JP2011036827A - Method for treating substance containing chromium oxide - Google Patents
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本発明は、クロム酸化物含有物質の処理方法に係り、とくに安価に、Cr+6の溶出を防止することができるクロム酸化物含有物質の処理方法に関する。 The present invention relates to a method for treating a chromium oxide-containing material, and particularly to a method for treating a chromium oxide-containing material that can prevent elution of Cr +6 at a low cost.
近年、ステンレス鋼の精錬の際に発生するステンレス鋼スラグや、重クロム酸ナトリウムなどのクロム化合物の製造の際に発生するクロム鉱滓を、路盤材、仮設材、土木埋立材などとして、利用することが検討されている。また、近年、ゴミ焼却灰、下水汚泥などを溶融処理することによりスラグ化して利用することも検討されている。
これらステンレス鋼スラグや、クロム鉱滓は、数％のクロム化合物を含有し、操業条件によっては、その一部がCr+6にまで酸化される場合がある。また、ゴミ焼却灰、下水汚泥などの種類によっては、生成したスラグ中にCr+6が含まれる場合がある。スラグを路盤材、仮設材、土木埋立材などとして利用する場合には、スラグ等から、Cr+6が溶出しないことが絶対条件である。
In recent years, use of stainless steel slag generated during refining of stainless steel and chromium ore generated during the manufacture of chromium compounds such as sodium dichromate as roadbed materials, temporary materials, and civil engineering materials Is being considered. In recent years, it has been studied to use slag by melting trash incineration ash, sewage sludge and the like.
These stainless steel slag and chromium ore contain a few percent of chromium compounds, and some of them may be oxidized to Cr +6 depending on the operating conditions. In addition, depending on the type of garbage incineration ash, sewage sludge, etc., the generated slag may contain Cr +6 . When slag is used as a roadbed material, temporary material, civil engineering landfill material, etc., it is an absolute condition that Cr +6 does not elute from the slag.
スラグ等からCr+6の溶出を防止するための技術として、種々の提案がなされている。例えば、特許文献１には、クロム酸化物含有物質と、硫黄および／または酸化数が＋５価以下の硫黄を含有するスラグおよび／または物質とを混合し、これら混合物に、水および／または高炉スラグの散水冷却時に発生する高炉スラグ溶出水を散水するか、あるいは水蒸気を吹き込むことを特徴とするクロム酸化物含有物質の処理方法が記載されている。特許文献１に記載された技術では、硫黄および／または酸化数が＋５価以下の硫黄を含有するスラグとして、未エ−ジング高炉徐冷スラグを用いることが好ましいとしている。 Various proposals have been made as techniques for preventing elution of Cr +6 from slag and the like. For example, in Patent Document 1, a chromium oxide-containing material is mixed with sulfur and / or slag and / or material containing sulfur having an oxidation number of +5 or less, and water and / or blast furnace slag is mixed with these mixtures. There is described a method for treating a chromium oxide-containing substance, characterized by spraying blast furnace slag elution water generated during water spray cooling or blowing steam. According to the technique described in Patent Document 1, it is preferable to use unaging blast furnace slow-cooled slag as slag containing sulfur and / or sulfur having an oxidation number of +5 or less.
特許文献１に記載された技術によれば、工業的に簡易に、クロム酸化物含有物質からのCr+6の溶出を防止することができる。しかし、水蒸気を使用する必要があるため、処理費用が高騰するという問題があった。また、特許文献１に記載された技術では、水蒸気処理を行った際に発生するドレインの処理費用が高価であるという問題もあった。このように、特許文献１に記載された技術は、クロム酸化物含有物質の処理方法としては有効であるが、処理費用が高価となるため、更に安価で、有効なクロム酸化物含有物質の処理方法が要望されていた。 According to the technique described in Patent Document 1, it is possible to easily prevent elution of Cr +6 from the chromium oxide-containing material industrially. However, since it is necessary to use water vapor, there is a problem that the processing cost increases. In addition, the technique described in Patent Document 1 has a problem that the cost for treating the drain generated when the steam treatment is performed is high. As described above, the technique described in Patent Document 1 is effective as a method for treating a chromium oxide-containing material, but the processing cost is expensive, and thus the treatment of the chromium oxide-containing material is more inexpensive and effective. A method was desired.
