（換算酸化還元電位：＋３９２ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．５倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８０であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｅ３０ｇと水１２０ｇを混合して得られた水スラリーを９５．１ｇ（固定化薬剤Ｅとして１９．０２ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｅを添加後の砒素含有廃液のｐＨは６．３３であった。固定化薬剤Ｅ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９３時間保持して熟成し、含水率４３重量％の固定化処理物３７ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率４３重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
The immobilization drug E was used in place of the immobilization drug A.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 380 mg / l, a pH of 9.63, an oxidation-reduction potential of +414 mV (equivalent oxidation-reduction potential: +392 mV) was added and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 10.5 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.80.
Next, 95.1 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilizing agent E and 120 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 19.02 g) was added as chemical agent E, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent E was 6.33. After the reaction of adding the immobilizing agent E, the stirring is stopped, and then left to stand for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 93 hours in air at room temperature to obtain 37 g of immobilization treatment product having a water content of 43% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
In addition, acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 43% by weight. The results are shown in Table 2.

実施例６
（有害成分の固定化薬剤の調製）
シリカ材料として、はくとう土（和光純薬工業（株）製）を用いた。
該はくとう土は、Ｓｉ成分をＳｉＯ２に換算して７６．２重量％、Ｃａ成分をＣａＯに換算して０．０６重量％、水分を１．７重量％含有し、平均粒子径が４．４μｍ、比表面積が７６，０００ｃｍ２／ｇで結晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該はくとう土５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％のはくとう土と５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｆ（ＳｉＯ２：Ｍｇ＝１００：５３）を調製した。 Example 6
(Preparation of immobilized drug for harmful components)
As the silica material, Hakuto soil (manufactured by Wako Pure Chemical Industries, Ltd.) was used.
The bald soil, 76.2 wt% in terms of Si component in SiO 2, 0.06 wt% in terms of Ca component in CaO, moisture contained 1.7 wt%, average particle diameter It is 4.4 μm and has a specific surface area of 76,000 cm 2 / g and is crystalline.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the clay and 50 parts by weight of the magnesium hydroxide are mixed, and the immobilization agent F (SiO 2 : Mg = 50% by weight of the clay and 50% by weight of magnesium hydroxide is mixed. 100: 53).

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｆを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４５０ｍｇ／ｌ、ｐＨ９．８４、酸化還元電位＋４３４ｍＶ（換算酸化還元電位：＋４２５ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が８．９倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８３であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｆ３０ｇと水１２０ｇを混合して得られた水スラリーを９２．３ｇ（固定化薬剤Ｆとして１８．４６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｆを添加後の砒素含有廃液のｐＨは６．１３であった。固定化薬剤Ｆ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率４２重量％の固定化処理物３７ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率４２重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug F was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 450 mg / l, a pH of 9.84, an oxidation-reduction potential of +434 mV (converted oxidation-reduction potential: +425 mV), and stirring at room temperature, A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 8.9 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.83.
Next, 92.3 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilized chemical F and 120 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 18.46 g) was added as a chemical agent F, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent F was 6.13. After the reaction of adding the immobilizing agent F, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 89 hours to obtain 37 g of immobilization treatment product having a water content of 42% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 42% by weight. The results are shown in Table 2.

実施例７
（有害成分の固定化薬剤の調製）
シリカ材料として珪砂（オーストラリア産）を用いた。
該珪砂は、Ｓｉ成分をＳｉＯ２に換算して９８．４重量％、Ｃａ成分をＣａＯに換算して０．０１重量％未満、水分を０．０１重量％未満含有し、平均粒子径が３３４μｍ、比表面積が４００ｃｍ２／ｇで結晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該珪砂５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％の珪砂と５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｇ（ＳｉＯ２：Ｍｇ＝１００：４１）を調製した。 Example 7
(Preparation of immobilized drug for harmful components)
Silica sand (Australia) was used as the silica material.
該珪sand, 98.4 wt% in terms of Si component in SiO 2, in terms of the Ca component in CaO less than 0.01 wt%, a moisture content less than 0.01 wt%, average particle diameter of 334μm The specific surface area is 400 cm 2 / g and crystalline.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the silica sand and 50 parts by weight of the magnesium hydroxide are mixed to prepare an immobilizing agent G (SiO 2 : Mg = 100: 41) composed of 50% by weight of silica sand and 50% by weight of magnesium hydroxide. did.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｇを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３８０ｍｇ／ｌ、ｐＨ９．８８、酸化還元電位＋３３８ｍＶ（換算酸化還元電位：＋３３１ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．５倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８１であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｇ３０ｇと水１２０ｇを混合して得られた水スラリーを９４．９ｇ（固定化薬剤Ｇとして１８．９８ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｇを添加後の砒素含有廃液のｐＨは６．０１であった。固定化薬剤Ｇ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に６９時間保持して熟成し、含水率２６重量％の固定化処理物３３ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率２６重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
The immobilized drug G was used in place of the immobilized drug A.
A glass container equipped with a fluororesin stirring blade was charged with 2 L of an arsenic-containing waste liquid having an As concentration of 380 mg / l, pH 9.88, oxidation-reduction potential +338 mV (converted oxidation-reduction potential: +331 mV), and stirring in a room temperature atmosphere. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 10.5 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.81.
Next, 94.9 g of water slurry obtained by mixing 30 g of immobilizing agent G and 120 g of water so that the pH of the waste liquid is about 6 while stirring the pretreated arsenic-containing waste liquid at room temperature. (18.98 g) as a chemical agent G was added, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug G was 6.01. After the reaction of adding the immobilizing agent G, stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 69 hours in air at room temperature to obtain 33 g of immobilization treatment product having a water content of 26% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 26% by weight. The results are shown in Table 2.

実施例８
（有害成分の固定化薬剤の調製）
シリカ材料としてシリカゲル（ＡＬＤＲＩＣＨ製）を用いた。
該シリカゲルは、Ｓｉ成分をＳｉＯ２に換算して８８．８重量％、Ｃａ成分をＣａＯに換算して０．０８重量％、水分を６．１重量％含有し、平均粒子径が５９．９μｍ、比表面積が４，６２８，０００ｃｍ２／ｇで非晶質のものである。
マグネシウム化合物として水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)２純度：９５重量％以上）を用いた。
該シリカゲル５０重量部と、該水酸化マグネシウム５０重量部を混合し、５０重量％のシリカゲルと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｈ（ＳｉＯ２：Ｍｇ＝１００：４６）を調製した。 Example 8
(Preparation of immobilized drug for harmful components)
Silica gel (ALDRICH) was used as the silica material.
The silica gel, 88.8 wt% in terms of Si component in SiO 2, 0.08 wt% in terms of Ca component in CaO, water contained 6.1 weight%, average particle diameter 59.9μm The specific surface area is 4,628,000 cm 2 / g and is amorphous.
Magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the magnesium compound.
50 parts by weight of the silica gel and 50 parts by weight of the magnesium hydroxide are mixed to prepare an immobilizing agent H (SiO 2 : Mg = 100: 46) composed of 50% by weight silica gel and 50% by weight magnesium hydroxide. did.

（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに前記固定化薬剤Ｈを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４５０ｍｇ／ｌ、ｐＨ９．７２、酸化還元電位＋４２５ｍＶ（換算酸化還元電位：＋４０８ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が８．９倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８２であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｈ３０ｇと水１２０ｇを混合して得られた水スラリーを９４．１ｇ（固定化薬剤Ｈとして１８．８２ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｈを添加後の砒素含有廃液のｐＨは６．２５であった。固定化薬剤Ｈ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率４９重量％の固定化処理物４３ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率４９重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 (Immobilization of waste liquid containing arsenic)
The immobilization drug H was used in place of the immobilization drug A.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 450 mg / l, pH of 9.72, and an oxidation-reduction potential of +425 mV (converted oxidation-reduction potential: +408 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) was 52.1 g (Fe 3+ / As molar ratio was 8.9 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.82.
Next, 94.1 g (fixed) of an aqueous slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilized chemical H and 120 g of water so that the pH of the waste liquid is about 6 while stirring in a room temperature atmosphere. 18.82 g) was added as a chemical agent H, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug H was 6.25. After the reaction of adding the immobilized drug H, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Next, the immobilization-treated product on the filter paper was aged by holding it in air at room temperature for 89 hours to obtain 43 g of an immobilization-treated product having a water content of 49% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 49% by weight. The results are shown in Table 2.