本発明は、上記したような従来技術の問題を有利に解決し、工業的に簡易にしかも安価に、クロム酸化物含有物質からのCr+6の溶出を防止することができる、クロム酸化物含有物質の処理方法を提供することを目的とする。 The present invention advantageously solves the problems of the prior art as described above, can prevent elution of Cr +6 from the chromium oxide-containing material, industrially simple and inexpensive, containing chromium oxide It aims at providing the processing method of a substance.
本発明者らは、上記した目的を達成するために、クロム酸化物含有物質中のCr+6の安価な還元処理方法について鋭意研究した。その結果、クロム酸化物含有物質からのCr+6の溶出量が少ない場合には、水蒸気を吹き込む高価な蒸気エージング処理を適用する必要はなく、安価な処理方法でCr+6を還元できることに思い至り、クロム酸化物含有物質からのCr+6の溶出量に基づいて、処理方法を変更することを想到した。クロム酸化物含有物質からのCr+6の溶出量が所定値以上である場合には、クロム酸化物含有物質と還元性硫黄を含む物質とを混合した混合物に水蒸気を吹き込む蒸気エージング処理を適用し、一方、クロム酸化物含有物質からのCr+6の溶出量が所定値未満である場合には、クロム酸化物含有物質を還元水中に浸漬する浸漬エージング処理とすることにより、安価にクロム酸化物含有物質の処理が可能であることを知見した。さらに、蒸気エージング処理で発生する凝縮水を利用してクロム酸化物含有物質の浸漬エージング処理を行えば、さらに経済的に有利となることも知見した。 In order to achieve the above-mentioned object, the present inventors diligently studied an inexpensive method for reducing Cr +6 in a chromium oxide-containing material. As a result, when the leaching amount of Cr +6 from the chromium oxide-containing material is small, it is not necessary to apply an expensive steam aging process in which steam is blown, and it is possible to reduce Cr +6 by an inexpensive processing method. The present inventors have come up with the idea of changing the treatment method based on the amount of Cr +6 eluted from the chromium oxide-containing material. When the elution amount of Cr +6 from the chromium oxide-containing material is greater than or equal to a predetermined value, a steam aging treatment is applied in which water vapor is blown into a mixture of the chromium oxide-containing material and the reducing sulfur-containing material. On the other hand, when the elution amount of Cr +6 from the chromium oxide-containing material is less than a predetermined value, the chromium oxide can be inexpensively produced by immersing the chromium oxide-containing material in reduced water. It was found that the contained substances can be processed. Furthermore, it has also been found that the immersion aging treatment of the chromium oxide-containing substance using the condensed water generated by the steam aging treatment is more economically advantageous.
本発明は、上記した知見に基づき、さらに検討を加えて完成されたものである。すなわち、本発明の要旨は次のとおりである。
（１）クロム酸化物含有物質を処理するにあたり、予め該クロム酸化物含有物質からのCr+6の溶出量を測定し、該クロム酸化物含有物質からのCr+6の溶出量が所定値以上の場合には、該クロム酸化物含有物質に、硫黄および／または酸化数が＋５価以下の硫黄を含有する物質を混合して混合物としたのち、該混合物に水蒸気を吹き込む蒸気エージング処理を施し、前記クロム酸化物含有物質からのCr+6の溶出量が所定値未満である場合には、該クロム酸化物含有物質を硫黄および／または酸化数が＋５価以下の硫黄を含む液中に浸漬する浸漬エージング処理を施すことを特徴とするクロム酸化物含有物質の処理方法。
The present invention has been completed based on the above findings and further studies. That is, the gist of the present invention is as follows.
(1) Upon processing chromium oxide-containing substances, pre-elution amount of Cr +6 from the chromium oxide-containing substances was measured and dissolution amount of Cr +6 from the chromium oxide-containing substances is equal to or higher than a predetermined value In this case, the chromium oxide-containing material is mixed with sulfur and / or a substance containing sulfur having an oxidation number of +5 or less to form a mixture, and then subjected to steam aging treatment in which steam is blown into the mixture, When the elution amount of Cr +6 from the chromium oxide-containing material is less than a predetermined value, the chromium oxide-containing material is immersed in a liquid containing sulfur and / or sulfur having an oxidation number of +5 or less. A method for treating a chromium oxide-containing material, characterized by performing immersion aging treatment.
（２）（１）において、前記硫黄および／または酸化数が＋５価以下の硫黄を含有する物質が、未エージング高炉徐冷スラグであることを特徴とするクロム酸化物含有物質の処理方法。
（３）（１）または（２）において、前記硫黄および／または酸化数が＋５価以下の硫黄を含む液が、前記蒸気エージング処理で発生する蒸気ドレインまたは該蒸気ドレインを含む水であることを特徴とするクロム酸化物含有物質の処理方法。
(2) The method for treating a chromium oxide-containing material according to (1), wherein the substance containing sulfur and / or sulfur having an oxidation number of +5 or less is unaged blast furnace slag.
(3) In (1) or (2), the liquid containing sulfur and / or sulfur having an oxidation number of +5 or less is a steam drain generated in the steam aging treatment or water containing the steam drain. A method for treating a chromium oxide-containing material.
（４）（１）ないし（３）のいずれかにおいて、前記所定値が1.0mg/ｌであることを特徴とするクロム酸化物含有物質の処理方法。 (4) The method for treating a chromium oxide-containing material according to any one of (1) to (3), wherein the predetermined value is 1.0 mg / l.
本発明によれば、ステンレス鋼スラグ、クロム鉱滓、産業廃棄物溶融スラグ、下水汚泥、下水汚泥溶融スラグなどのクロム酸化物含有物質からのCr+6の溶出を、工業的に簡易にしかも安価に防止することができ、産業上格段の効果を奏する。また、本発明によれば、クロム酸化物含有物質の路盤材、仮設材、土木埋立材などへの再利用を容易にするという効果もある。 According to the present invention, elution of Cr +6 from chromium oxide-containing materials such as stainless steel slag, chromium slag, industrial waste molten slag, sewage sludge, sewage sludge molten slag, etc. can be industrially simplified and inexpensive. It can be prevented and has an industrially significant effect. In addition, according to the present invention, there is an effect of facilitating the reuse of the chromium oxide-containing material for roadbed materials, temporary materials, civil engineering landfill materials, and the like.
本発明で処理対象とするクロム酸化物含有物質は、クロム酸化物を含みCr+6を溶出する可能性がある物質であり、ステンレス鋼の精錬の際に発生するステンレス鋼スラグや、重クロム酸ナトリウムなどのクロム化合物の製造の際に発生するクロム鉱滓、産業廃棄物溶融スラグ、下水汚泥、下水汚泥溶融スラグ等が例示されるが、それらに限定されるものではない。 The chromium oxide-containing substance to be treated in the present invention is a substance that contains chromium oxide and has the possibility of eluting Cr +6. Stainless steel slag generated during refining of stainless steel and dichromic acid Examples include, but are not limited to, chromium slag, industrial waste melted slag, sewage sludge, sewage sludge melted slag and the like generated during the production of chromium compounds such as sodium.
本発明では、まず、処理対象のクロム酸化物含有物質について、例えばロットごとに、予めCr+6の溶出量を測定しておく。なお、Cr+6の溶出量の測定は、環境庁告示46号法による溶出試験法、あるいは該溶出試験法に準じて溶出した溶出水を市販のパックテスト（共立理化研究所の登録商標）を用いて行うものとする。なお、この段階では、以後のエージング処理方法を選択するための分別であり、後者の方法を用いるのが好ましい。そして、測定されたCr+6溶出量により、処理対象とするクロム酸化物含有物質を所定値以上のものと、所定値未満のものに分別する。所定値としては、１mg/ｌとすることが好ましい。 In the present invention, for the chromium oxide-containing substance to be treated, for example, the elution amount of Cr +6 is measured in advance for each lot. The elution amount of Cr +6 can be measured by using the elution test method according to the Environmental Agency Notification No. 46 method, or using a commercially available pack test (registered trademark of Kyoritsu Rika Institute) Shall be used. It should be noted that at this stage, classification is performed for selecting a subsequent aging treatment method, and the latter method is preferably used. Then, based on the measured Cr +6 elution amount, the chromium oxide-containing material to be treated is separated into those having a predetermined value or more and those having a predetermined value or less. The predetermined value is preferably 1 mg / l.