比較例１
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｉとして水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５重量％以上）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４３０ｍｇ／ｌ、ｐＨ９．７０、酸化還元電位＋３５８ｍＶ（換算酸化還元電位：＋３４０ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が９．３倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８３であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｉ２０ｇと水８０ｇを混合して得られた水スラリーを５７．７ｇ（固定化薬剤Ｉとして１１．５４ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｉを添加後の砒素含有廃液のｐＨは６．０４であった。固定化薬剤Ｉ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８８時間保持して熟成し、含水率４７重量％の固定化処理物５１ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率４７重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 1
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Ca (OH) 2 purity: 95% by weight or more) was used as the immobilized drug I.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 430 mg / l, a pH of 9.70, and an oxidation-reduction potential of +358 mV (converted oxidation-reduction potential: +340 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 9.3 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.83.
Next, 57.7 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilizing agent I and 80 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 11.54 g) was added as chemical agent I, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing drug I was 6.04. After the reaction of immobilizing the drug I, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 88 hours, to obtain 51 g of immobilization treatment product having a water content of 47% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 for 20 g of the obtained immobilized processed product having a water content of 47% by weight. The results are shown in Table 2.

比較例２
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｊとして水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)2純度：９５重量％以上）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度４１０ｍｇ／ｌ、ｐＨ９．３８、酸化還元電位＋３８４ｍＶ（換算酸化還元電位：＋３４７ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝５．９８）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が９．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８３であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｊ２０ｇと水８０ｇを混合して得られた水スラリーを４９．８ｇ（固定化薬剤Ｊとして９．９６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｊを添加後の砒素含有廃液のｐＨは６．５０であった。固定化薬剤Ｊ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率３１重量％の固定化処理物１８ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３１重量％の固定化処理物１５ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 2
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) was used as the immobilized drug J.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 410 mg / l, pH 9.38, oxidation-reduction potential +384 mV (converted oxidation-reduction potential: +347 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 5.98) was 52.1 g (Fe 3+ / As molar ratio was 9.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.83.
Next, 49.8 g (fixed) of an aqueous slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilized chemical J and 80 g of water so that the pH of the waste liquid is about 6 while stirring in a room temperature atmosphere. 9.96 g) as a chemical agent J was added, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent J was 6.50. After the reaction of adding the immobilizing agent J, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 89 hours to obtain 18 g of immobilization treatment product having a water content of 31% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 for 15 g of the obtained immobilization treatment product having a water content of 31% by weight. The results are shown in Table 2.

比較例３
（有害成分の固定化薬剤の調製）
火山灰である前記シルトＦ５０重量部と水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５％以上）５０重量部を混合し、５０重量％の火山灰と５０重量％の水酸化カルシウムとからなる固定化薬剤Ｋを調製した。
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｋを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３６０ｍｇ／ｌ、ｐＨ９．９０、酸化還元電位＋４２６ｍＶ（換算酸化還元電位：＋４２０ｍＶ）の砒素含有廃液１Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を２６．１ｇ（Ｆｅ３＋／Ａｓモル比が１１．１倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８２であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｋ２０ｇと水８０ｇを混合して得られた水スラリーを５６．５ｇ（固定化薬剤Ｋとして１１．３０ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｋを添加後の砒素含有廃液のｐＨは６．０５であった。固定化薬剤Ｋ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約１Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率４４重量％の固定化処理物３３ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率４４重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 3
(Preparation of immobilized drug for harmful components)
50 parts by weight of the silt F, which is volcanic ash, and 50 parts by weight of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Ca (OH) 2 purity: 95% or more) are mixed, and 50% by weight of volcanic ash and 50% by weight of volcanic ash are mixed. An immobilized drug K consisting of calcium hydroxide was prepared.
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug K was used.
In a glass container equipped with a fluororesin stirring blade, 1 L of an arsenic-containing waste liquid having an As concentration of 360 mg / l, a pH of 9.90, an oxidation-reduction potential +426 mV (converted oxidation-reduction potential: +420 mV), and stirring in a room temperature atmosphere, A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 26.1 g (Fe 3+ / As molar ratio was 11.1 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.82.
Next, 56.5 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilized chemical K and 80 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 11.30 g) was added as chemical agent K, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing agent K was 6.05. After the reaction of adding the immobilized drug K, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 1 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 89 hours to obtain 33 g of immobilization treatment product having a water content of 44% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 44% by weight. The results are shown in Table 2.

比較例４
（有害成分の固定化薬剤の調製）
けい酸アルミニウム（和光純薬工業（株）製、Ａｌ２Ｏ３・３ＳｉＯ２）５０重量部と水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)2純度：９５重量％以上）５０重量部を混合し、５０重量％のけい酸アルミニウムと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｌを調製した。
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｌを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３７０ｍｇ／ｌ、ｐＨ１０．１０、酸化還元電位＋４０６ｍＶ（換算酸化還元電位：＋４１２ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８１であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｌ２０ｇと水８１ｇを混合して得られた水スラリーを９８．０ｇ（固定化薬剤Ｌとして１９．３７ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｌを添加後の砒素含有廃液のｐＨは６．００であった。固定化薬剤Ｌ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に１１３時間保持して熟成し、含水率３３重量％の固定化処理物２９ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３３重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 4
(Preparation of immobilized drug for harmful components)
50 parts by weight of aluminum silicate (Wako Pure Chemical Industries, Al 2 O 3 / 3SiO 2 ) and magnesium hydroxide (Wako Pure Chemical Industries, Mg (OH) 2 purity: 95% by weight or more) 50 parts by weight of the mixture was mixed to prepare an immobilized drug L composed of 50% by weight of aluminum silicate and 50% by weight of magnesium hydroxide.
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug L was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid with an As concentration of 370 mg / l, pH 10.10, oxidation-reduction potential +406 mV (converted oxidation-reduction potential: +412 mV) was added and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 10.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.81.
Next, 98.0 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilizing agent L and 81 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 19.37 g) was added as a chemical agent L, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing drug L was 6.00. After the reaction of adding the immobilized drug L, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 113 hours to obtain 29 g of immobilization treatment product having a water content of 33% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 33% by weight. The results are shown in Table 2.

比較例５
（有害成分の固定化薬剤の調製）
けい酸カルシウム（和光純薬工業（株）製、ＣａＯ含有率：４０〜４８重量％、ＳｉＯ２含有率：５１〜５７重量％）５０重量部と水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)2純度：９５重量％以上）５０重量部を混合し、５０重量％のけい酸カルシウムと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｍを調製した。
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｍを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３６０ｍｇ／ｌ、ｐＨ９．７０、酸化還元電位＋４３０ｍＶ（換算酸化還元電位：＋４１２ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１１．１倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８１であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｍ２０ｇと水８０ｇを混合して得られた水スラリーを６７．０ｇ（固定化薬剤Ｍとして１３．４０ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｍを添加後の砒素含有廃液のｐＨは６．０１であった。固定化薬剤Ｍ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８９時間保持して熟成し、含水率３５重量％の固定化処理物２６ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３５重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 5
(Preparation of immobilized drug for harmful components)
50 parts by weight of calcium silicate (Wako Pure Chemical Industries, CaO content: 40 to 48 wt%, SiO 2 content: 51 to 57 wt%) and magnesium hydroxide (Wako Pure Chemical Industries, Ltd.) , Mg (OH) 2 purity: 95 wt% or more) was mixed to prepare an immobilizing drug M consisting of 50 wt% calcium silicate and 50 wt% magnesium hydroxide.
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, the immobilized drug M was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 360 mg / l, a pH of 9.70, and an oxidation-reduction potential of +430 mV (converted oxidation-reduction potential: +412 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 11.1 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.81.
Next, 67.0 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilized chemical M and 80 g of water so that the pH of the waste liquid becomes about 6 while stirring at room temperature. 13.40 g) was added as chemical agent M, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent M was 6.01. After the reaction of adding the immobilizing agent M, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by keeping it in air at room temperature for 89 hours to obtain 26 g of immobilization treatment product having a water content of 35% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
In addition, acid washing elution test 1 was performed in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 35% by weight. The results are shown in Table 2.