本発明では、Cr+6溶出量が所定値以上のクロム酸化物含有物質には、蒸気エージング処理を、一方、Cr+6溶出量が所定値未満のクロム酸化物含有物質には、浸漬エージング処理を施す。
蒸気エージング処理は、対象とするクロム酸化物含有物質に、硫黄および／または酸化数が＋５価以下の硫黄（以下、還元性硫黄ともいう）を含有する物質を混合して混合物としたのち、該混合物に水蒸気を吹き込む処理とする。この蒸気エージング処理により、クロム酸化物含有物質中のCr+6が還元されて、Cr+6溶出量が環境基準値（0.05mg/ｌ未満）以下のクロム酸化物含有物質とすることができる。クロム酸化物含有物質に水蒸気を吹き込むことにより、クロム酸化物含有物質中のCr+6が溶出しやすい状態となり、さらに、還元性硫黄を含有する物質から、還元性硫黄が溶け出し、還元性硫黄が酸化することにより、クロム酸化物含有物質中のCr+6が還元される。なお、Cr+6溶出量を環境基準値（0.05mg/ｌ未満）以下とするためには、蒸気エージング処理は少なくとも72時間とすることが好ましい。
In the present invention, the vapor aging treatment is applied to the chromium oxide-containing material having a Cr +6 elution amount of a predetermined value or more, while the immersion aging treatment is applied to the chromium oxide-containing material having a Cr +6 elution amount of less than the predetermined value. Apply.
The steam aging treatment is performed by mixing a target chromium oxide-containing substance with a substance containing sulfur and / or sulfur having an oxidation number of +5 or less (hereinafter also referred to as reducing sulfur), It is set as the process which injects water vapor | steam into a mixture. By this steam aging treatment, Cr +6 in the chromium oxide-containing material is reduced, and the chromium +6 elution amount can be reduced to an environmental standard value (less than 0.05 mg / l) or less. By blowing water vapor into the chromium oxide-containing material, Cr +6 in the chromium oxide-containing material is easily eluted, and further, the reducing sulfur dissolves from the reducing sulfur-containing material, and the reducing sulfur As a result of oxidation, Cr +6 in the chromium oxide-containing material is reduced. In order to keep the Cr +6 elution amount below the environmental standard value (less than 0.05 mg / l), the steam aging treatment is preferably at least 72 hours.
クロム酸化物含有物質に混合する、還元性硫黄を含有する物質としては、還元性硫黄を含有するスラグを利用することが経済的観点から望ましい。還元性硫黄を含有するスラグとしては、自然エージング３ヶ月未満の高炉徐冷スラグ（未エージング高炉徐冷スラグ）、あるいは溶銑脱硫スラグ等が例示できる。なお、これらスラグの粒度は、特に限定されないが、微粉であるほど、Cr酸化物含有物質中のCr+6をCr+3に還元する能力が高く好ましい。 From the economical viewpoint, it is desirable to use slag containing reducing sulfur as the substance containing reducing sulfur to be mixed with the chromium oxide-containing substance. Examples of slag containing reducing sulfur include blast furnace slow-cooled slag of less than 3 months of natural aging (unaged blast furnace slow-cooled slag), hot metal desulfurization slag, and the like. The particle size of these slags is not particularly limited, but the finer the powder, the better the ability to reduce Cr +6 in the Cr oxide-containing material to Cr +3 .
また、処理対象とするクロム酸化物含有物質に混合する還元性硫黄を含有する物質としては、上記したスラグ以外に、還元性硫黄の含有量が10mass％以上である硫黄含有物質を用いてもよい。還元性硫黄の含有量が10mass％以上である硫黄含有物質としては、単体硫黄、硫黄含有物質から精製した湯の花（単体硫黄含有物質）や、チオ硫酸ナトリウム、硫化鉄、硫化水素等の＋５価以下の硫黄化合物が例示できる。なお、これらの物質を２種以上併用してもよいことは言うまでも無い。 Further, as the substance containing reducing sulfur to be mixed with the chromium oxide-containing substance to be treated, in addition to the above-described slag, a sulfur-containing substance having a reducing sulfur content of 10 mass% or more may be used. . Sulfur-containing substances with a reductive sulfur content of 10 mass% or more include elemental sulfur, Yunohana refined from sulfur-containing substances (elemental sulfur-containing substances), sodium thiosulfate, iron sulfide, hydrogen sulfide, etc. The sulfur compound can be illustrated. Needless to say, two or more of these substances may be used in combination.