比較例６
（有害成分の固定化薬剤の調製）
けい酸マグネシウム五水和物（和光純薬工業（株）製、Ｍｇ２Ｓｉ３Ｏ８・５Ｈ２Ｏ）５７．３重量部と水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)2純度：９５重量％以上）４２．７重量部を混合し、５７．３重量％のけい酸マグネシウム五水和物と４２．７重量％の水酸化マグネシウムとからなる固定化薬剤Ｎを調製した。
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｎを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３７０ｍｇ／ｌ、ｐＨ１０．１２、酸化還元電位＋４２２ｍＶ（換算酸化還元電位：＋４２９ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８１であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｎ２３．４ｇと水７６．６ｇを混合して得られた水スラリーを７１．１ｇ（無水物に換算した固定化薬剤Ｎの量として１４．１９ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｎを添加後の砒素含有廃液のｐＨは６．００であった。固定化薬剤Ｎ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９４時間保持して熟成し、含水率３７重量％の固定化処理物２７ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３７重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 6
(Preparation of immobilized drug for harmful components)
Magnesium silicate pentahydrate (Wako Pure Chemical Industries, Ltd., Mg 2 Si 3 O 8 · 5H 2 O) 57.3 parts by weight of magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH 2 ) Purity: 95% by weight or more) 42.7 parts by weight are mixed to prepare an immobilized drug N composed of 57.3% by weight magnesium silicate pentahydrate and 42.7% by weight magnesium hydroxide. did.
(Immobilization of waste liquid containing arsenic)
Instead of immobilized drug A, immobilized drug N was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 370 mg / l, a pH of 10.12, an oxidation-reduction potential of +422 mV (converted oxidation-reduction potential: +429 mV) was added, and the mixture was stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 10.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.81.
Next, 71 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 23.4 g of the immobilizing agent N and 76.6 g of water so that the pH of the waste liquid becomes about 6 while stirring at room temperature. 0.1 g (14.19 g as the amount of immobilized drug N converted to anhydride) was added, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug N was 6.00. After the reaction of adding the immobilized drug N, the stirring was stopped, and then left to stand for 30 minutes to settle the generated cake (immobilized product), which was filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 94 hours in air at room temperature to obtain 27 g of immobilization treatment product having a water content of 37% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 37% by weight. The results are shown in Table 2.

比較例７
（有害成分の固定化薬剤の調製）
けい酸ナトリウム（和光純薬工業（株）製、Ｎａ２Ｏ含有率：１７〜２３重量％、ＳｉＯ２含有率：５１〜６１重量％、ＳｉＯ２／Ｎａ２Ｏモル比：２．０〜３．５）５０重量部と水酸化マグネシウム（和光純薬工業（株）製、Ｍｇ(ＯＨ)2純度：９５重量％以上）５０重量部を混合し、５０重量％のけい酸ナトリウムと５０重量％の水酸化マグネシウムとからなる固定化薬剤Ｏを調製した。
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｏを用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３７０ｍｇ／ｌ、ｐＨ１０．０３、酸化還元電位＋４２２ｍＶ（換算酸化還元電位：＋４２４ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８２であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｏ２０ｇと水８０ｇを混合して得られた水スラリーを９５．３ｇ（固定化薬剤Ｏとして１９．０６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｏを添加後の砒素含有廃液のｐＨは６．０４であった。固定化薬剤Ｏ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に１１８時間保持して熟成し、含水率５１重量％の固定化処理物３５ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率５１重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 7
(Preparation of immobilized drug for harmful components)
Sodium silicate (manufactured by Wako Pure Chemical Industries, Ltd., Na 2 O content: 17-23 wt%, SiO 2 content: 51-61 wt%, SiO 2 / Na 2 O molar ratio: 2.0-3 .5) 50 parts by weight and 50 parts by weight of magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Mg (OH) 2 purity: 95% by weight or more) are mixed, and 50% by weight of sodium silicate and 50% by weight An immobilized drug O consisting of magnesium hydroxide was prepared.
(Immobilization of waste liquid containing arsenic)
Instead of immobilized drug A, immobilized drug O was used.
In a glass container equipped with a fluororesin stirring blade, 2 L of arsenic-containing waste liquid with an As concentration of 370 mg / l, pH 10.03, oxidation-reduction potential +422 mV (equivalent oxidation-reduction potential: +424 mV) was added, and the mixture was stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 10.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.82.
Next, 95.3 g (fixed) of an aqueous slurry obtained by mixing the pretreated arsenic-containing waste liquid with 20 g of immobilized chemical O and 80 g of water so that the pH of the waste liquid becomes about 6 while stirring at room temperature. 19.06 g) was added as a chemical agent O, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent O was 6.04. After the reaction of adding the immobilizing agent O, stirring is stopped, and then the resulting cake (immobilized product) is allowed to stand for 30 minutes to settle, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by being kept in air at room temperature for 118 hours to obtain 35 g of immobilization treatment product having a water content of 51% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 for 20 g of the obtained immobilized processed product having a water content of 51% by weight. The results are shown in Table 2.

比較例８
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｐとしてけい酸アルミニウム（和光純薬工業（株）製、Ａｌ２Ｏ３・３ＳｉＯ２）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度５００ｍｇ／ｌ、ｐＨ９．９３、酸化還元電位＋４２２ｍＶ（換算酸化還元電位：＋４１８ｍＶ）の砒素含有廃液１Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を２６．０ｇ（Ｆｅ３＋／Ａｓモル比が８．０倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．７９であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｐ２００ｇと水５００ｇを混合して得られた水スラリーを７００ｇ（固定化薬剤Ｐとして２００ｇ）添加し、更に３０分間反応させた。固定化薬剤Ｐを添加後の砒素含有廃液のｐＨは３．６１であった。固定化薬剤Ｐ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約１Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に１１２時間保持して熟成し、含水率６７重量％の固定化処理物４５２ｇを得た。このときの濾液の砒素濃度を表２に示す。
この濾液の砒素濃度が、排水基準（０．１ｍｇ／ｌ以下）を達成していないため、得られた固定化処理物の酸洗浄溶出試験１は行わなかった。
この場合、固定化薬剤ＰのｐＨ調整機能が不十分であるため、固定化薬剤Ｐを２００ｇ添加しても、ｐＨは３．６であった。これ以上、固定化薬剤Ｐを添加してもｐＨの調整は望めず、また、このときの熟成前の固定化処理物の量は５９０ｇであり、更に固定化処理物の発生量が多くなる。 Comparative Example 8
(Immobilization of waste liquid containing arsenic)
Instead of the immobilizing agent A, aluminum silicate (Wako Pure Chemical Industries, Ltd., Al 2 O 3 / 3SiO 2 ) was used as the immobilizing agent P.
In a glass container equipped with a fluororesin stirring blade, 1 L of an arsenic-containing waste liquid having an As concentration of 500 mg / l, a pH of 9.93, an oxidation-reduction potential of +422 mV (converted oxidation-reduction potential: +418 mV), and stirring at room temperature, A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 26.0 g (Fe 3+ / As molar ratio was 8.0 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.79.
Next, 700 g of the water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 200 g of the immobilized chemical P and 500 g of water so that the pH of the waste liquid becomes about 6 while stirring in a room temperature atmosphere (immobilized chemical). 200 g) was added as P, and the mixture was further reacted for 30 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug P was 3.61. After the reaction of adding the immobilized drug P, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 1 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 112 hours in air at room temperature to obtain 452 g of immobilization treatment product having a water content of 67% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Since the arsenic concentration of this filtrate did not achieve the waste water standard (0.1 mg / l or less), the acid washing elution test 1 of the obtained immobilization treatment was not performed.
In this case, since the pH adjustment function of the immobilized drug P was insufficient, the pH was 3.6 even when 200 g of the immobilized drug P was added. No more adjustment of the pH can be expected even when the immobilized drug P is added, and the amount of the immobilization treatment product before aging at this time is 590 g, and the generation amount of the immobilization treatment product is further increased.