クロム酸化物含有物質に混合する還元性硫黄を含む物質の混合量は、処理対象であるクロム酸化物含有物質に含まれる還元すべきCr量（被還元Cr量）と等量以上の還元性硫黄を含むように調整することが肝要である。上記したスラグまたは物質を使用する場合には、これらスラグまたは物質の混合量は混合物全量に対するmass％で10％以上とすることが好ましい。なお、より好ましくは20％以上である。 The amount of the reducing sulfur-containing material mixed with the chromium oxide-containing material is equal to or greater than the amount of Cr to be reduced (reduced Cr amount) contained in the chromium oxide-containing material to be treated. It is important to adjust to include When using the above-mentioned slag or substance, the mixing amount of these slags or substances is preferably 10% or more in terms of mass% with respect to the total amount of the mixture. More preferably, it is 20% or more.
また、混合物に水蒸気を吹き込む際には、堆積した混合物の表層に水蒸気を吹き込む方法、混合物の内部に水蒸気を吹き込む方法、堆積した混合物の下部に水蒸気を吹き込む方法が考えられるが、いずれの方法を用いてもよいことは言うまでもない。また、混合物中に吹き込む水蒸気は、水蒸気単独に限定されず、空気、窒素等のガスとともに吹き込んでもよい。また、吹き込む水蒸気の温度はとくに限定されない。大気中で水蒸気を吹き込む場合、水蒸気の温度は通常100℃程度であるが、堆積した混合物の内部に水蒸気を吹き込むと内部が高圧となり水蒸気の温度も圧力に応じて高温となる。 In addition, when water vapor is blown into the mixture, a method of blowing water vapor into the surface of the deposited mixture, a method of blowing water vapor into the mixture, or a method of blowing water vapor into the lower part of the deposited mixture can be considered. Needless to say, it may be used. Moreover, the water vapor | steam blown in in a mixture is not limited to water vapor alone, You may blow in with gas, such as air and nitrogen. Moreover, the temperature of the water vapor | steam blown in is not specifically limited. When steam is blown in the atmosphere, the temperature of the steam is usually about 100 ° C. However, when steam is blown into the deposited mixture, the pressure inside the mixture becomes high, and the temperature of the steam also increases according to the pressure.
なお、上記した蒸気エージング処理では、還元性硫黄を多量に含む凝縮水（ドレン水または蒸気ドレインと呼ぶ）が生成される。
本発明では、処理対象とするクロム酸化物含有物質のCr+6溶出量が１mg/ｌ未満であれば、還元性硫黄（硫黄および／または酸化数が＋５価以下の硫黄）を含む液中に浸漬する、浸漬エージング処理を施す。クロム酸化物含有物質のCr+6溶出量が１mg/ｌ未満の場合には、このような安価な浸漬エージング処理によっても、少なくとも72時間以内に、クロム酸化物含有物質からのCr+6溶出量を環境基準値（＝0.05mg/ｌ未満）以下にすることができる。なお、クロム酸化物含有物質のCr+6溶出量が環境基準値以下の0.05mg/ｌ未満のものは、処理対象から外れるのは言うまでもない。
In the steam aging treatment described above, condensed water containing a large amount of reducing sulfur (referred to as drain water or steam drain) is generated.
In the present invention, if the Cr +6 elution amount of the chromium oxide-containing substance to be treated is less than 1 mg / l, it is contained in a liquid containing reducing sulfur (sulfur and / or sulfur having an oxidation number of +5 or less). Immersion aging treatment is performed. When the Cr +6 elution amount of the chromium oxide-containing material is less than 1 mg / l, even with such an inexpensive immersion aging treatment, the Cr +6 elution amount from the chromium oxide-containing material is within at least 72 hours. Can be made not more than the environmental standard value (= less than 0.05 mg / l). Needless to say, a chromium oxide-containing substance with a Cr +6 elution amount of less than 0.05 mg / l, which is below the environmental standard value, is excluded from the treatment target.