比較例９
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｑとしてけい酸カルシウム（和光純薬工業（株）製、ＣａＯ含有率：４０〜４８重量％、ＳｉＯ２含有率：５１〜５７重量％）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度５００ｍｇ／ｌ、ｐＨ９．９６、酸化還元電位＋４３５ｍＶ（換算酸化還元電位：＋４３３ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が８．０倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．７９であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｑ３０ｇと水１２０ｇを混合して得られた水スラリーを１２５．３ｇ（固定化薬剤Ｑとして２５．０６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｑを添加後の砒素含有廃液のｐＨは６．０２であった。固定化薬剤Ｑ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に１１７時間保持して熟成し、含水率３７重量％の固定化処理物６６ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３７重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 9
(Immobilization of waste liquid containing arsenic)
Calcium silicate (manufactured by Wako Pure Chemical Industries, Ltd., CaO content: 40 to 48% by weight, SiO 2 content: 51 to 57% by weight) is used as the immobilized drug Q instead of the immobilized drug A. It was.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 500 mg / l, a pH of 9.96, an oxidation-reduction potential of +435 mV (converted oxidation-reduction potential: +433 mV), and stirring at room temperature, A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 8.0 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.79.
Next, 125.3 g (fixed) of the water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 30 g of immobilized chemical Q and 120 g of water so that the pH of the waste liquid is about 6 while stirring in a room temperature atmosphere. 25.06 g) was added as chemical agent Q, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing drug Q was 6.02. After the reaction of adding the immobilized drug Q, the stirring is stopped, and then left to stand for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 117 hours in air at room temperature to obtain 66 g of immobilization treatment product having a water content of 37% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 37% by weight. The results are shown in Table 2.

比較例１０
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｒとしてけい酸マグネシウム五水和物（和光純薬工業（株）製、Ｍｇ２Ｓｉ３Ｏ８・５Ｈ２Ｏ）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度３７０ｍｇ／ｌ、ｐＨ９．９８、酸化還元電位＋４２７ｍＶ（換算酸化還元電位：＋４２６ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が１０．８倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．７８であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｒ４０ｇと水１６０ｇを混合して得られた水スラリーを１８７．４ｇ（無水物に換算した固定化薬剤Ｒの量として２７．８７ｇ）添加し、更に３０分間反応させた。固定化薬剤Ｒを添加後の砒素含有廃液のｐＨは６．０６であった。固定化薬剤Ｒ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９３時間保持して熟成し、含水率３９重量％の固定化処理物５２ｇを得た。このときの濾液の砒素濃度を表２に示す。
また、得られた含水率３９重量％の固定化処理物２０ｇについて、実施例１と同様に酸洗浄溶出試験１を行った。結果を表２に示す。 Comparative Example 10
(Immobilization of waste liquid containing arsenic)
Magnesium silicate pentahydrate as an immobilizing agent R instead of fixing agent A (manufactured by Wako Pure Chemical Industries, Ltd., Mg 2 Si 3 O 8 · 5H 2 O) was performed using.
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid with an As concentration of 370 mg / l, pH 9.98, oxidation-reduction potential +427 mV (converted oxidation-reduction potential: +426 mV) was added, and the mixture was stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 10.8 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.78.
Next, 187.4 g (anhydrous) of an aqueous slurry obtained by mixing the pretreated arsenic-containing waste liquid with 40 g of immobilized chemical R and 160 g of water so that the pH of the waste liquid is about 6 while stirring in a room temperature atmosphere. 27.87 g) was added as the amount of immobilized drug R converted to a product, and the mixture was further reacted for 30 minutes. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent R was 6.06. After the reaction of adding the immobilizing agent R, stirring is stopped, and then the mixture is allowed to stand for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 93 hours in air at room temperature to obtain 52 g of immobilization treatment product having a water content of 39% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Further, the acid washing elution test 1 was conducted in the same manner as in Example 1 on 20 g of the obtained immobilized processed product having a water content of 39% by weight. The results are shown in Table 2.

比較例１１
（砒素含有廃液の固定化）
固定化薬剤Ａの代わりに、固定化薬剤Ｓとしてけい酸ナトリウム（和光純薬工業（株）製、Ｎａ２Ｏ含有率：１７〜２３重量％、ＳｉＯ２含有率：５１〜６１重量％、ＳｉＯ２／Ｎａ２Ｏモル比：２．０〜３．５）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度５００ｍｇ／ｌ、ｐＨ９．８６、酸化還元電位＋４４８ｍＶ（換算酸化還元電位：＋４４０ｍＶ）の砒素含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．１９）を用いて調製した４１重量％水溶液を５２．１ｇ（Ｆｅ３＋／Ａｓモル比が８．０倍となる量）添加し、３０分間反応させて前処理を行った。反応後のｐＨは１．８０であった。
次に、前処理した砒素有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ｓ６０ｇと水２４０ｇを混合して得られた水スラリーを２７３．７ｇ（固定化薬剤Ｓとして５４．７４ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｓを添加後の砒素含有廃液のｐＨは６．０３であった。
固定化薬剤Ｓ添加反応後の砒素含有廃液は、粒子保持能力１．０μｍのガラス繊維製濾紙では濾過することが非常に困難であり、一部得られた濾液の砒素濃度を表２に示す。
この濾液の砒素濃度が、砒素の排水基準（０．１ｍｇ／ｌ以下）を達成していないため、得られた固定化処理物の酸洗浄溶出試験１は行わなかった。 Comparative Example 11
(Immobilization of waste liquid containing arsenic)
Instead of the immobilized drug A, sodium silicate (manufactured by Wako Pure Chemical Industries, Ltd., Na 2 O content: 17 to 23% by weight, SiO 2 content: 51 to 61% by weight, SiO as the immobilized drug S 2 / Na 2 O molar ratio: 2.0 to 3.5).
In a glass container equipped with a fluororesin stirring blade, 2 L of an arsenic-containing waste liquid having an As concentration of 500 mg / l, pH 9.86, oxidation-reduction potential +448 mV (converted oxidation-reduction potential: +440 mV) was stirred and stirred at room temperature. A 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.19) was 52.1 g (Fe 3+ / As molar ratio was 8.0 times). And a pretreatment was performed by reacting for 30 minutes. The pH after the reaction was 1.80.
Next, 273.7 g of water slurry obtained by mixing the pretreated arsenic-containing waste liquid with 60 g of immobilizing agent S and 240 g of water so that the pH of the waste liquid becomes about 6 while stirring at room temperature. 54.74 g) was added as a chemical agent S, and the mixture was further reacted for 15 minutes. The pH of the arsenic-containing waste liquid after addition of the immobilizing agent S was 6.03.
The arsenic-containing waste liquid after the addition reaction of the immobilized chemical S is very difficult to filter with a glass fiber filter paper having a particle retention capacity of 1.0 μm, and Table 2 shows the arsenic concentration of the obtained filtrate.
Since the arsenic concentration of this filtrate did not achieve the arsenic drainage standard (0.1 mg / l or less), the acid-washed elution test 1 of the obtained immobilization treatment was not performed.

比較例１２
（砒素含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度５００ｍｇ／ｌ、ｐＨ９．８９、酸化還元電位＋４５１ｍＶ（換算酸化還元電位：＋４４５ｍＶ）の砒素含有廃液１Ｌを入れ、室温雰囲気で撹拌しながら、前処理を行わず、固定化薬剤Ａ９ｇと水３６ｇを混合して得られた水スラリーを４５．０ｇ（固定化薬剤Ａとして９．００ｇ）全量添加し、１５分間反応させた。固定化薬剤Ａの添加量は、砒素含有廃液１Ｌ当りの添加量が実施例１とほぼ同等量になるようにした。固定化薬剤Ａを添加後の砒素含有廃液のｐＨは１０．１８であった。固定化薬剤Ａ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約１Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に１１７時間保持して熟成し、含水率２．３重量％の固定化処理物８．４ｇを得た。このときの濾液の砒素濃度を表２に示す。
この濾液の砒素濃度が、排水基準（０．１ｍｇ／ｌ以下）を達成していないため、得られた固定化処理物の酸洗浄溶出試験１は行わなかった。
この場合、前処理を行わなかったため、砒素の固定化が不十分である。 Comparative Example 12
(Immobilization of waste liquid containing arsenic)
In a glass container equipped with a fluororesin stirring blade, put 1 L of arsenic-containing waste liquid with an As concentration of 500 mg / l, pH 9.89, oxidation-reduction potential +451 mV (converted oxidation-reduction potential: +445 mV), and stirring at room temperature, Without pretreatment, 45.0 g of water slurry obtained by mixing 9 g of immobilized drug A and 36 g of water (9.00 g as immobilized drug A) was added and allowed to react for 15 minutes. The addition amount of the immobilizing agent A was set so that the addition amount per liter of arsenic-containing waste liquid was almost the same as that in Example 1. The pH of the arsenic-containing waste liquid after the addition of the immobilizing agent A was 10.18. After the reaction of adding the immobilized drug A, stirring is stopped, and then the resulting cake (immobilized product) is allowed to stand for 30 minutes to settle, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 1 L of filtrate was obtained. Subsequently, the immobilization-treated product on the filter paper was aged by being kept in air at room temperature for 117 hours to obtain 8.4 g of the immobilization-treated product having a water content of 2.3% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Since the arsenic concentration of this filtrate did not achieve the waste water standard (0.1 mg / l or less), the acid washing elution test 1 of the obtained immobilization treatment was not performed.
In this case, arsenic was not sufficiently fixed because no pretreatment was performed.

比較例１３
（砒素含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ａｓ濃度５００ｍｇ／ｌ、ｐＨ９．４６、酸化還元電位＋４４７ｍＶ（換算酸化還元電位：＋４１５ｍＶ）の砒素含有廃液１Ｌを入れ、室温雰囲気で撹拌しながら、前処理を行わず、固定化薬剤Ｔとして火山灰の前記シルトＦ（丸中白土（株）製）を４．５ｇ添加し、１５分間反応させた。固定化薬剤Ｔの添加量は、砒素含有廃液１Ｌ当りの添加量が実施例１の固定化薬剤Ａ添加量中のシルトＦとほぼ同等量になるようにした。固定化薬剤Ｔを添加後の砒素含有廃液のｐＨは９．２０であった。固定化薬剤Ｔ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約１Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９２時間保持して熟成し、含水率３．０重量％の固定化処理物０．９ｇを得た。このときの濾液の砒素濃度を表２に示す。
この濾液の砒素濃度が、排水基準（０．１ｍｇ／ｌ以下）を達成していないため、得られた固定化処理物の酸洗浄溶出試験１は行わなかった。
この場合、前処理を行わなかったため、および固定化薬剤の組成が不十分であるため、砒素の固定化が不十分である。 Comparative Example 13
(Immobilization of waste liquid containing arsenic)
In a glass container equipped with a fluororesin stirring blade, 1 L of an arsenic-containing waste liquid having an As concentration of 500 mg / l, pH 9.46, oxidation-reduction potential +447 mV (converted oxidation-reduction potential: +415 mV) was stirred while stirring at room temperature. Without pretreatment, 4.5 g of the silt F of volcanic ash (manufactured by Marunaka Shirato Co., Ltd.) was added as an immobilizing agent T and allowed to react for 15 minutes. The added amount of the immobilized drug T was set so that the added amount per liter of the arsenic-containing waste liquid was almost the same as the silt F in the added amount of the immobilized drug A of Example 1. The pH of the arsenic-containing waste liquid after the addition of the immobilizing drug T was 9.20. After the reaction of adding the immobilized drug T, the stirring is stopped, and then the resulting cake (immobilized product) is allowed to stand for 30 minutes to settle, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 1 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 92 hours in air at room temperature to obtain 0.9 g of immobilization treatment product having a water content of 3.0% by weight. The arsenic concentration of the filtrate at this time is shown in Table 2.
Since the arsenic concentration of this filtrate did not achieve the waste water standard (0.1 mg / l or less), the acid washing elution test 1 of the obtained immobilization treatment was not performed.
In this case, arsenic was not sufficiently fixed because no pretreatment was performed and the composition of the immobilizing agent was insufficient.

Figure 2007125536
Figure 2007125536

実施例９
（有害成分の固定化薬剤の調製）
実施例１と同様に、前記シルトＦ５０重量部と、前記水酸化マグネシウム５０重量部を混合し、５０重量％の火山灰と５０重量％の水酸化マグネシウムとからなる固定化薬剤Ａ（ＳｉＯ２：Ｍｇ＝１００：５７）を調製した。 Example 9
(Preparation of immobilized drug for harmful components)
In the same manner as in Example 1, 50 parts by weight of Silt F and 50 parts by weight of magnesium hydroxide were mixed, and immobilized drug A (SiO 2 : Mg consisting of 50% by weight of volcanic ash and 50% by weight of magnesium hydroxide). = 100: 57) was prepared.

（鉛含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ｐｂ濃度３７０ｍｇ／ｌ、ｐＨ５．２５、酸化還元電位＋５７７ｍＶ（換算酸化還元電位：＋２９７ｍＶ）の鉛含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液４．７ｇと硫酸第一鉄七水和物（和光純薬工業（株）製、ＦｅＳＯ４・７Ｈ２Ｏ純度：９９重量％以上）を用いて調製した５重量％水溶液２９．３ｇとを混合して得た混合硫酸鉄水溶液を３４ｇ（Ｆｅ３＋／Ｆｅ２＋モル比が１、且つＦｅ／Ｐｂモル比が５．４倍となる量）添加し、３０分間反応させ前処理１を行った。反応後のｐＨは２．５９であった。次に、リン酸二水素マグネシウム（シグマ アルドリッチジャパン（株）製）を用いて調製した１０重量％水スラリーを８４ｇ（ＰＯ４ ３−／Ｐｂモル比が２１．６倍となる量）添加し、３０分間反応させ前処理２を行った。反応後のｐＨは３．００であった。 (Immobilization of lead-containing waste liquid)
In a glass container equipped with a fluororesin stirring blade, 2 L of lead-containing waste liquid having a Pb concentration of 370 mg / l, pH 5.25, oxidation-reduction potential +577 mV (equivalent oxidation-reduction potential: +297 mV) was added, and stirred at room temperature. 4.7 g of a 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) and ferrous sulfate heptahydrate (Wako Pure Chemical Industries, Ltd.) Ltd., FeSO 4 · 7H 2 O purity: 99 wt% or more) mixing iron sulfate solution obtained by mixing 5 wt% aqueous solution of 29.3g prepared using the 34g (Fe 3+ / Fe 2+ mol The ratio was 1 and the Fe / Pb molar ratio was 5.4 times), and the mixture was reacted for 30 minutes for pretreatment 1. The pH after the reaction was 2.59. Next, 84 g of 10 wt% water slurry prepared using magnesium dihydrogen phosphate (manufactured by Sigma-Aldrich Japan Co., Ltd.) is added (amount in which the PO 4 3− / Pb molar ratio is 21.6 times). Pretreatment 2 was performed by reacting for 30 minutes. The pH after the reaction was 3.00.