浸漬エージング処理では、対象とするクロム酸化物含有物質を浸漬等に装入したのち、還元性硫黄を含む液を注入して浸漬することが好ましい。還元性硫黄を含む液としては、工業用水や水道水に還元性硫黄を含む物質を溶解して作製してもよいが、蒸気エージング処理して得られる凝縮水である蒸気ドレイン、あるいは高炉スラグを散水冷却して得られる高炉スラグ自然エージング処理の溶出水を利用することが好ましい。蒸気エージング処理の蒸気ドレイン、高炉スラグ自然エージング処理の溶出水を利用することにより、新たに浸漬エージング処理用の還元性硫黄を含む液を作製する手間が省け、処理能率が向上するとともに、経済的にも有利となる。 In the immersion aging treatment, it is preferable that the target chromium oxide-containing substance is introduced into the immersion, and then immersed by injecting a liquid containing reducing sulfur. The liquid containing reducing sulfur may be prepared by dissolving a substance containing reducing sulfur in industrial water or tap water, but a steam drain or blast furnace slag, which is condensed water obtained by steam aging treatment, may be used. It is preferable to use elution water of blast furnace slag natural aging treatment obtained by water spray cooling. By using the steam drain of the steam aging treatment and the elution water of the natural aging treatment of the blast furnace slag, there is no need to newly prepare a liquid containing reducing sulfur for the immersion aging treatment. Is also advantageous.
処理対象のクロム酸化物含有物質として、表１に示すステンレス鋼の精錬の際に発生するステンレス鋼スラグを用いた。
各クロム酸化物含有物質は、予め環境庁告示46号法による溶出試験法に準拠して、Cr+6溶出量を測定した。その結果を、表２に併記した。
これら処理対象のクロム酸化物含有物質のうち、Cr+6溶出量が所定値である１mg/ｌ以上のクロム酸化物含有物質Ａ〜Ｃには、蒸気エージング処理を施した。
As the chromium oxide-containing material to be treated, stainless steel slag generated during refining of stainless steel shown in Table 1 was used.
Each chromium oxide-containing substance was measured for the Cr +6 elution amount in accordance with the elution test method in accordance with the Environmental Agency Notification No. 46 method in advance. The results are also shown in Table 2.
Among these chromium oxide-containing substances to be treated, the chromium oxide-containing substances A to C having an elution amount of Cr +6 of 1 mg / l or more having a predetermined value were subjected to steam aging treatment.
蒸気エージング処理は、表１に示すクロム酸化物含有物質Ａ〜Ｃに、表２に示す種類、配合量の、硫黄および／または酸化数が＋５価以下の硫黄を含有するスラグ（硫黄含有スラグ）を配合した。ついで、これら混合物を堆積させ、該混合物の内部に水蒸気（温度：100℃）を表２に示す期間吹き込む処理とした。クロム酸化物含有物質に混合する硫黄含有スラグは、未エージング高炉徐冷スラグとた。 The steam aging treatment is a slag containing sulfur and / or sulfur having an oxidation number of +5 or less in the types and blending amounts shown in Table 2 in the chromium oxide-containing materials A to C shown in Table 1 (sulfur-containing slag). Was formulated. Subsequently, these mixtures were deposited, and steam (temperature: 100 ° C.) was blown into the mixture for a period shown in Table 2. The sulfur-containing slag to be mixed with the chromium oxide-containing material was an unaged blast furnace slow-cooled slag.
蒸気エージング処理後の混合物について、環境庁告示46号法による溶出試験法に準拠して、Cr+6溶出量を測定した。得られた結果を表２に示す。なお、上記した各クロム酸化物含有物質への蒸気エージング処理により、表２に示す還元性硫黄濃度の蒸気ドレインが得られた。
一方、Cr+6溶出量が所定値である１mg/ｌ未満であるクロム酸化物含有物質Ｄ〜Ｆには、浸漬エージング処理を施した。
For the mixture after the steam aging treatment, the dissolution amount of Cr +6 was measured in accordance with the dissolution test method based on the Environmental Agency Notification No. 46 method. The obtained results are shown in Table 2. In addition, the vapor | steam drain of the reducible sulfur density | concentration shown in Table 2 was obtained by the vapor aging process to each above-mentioned chromium oxide containing substance.
On the other hand, the chromium oxide-containing materials D to F having a Cr +6 elution amount of less than 1 mg / l which is a predetermined value were subjected to immersion aging treatment.