次に、前処理した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように前記固定化薬剤Ａを添加した。具体的には、固定化薬剤Ａ２０ｇと水８０ｇを混合して得られた水スラリーを２４．８ｇ（固定化薬剤Ａとして４．９６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ａ添加後の鉛含有廃液のｐＨは６．２２であった。次に、固定化薬剤Ａを添加した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約９になるようにｐＨ調整剤として水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)２純度：９５重量％以上）を添加しｐＨ調整した。具体的には、水酸化カルシウム１０ｇと水４０ｇを混合して得られた水スラリーを１４．８ｇ（水酸化カルシウムとして２．９６ｇ）添加し、更に１５分間反応させた。水酸化カルシウム添加後の鉛含有廃液のｐＨは９．０２であった。水酸化カルシウム添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９０時間保持して熟成し、含水率５３重量％の固定化処理物３８ｇを得た。濾液の鉛濃度は０．０１ｍｇ／ｌ未満であった。又濾液の燐濃度は７．７ｍｇ／ｌであった。 Next, the immobilized chemical A was added to the pretreated lead-containing waste liquid while stirring in a room temperature atmosphere so that the pH of the waste liquid was about 6. Specifically, 24.8 g of water slurry obtained by mixing 20 g of immobilized drug A and 80 g of water (4.96 g as immobilized drug A) was added, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after the addition of the immobilizing agent A was 6.22. Next, calcium hydroxide (made by Wako Pure Chemical Industries, Ltd., Ca) is used as a pH adjusting agent so that the pH of the waste liquid becomes about 9 while stirring the lead-containing waste liquid to which the immobilized medicine A is added at room temperature. (OH) 2 purity: 95 wt% or more) was added to adjust the pH. Specifically, 14.8 g (2.96 g as calcium hydroxide) of an aqueous slurry obtained by mixing 10 g of calcium hydroxide and 40 g of water was added, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after addition of calcium hydroxide was 9.02. After the calcium hydroxide addition reaction, stirring is stopped, and then the resulting cake (immobilized product) is allowed to settle for 30 minutes, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 90 hours in air at room temperature to obtain 38 g of immobilization treatment product having a water content of 53% by weight. The lead concentration in the filtrate was less than 0.01 mg / l. The phosphorus concentration in the filtrate was 7.7 mg / l.

（酸洗浄溶出試験２）
次に、得られた含水率５３重量％の固定化処理物２０ｇをフッ素樹脂製撹拌羽根を備えたガラス製容器に入れ、次いでｐＨ３．０に調整した塩酸溶液を固定化処理物の３０倍量を加えてスラリー化した後、室温雰囲気で攪拌しながら、スラリーのｐＨが常に３．０〜３．１となるように５ｍｏｌ／ｌ塩酸溶液および０．５ｍｏｌ／ｌ塩酸溶液でｐＨ調整しながら、６時間攪拌した。次に、このスラリーを粒子保持能力１．０μｍのガラス繊維製濾紙で濾過し、この濾液の鉛濃度を測定した。濾液の鉛濃度は０．０１ｍｇ／ｌ未満であった。
なお、以下の比較例では、５ｍｏｌ／ｌ塩酸溶液および／または０．５ｍｏｌ／ｌ塩酸溶液を用いてｐＨ調整を行った。 (Acid washing dissolution test 2)
Next, 20 g of the obtained immobilized product having a water content of 53% by weight is placed in a glass container equipped with a fluororesin stirring blade, and then the hydrochloric acid solution adjusted to pH 3.0 is 30 times the amount of the immobilized product. After adding slurry to make a slurry, while stirring in a room temperature atmosphere, adjusting the pH with a 5 mol / l hydrochloric acid solution and a 0.5 mol / l hydrochloric acid solution so that the pH of the slurry is always 3.0 to 3.1, Stir for 6 hours. Next, the slurry was filtered through a glass fiber filter paper having a particle holding capacity of 1.0 μm, and the lead concentration of the filtrate was measured. The lead concentration in the filtrate was less than 0.01 mg / l.
In the following comparative examples, pH adjustment was performed using a 5 mol / l hydrochloric acid solution and / or a 0.5 mol / l hydrochloric acid solution.

比較例１４
（鉛含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｉとして水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５重量％以上）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ｐｂ濃度４００ｍｇ／ｌ、ｐＨ５．２０、酸化還元電位＋５６８ｍＶ（換算酸化還元電位：＋２８５ｍＶ）の鉛含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液を１８．８ｇ（Ｆｅ３＋／Ｐｂモル比が１０倍となる量）添加し、３０分間反応させ前処理を行った。反応後のｐＨは２．１４であった。
次に、前処理した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約９になるように固定化薬剤Ｉ１０ｇと水４０ｇを混合して得られた水スラリーを２５．９ｇ（固定化薬剤Ｉとして５．１８ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｉ添加後の鉛含有廃液のｐＨは９．００であった。固定化薬剤Ｉ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に６８時間保持して熟成し、含水率２０重量％の固定化処理物７．１ｇを得た。このときの濾液の鉛濃度を表３に示す。
また、得られた含水率２０重量％の固定化処理物５ｇについて、実施例９と同様に酸洗浄溶出試験２を行った。結果を表３に示す。 Comparative Example 14
(Immobilization of lead-containing waste liquid)
Instead of the immobilized drug A, calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Ca (OH) 2 purity: 95% by weight or more) was used as the immobilized drug I.
In a glass container equipped with a fluororesin stirring blade, 2 L of lead-containing waste liquid having a Pb concentration of 400 mg / l, pH 5.20, oxidation-reduction potential +568 mV (converted oxidation-reduction potential: +285 mV) was added, while stirring in a room temperature atmosphere. 18.8 g (Fe 3+ / Pb molar ratio of 10 times) of a 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) ) And reacted for 30 minutes for pretreatment. The pH after the reaction was 2.14.
Next, 25.9 g of water slurry obtained by mixing the pretreated lead-containing waste liquid with 10 g of immobilizing agent I and 40 g of water so that the pH of the waste liquid is about 9 while stirring at room temperature. 5.18 g) as chemical agent I was added, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after the addition of the immobilizing drug I was 9.00. After the reaction of immobilizing the drug I, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Next, the immobilization-treated product on the filter paper was aged by holding it in air at room temperature for 68 hours to obtain 7.1 g of an immobilization-treated product having a water content of 20% by weight. The lead concentration of the filtrate at this time is shown in Table 3.
Further, the acid washing elution test 2 was conducted in the same manner as in Example 9 on 5 g of the obtained immobilized processed product having a water content of 20% by weight. The results are shown in Table 3.

比較例１５
（鉛含有廃液の固定化）
固定化薬剤Ａの代わりに固定化薬剤Ｉとして水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５重量％以上）を用いて行った。
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ｐｂ濃度４００ｍｇ／ｌ、ｐＨ５．１９、酸化還元電位＋５９２ｍＶ（換算酸化還元電位：＋３０８ｍＶ）の鉛含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第一鉄七水和物（和光純薬工業（株）製、ＦｅＳＯ４・７Ｈ２Ｏ純度：９９重量％以上）を用いて調製した５重量％水溶液を１１７．３ｇ（Ｆｅ２＋／Ｐｂモル比が１０倍となる量）添加し、３０分間反応させ前処理を行った。反応後のｐＨは４．１４であった。
次に、前処理した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約９になるように固定化薬剤Ｉ１０ｇと水４０ｇを混合して得られた水スラリーを１２．２ｇ（固定化薬剤Ｉとして２．４４ｇ）添加し、更に１５分間反応させた。固定化薬剤Ｉ添加後の鉛含有廃液のｐＨは９．００であった。固定化薬剤Ｉ添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に９３時間保持して熟成し、含水率７．２重量％の固定化処理物５．４ｇを得た。このときの濾液の鉛濃度を表３に示す。
この濾液の鉛濃度が、排水基準（０．１ｍｇ／ｌ以下）を達成していないため、得られた固定化処理物の酸洗浄溶出試験２は行わなかった。 Comparative Example 15
(Immobilization of lead-containing waste liquid)
Instead of the immobilized drug A, calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Ca (OH) 2 purity: 95% by weight or more) was used as the immobilized drug I.
In a glass container equipped with a fluororesin stirring blade, 2 L of lead-containing waste liquid having a Pb concentration of 400 mg / l, pH 5.19, oxidation-reduction potential +592 mV (converted oxidation-reduction potential: +308 mV) was added, and stirred at room temperature. 117.3 g (Fe 2+ / Pb mol) of a 5 wt% aqueous solution prepared using ferrous sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd., FeSO 4 · 7H 2 O purity: 99 wt% or more) The amount was 10 times), and the mixture was reacted for 30 minutes and pretreated. The pH after the reaction was 4.14.
Next, 12.2 g of water slurry obtained by mixing the pretreated lead-containing waste liquid with 10 g of immobilizing agent I and 40 g of water so that the pH of the waste liquid is about 9 while stirring at room temperature. 2.44 g) was added as chemical agent I, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after the addition of the immobilizing drug I was 9.00. After the reaction of immobilizing the drug I, the stirring is stopped, and then left for 30 minutes to settle the generated cake (immobilized product), which is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged for 93 hours in air at room temperature to obtain 5.4 g of immobilization treatment product having a water content of 7.2% by weight. The lead concentration of the filtrate at this time is shown in Table 3.
Since the lead concentration of this filtrate did not achieve the drainage standard (0.1 mg / l or less), the acid washing elution test 2 of the obtained immobilization treatment was not performed.

比較例１６
（鉛含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ｐｂ濃度３７０ｍｇ／ｌ、ｐＨ５．２３、酸化還元電位＋５６６ｍＶ（換算酸化還元電位：＋２８５ｍＶ）の鉛含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、硫酸第二鉄ｎ水和物（和光純薬工業（株）製：ｎ＝６．２２）を用いて調製した４１重量％水溶液４．７ｇと硫酸第一鉄七水和物（和光純薬工業（株）製、ＦｅＳＯ４・７Ｈ２Ｏ純度：９９重量％以上）を用いて調製した５重量％水溶液２９．３ｇとを混合して得た混合硫酸鉄水溶液を３４ｇ（Ｆｅ３＋／Ｆｅ２＋モル比が１、且つＦｅ／Ｐｂモル比が５．４倍となる量）添加し、３０分間反応させ前処理を行った。反応後のｐＨは２．５８であった。
次に、前処理した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ａ２０ｇと水８０ｇを混合して得られた水スラリーを１８．９ｇ（固定化薬剤Ａとして３．７８ｇ）添加し、更に１５分間反応させた。固定化薬剤Ａ添加後の鉛含有廃液のｐＨは６．４８であった。次に、固定化薬剤Ａを添加した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約９になるように、ｐＨ調整剤として水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５重量％以上）１０ｇと水４０ｇを混合して得られた水スラリーを３．０ｇ（粉末換算０．６０ｇ）添加し、更に１５分間反応させた。水酸化カルシウム添加後の鉛含有廃液のｐＨは９．０４であった。水酸化カルシウム添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８８時間保持して熟成し、含水率７．５重量％の固定化処理物５．８ｇを得た。このときの濾液の鉛濃度を表３に示す。
また、得られた含水率７．５重量％の固定化処理物５ｇについて、実施例９と同様に酸洗浄溶出試験２を行った。結果を表３に示す。
この場合、鉄塩の前処理だけでは鉛を固定化し易い形態にできないため、鉛の固定化が不十分である。 Comparative Example 16
(Immobilization of lead-containing waste liquid)
In a glass container equipped with a fluororesin stirring blade, 2 L of lead-containing waste liquid with a Pb concentration of 370 mg / l, pH 5.23, oxidation-reduction potential +566 mV (converted oxidation-reduction potential: +285 mV) was added, and the mixture was stirred at room temperature. 4.7 g of a 41 wt% aqueous solution prepared using ferric sulfate n-hydrate (manufactured by Wako Pure Chemical Industries, Ltd .: n = 6.22) and ferrous sulfate heptahydrate (Wako Pure Chemical Industries, Ltd.) Ltd., FeSO 4 · 7H 2 O purity: 99 wt% or more) mixing iron sulfate solution obtained by mixing 5 wt% aqueous solution of 29.3g prepared using the 34g (Fe 3+ / Fe 2+ mol The ratio was 1 and the Fe / Pb molar ratio was 5.4 times), and the mixture was reacted for 30 minutes for pretreatment. The pH after the reaction was 2.58.
Next, 18.9 g of water slurry obtained by mixing the pretreated lead-containing waste liquid with 20 g of immobilized chemical A and 80 g of water so that the pH of the waste liquid is about 6 while stirring at room temperature. 3.78 g) as chemical agent A) was added, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after the addition of the immobilizing agent A was 6.48. Next, calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) is used as a pH adjuster so that the pH of the waste liquid is about 9 while stirring in a lead-containing waste liquid to which the immobilized drug A is added at room temperature. 3.0 g (0.60 g in terms of powder) of an aqueous slurry obtained by mixing 10 g of Ca (OH) 2 purity: 95% by weight or more) and 40 g of water was added, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after addition of calcium hydroxide was 9.04. After the calcium hydroxide addition reaction, stirring is stopped, and then the resulting cake (immobilized product) is allowed to settle for 30 minutes, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Subsequently, the immobilization treatment product on the filter paper was aged by keeping it in air at room temperature for 88 hours to obtain 5.8 g of immobilization treatment product having a water content of 7.5% by weight. The lead concentration of the filtrate at this time is shown in Table 3.
Further, the acid washing elution test 2 was performed in the same manner as in Example 9 on 5 g of the obtained immobilized processed product having a water content of 7.5% by weight. The results are shown in Table 3.
In this case, the lead cannot be easily fixed only by the pretreatment of the iron salt, so that the lead is not sufficiently fixed.