浸漬エージング処理は、表１に示すクロム酸化物含有物質Ｄ〜Ｆを浸漬に装入し、表２に示す、種類、還元性硫黄濃度、量の還元性硫黄含有水を注入して、表２に示す期間浸漬する処理とした。使用した還元性硫黄含有水は、表２に示す、蒸気エージング処理に際して得られた蒸気ドレイン水を水道水で希釈し、処理対象物質に応じた適正な還元性硫黄濃度に調整したものを用いた。 In the immersion aging treatment, the chromium oxide-containing materials D to F shown in Table 1 are charged into the immersion, and the kinds, reducing sulfur concentrations, and amounts of reducing sulfur-containing water shown in Table 2 are injected, and Table 2 It was set as the process immersed in the period shown to. The reducible sulfur-containing water used was prepared by diluting the steam drain water obtained in the steam aging treatment shown in Table 2 with tap water and adjusting it to an appropriate reductive sulfur concentration according to the substance to be treated. .
なお、クロム酸化物含有物質のCr+6溶出量が１mg/ｌ未満であるクロム酸化物含有物質に、蒸気エージング処理を施した場合を比較例とした。なお、クロム酸化物含有物質の処理量は900〜1300tonであった。
浸漬エージング処理後のクロム酸化物含有物質について、環境庁告示46号法による溶出試験法に準拠して、Cr+6溶出量を測定した。得られた結果を表２に示す。なお、処理の費用を、比較例（処理No.７〜９）を基準（1.0）として、それに対する比として示す。
In addition, the case where the vapor aging process was performed to the chromium oxide containing material whose Cr +6 elution amount of a chromium oxide containing material is less than 1 mg / l was made into the comparative example. The processing amount of the chromium oxide-containing material was 900 to 1300 tons.
For the chromium oxide-containing material after the immersion aging treatment, the dissolution amount of Cr +6 was measured according to the dissolution test method according to the Environmental Agency Notification No. 46 method. The obtained results are shown in Table 2. In addition, the expense of a process is shown as a ratio with respect to the comparative example (process No. 7-9) as a reference | standard (1.0).
本発明例はいずれも、処理後のCr+6溶出量が環境基準値（0.05mg/ｌ未満）以下を十分に満足している。また、処理前のCr+6溶出量が１mg/ｌ未満であるクロム酸化物含有物質については、蒸気エージング処理で発生した蒸気ドレインを利用した浸漬エージング処理を行うことにより、蒸気エージングを行うことなく、Cr+6溶出量を環境基準値（0.05mg/ｌ未満）以下に低下することができる。しかも、処理前のCr+6溶出量によって処理方法を選択する本発明方法によれば、クロム酸化物含有物質の処理費用を大幅に低減できることがわかる。 In all of the inventive examples, the Cr +6 elution amount after the treatment sufficiently satisfies the environmental standard value (less than 0.05 mg / l) or less. In addition, for chromium oxide-containing substances whose Cr +6 elution amount before treatment is less than 1 mg / l, by performing immersion aging treatment using a vapor drain generated by vapor aging treatment, vapor aging is not performed. , Cr +6 elution amount can be reduced below the environmental standard value (less than 0.05 mg / l). Moreover, according to the method of the present invention in which the treatment method is selected based on the Cr +6 elution amount before treatment, it can be seen that the treatment cost of the chromium oxide-containing material can be greatly reduced.
Claims (4)
該クロム酸化物含有物質からのCr+6の溶出量が所定値以上の場合には、該クロム酸化物含有物質に、硫黄および／または酸化数が＋５価以下の硫黄を含有する物質を混合して混合物としたのち、該混合物に水蒸気を吹き込む蒸気エージング処理を施し、
前記クロム酸化物含有物質からのCr+6の溶出量が所定値未満である場合には、該クロム酸化物含有物質を硫黄および／または酸化数が＋５価以下の硫黄を含む液中に浸漬する浸漬エージング処理を施すことを特徴とするクロム酸化物含有物質の処理方法。 In treating the chromium oxide-containing material, measure the amount of Cr +6 elution from the chromium oxide-containing material in advance,
When the elution amount of Cr +6 from the chromium oxide-containing substance is a predetermined value or more, a substance containing sulfur and / or sulfur having an oxidation number of +5 or less is mixed with the chromium oxide-containing substance. And then subjecting the mixture to steam aging treatment to blow water vapor,
When the elution amount of Cr +6 from the chromium oxide-containing material is less than a predetermined value, the chromium oxide-containing material is immersed in a liquid containing sulfur and / or sulfur having an oxidation number of +5 or less. A method for treating a chromium oxide-containing material, characterized by performing immersion aging treatment.
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