比較例１７
（鉛含有廃液の固定化）
フッ素樹脂製撹拌羽根を備えたガラス製容器に、Ｐｂ濃度４００ｍｇ／ｌ、ｐＨ５．１９、酸化還元電位＋６０３ｍＶ（換算酸化還元電位：＋３１９ｍＶ）の鉛含有廃液２Ｌを入れ、室温雰囲気で撹拌しながら、リン酸二水素マグネシウム（シグマ アルドリッチ ジャパン（株）製）を用いて調製した１０重量％水スラリーを８４ｇ（ＰＯ４ ３−／Ｐｂモル比が２０倍となる量）添加し、３０分間反応させ前処理を行った。反応後のｐＨは５．１７であった。
次に、前処理した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約６になるように固定化薬剤Ａ２０ｇと水８０ｇを混合して得られた水スラリーを５．８ｇ（固定化薬剤Ａとして１．１６ｇ）添加し、更に１５分間反応させた。固定化薬剤Ａ添加後の鉛含有廃液のｐＨは６．２３であった。次に、固定化薬剤Ａを添加した鉛含有廃液に、室温雰囲気で撹拌しながら、廃液のｐＨが約９になるように、ｐＨ調整剤として水酸化カルシウム（和光純薬工業（株）製、Ｃａ(ＯＨ)2純度：９５重量％以上）１０ｇと水４０ｇを混合して得られた水スラリーを１９．８ｇ（水酸化カルシウムとして３．９６ｇ）添加し、更に１５分間反応させた。水酸化カルシウム添加後の鉛含有廃液のｐＨは９．３５であった。水酸化カルシウム添加反応後、攪拌を停止し、その後、３０分間静置して発生ケーキ（固定化処理物）を沈降させ、これを粒子保持能力１．０μｍのガラス繊維製濾紙を用い濾過して濾液約２Ｌを得た。次いで濾紙上の固定化処理物を室温の空気中に８７時間保持して熟成し、含水率４２重量％の固定化処理物２４ｇを得た。このときの濾液の鉛濃度を表３に示す。
また、得られた含水率４２重量％の固定化処理物２０ｇについて、実施例９と同様に酸洗浄溶出試験２を行った。結果を表３に示す。
この濾液の燐濃度は１１ｍｇ／ｌであった。
この場合、リン酸塩の前処理だけでは鉛を固定化し易い形態にできないため、鉛の固定化が不十分である。 Comparative Example 17
(Immobilization of lead-containing waste liquid)
In a glass container equipped with a fluororesin stirring blade, 2 L of lead-containing waste liquid having a Pb concentration of 400 mg / l, pH 5.19, oxidation-reduction potential +603 mV (converted oxidation-reduction potential: +319 mV) was added and stirred at room temperature. 84 g of a 10 wt% water slurry prepared using magnesium dihydrogen phosphate (manufactured by Sigma Aldrich Japan Co., Ltd.) (amount in which the PO 4 3− / Pb molar ratio is 20 times) was added and reacted for 30 minutes. Processed. The pH after the reaction was 5.17.
Next, 5.8 g of water slurry obtained by mixing the pretreated lead-containing waste liquid with 20 g of immobilized drug A and 80 g of water so that the pH of the waste liquid is about 6 while stirring in a room temperature atmosphere (fixed) 1.16 g) was added as a chemical agent A, and the mixture was further reacted for 15 minutes. The pH of the lead-containing waste liquid after the addition of the immobilizing agent A was 6.23. Next, calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) is used as a pH adjuster so that the pH of the waste liquid is about 9 while stirring in a lead-containing waste liquid to which the immobilized drug A is added at room temperature. 19.8 g (3.96 g as calcium hydroxide) of water slurry obtained by mixing 10 g of Ca (OH) 2 purity: 95% by weight or more) and 40 g of water was added and reacted for another 15 minutes. The pH of the lead-containing waste liquid after addition of calcium hydroxide was 9.35. After the calcium hydroxide addition reaction, stirring is stopped, and then the resulting cake (immobilized product) is allowed to settle for 30 minutes, and this is filtered using a glass fiber filter paper having a particle holding capacity of 1.0 μm. About 2 L of filtrate was obtained. Next, the immobilization treatment product on the filter paper was aged by keeping it in air at room temperature for 87 hours to obtain 24 g of immobilization treatment product having a water content of 42% by weight. The lead concentration of the filtrate at this time is shown in Table 3.
Further, the acid washing elution test 2 was performed in the same manner as in Example 9 on 20 g of the obtained immobilized processed product having a moisture content of 42% by weight. The results are shown in Table 3.
The filtrate had a phosphorous concentration of 11 mg / l.
In this case, since the lead cannot be easily fixed only by the pretreatment of the phosphate, the lead is not sufficiently fixed.

Figure 2007125536
Figure 2007125536

Claims (10)

シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなることを特徴とする有害成分の固定化薬剤。   An agent for immobilizing harmful components comprising a silica material and a magnesium compound or a strontium compound. シリカ材料が、火山噴出物、ガラスカレット、ガラス研磨スラッジ、けいそう土、粘土鉱物、珪砂、石炭灰、シリカゲルおよびシリカヒュームからなる群より選ばれた少なくとも一種の材料である請求項１記載の有害成分の固定化薬剤。   The hazardous material according to claim 1, wherein the silica material is at least one material selected from the group consisting of volcanic ejecta, glass cullet, glass polishing sludge, diatomaceous earth, clay minerals, silica sand, coal ash, silica gel and silica fume. Ingredient immobilization drug. シリカ材料が、珪素成分をシリカ（ＳｉＯ２）換算で５０〜９９．９重量％含有することを特徴とする請求項１または２記載の有害成分の固定化薬剤。 Silica material, a silicon component silica (SiO 2) according to claim 1 or 2 harmful components immobilization agents described, characterized in that it contains 50 to 99.9 wt% in terms of. マグネシウム化合物がマグネシウムの水酸化物、酸化物または炭酸塩であり、ストロンチウム化合物がストロンチウムの水酸化物、酸化物または炭酸塩である請求項１記載の有害成分の固定化薬剤。   2. The harmful agent immobilization agent according to claim 1, wherein the magnesium compound is magnesium hydroxide, oxide or carbonate, and the strontium compound is strontium hydroxide, oxide or carbonate. シリカ材料とマグネシウム化合物とからなり、シリカ材料中の珪素成分をシリカ換算した重量とマグネシウム化合物中に含有されるマグネシウム原子の重量との比（ＳｉＯ２：Ｍｇ）が１００：５〜１,０００である請求項１〜４のいずれかに記載の有害成分の固定化薬剤。 It consists of a silica material and a magnesium compound, and the ratio (SiO 2 : Mg) of the weight in terms of silica of the silicon component in the silica material to the weight of magnesium atoms contained in the magnesium compound is 100: 5 to 1,000. The fixed chemical | medical agent of the harmful | toxic component in any one of Claims 1-4. シリカ材料とストロンチウム化合物とからなり、シリカ材料中の珪素成分をシリカ換算した重量とストロンチウム化合物中に含有されるストロンチウム原子の重量との比（ＳｉＯ２：Ｓｒ）が１００：２０〜１,５００である請求項１〜４のいずれかに記載の有害成分の固定化薬剤。 It consists of a silica material and a strontium compound, and the ratio (SiO 2 : Sr) between the weight of the silicon component in the silica material converted to silica and the weight of the strontium atoms contained in the strontium compound is 100: 20 to 1,500. The fixed chemical | medical agent of the harmful | toxic component in any one of Claims 1-4. 有害成分が、砒素、水銀、クロム、セレン、カドミウム、鉛、アンチモン、亜鉛、銅、マンガン、コバルト、ニッケル、モリブデン、スズおよび燐からなる群より選ばれた少なくとも一種の元素またはそれらの化合物である請求項１記載の有害成分の固定化薬剤。   The harmful component is at least one element selected from the group consisting of arsenic, mercury, chromium, selenium, cadmium, lead, antimony, zinc, copper, manganese, cobalt, nickel, molybdenum, tin, and phosphorus, or a compound thereof. The harmful agent immobilization drug according to claim 1. 有害成分を含有する水溶液および／または泥状物に、有害成分に応じた前処理を行った後、有害成分を含有する水溶液および／または泥状物のｐＨが４〜１２の範囲になるように、シリカ材料と、マグネシウム化合物またはストロンチウム化合物とからなる有害成分の固定化薬剤を添加すること、または該固定化薬剤を添加し、次いでｐＨ調整剤を添加することを特徴とする水溶液および／または泥状物中の有害成分の固定化方法。   The aqueous solution and / or mud containing the harmful component is pretreated according to the harmful component so that the pH of the aqueous solution and / or the mud containing the harmful component is in the range of 4 to 12. An aqueous solution and / or mud characterized by adding a fixing agent of a harmful component comprising a silica material and a magnesium compound or a strontium compound, or adding the fixing agent and then adding a pH adjusting agent. Method for immobilizing harmful components in the material. 前処理が、酸化剤、還元剤および共沈剤からなる群より選ばれた少なくとも一種の薬剤を有害成分を含有する水溶液および／または泥状物に添加し、ｐＨを１〜４の範囲に調整することを特徴とする請求項８記載の有害成分の固定化方法。   The pretreatment is performed by adding at least one chemical selected from the group consisting of an oxidizing agent, a reducing agent and a coprecipitation agent to an aqueous solution and / or mud containing a harmful component, and adjusting the pH to a range of 1 to 4. The method for immobilizing harmful components according to claim 8. ｐＨ調整剤が硫酸、塩酸、燐酸、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、酸化カルシウム、水酸化カルシウム、炭酸カルシウムまたは硫酸鉄の酸性硫酸塩である請求項８記載の有害成分の固定化方法。

The pH adjuster is an acidic sulfate of sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium oxide, calcium hydroxide, calcium carbonate or iron sulfate The method for immobilizing harmful components according to claim 8.

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