JP2004255233A - Method for treating boron-containing waste - Google Patents
Method for treating boron-containing waste Download PDFInfo
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- JP2004255233A JP2004255233A JP2003045674A JP2003045674A JP2004255233A JP 2004255233 A JP2004255233 A JP 2004255233A JP 2003045674 A JP2003045674 A JP 2003045674A JP 2003045674 A JP2003045674 A JP 2003045674A JP 2004255233 A JP2004255233 A JP 2004255233A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ホウ素含有廃棄物の処理方法に関し、特に、ホウ素成分を含有する物品に焼却などの酸化熱処理を加えた処理物をホウ素含有廃棄物として廃棄する前にホウ素の溶出を低減させるようにホウ素含有廃棄物を処理するホウ素含有廃棄物の処理方法に関する。
【０００２】
【従来の技術】
ホウ素成分を含有する物品に焼却などの酸化熱処理を加えた処理物、例えば、一般廃棄物または産業廃棄物などの焼却処理による飛灰を廃棄する前に、この飛灰に含まれるホウ素の溶出を低減させる処理を行うことが、環境対策上望まれている。
【０００３】
このような飛灰を固化する処理方法として、アルカリ金属およびアルカリ土類金属を含むケイ酸塩化合物を主体とする混合物からなる処理材を飛灰に混入して溶融固化することにより金属類の溶出を防止する方法が知られている（例えば、特許文献１参照）。
【０００４】
【特許文献１】
特開平９−２７１７３８号公報（段落番号００１２）
【０００５】
【発明が解決しようとする課題】
しかし、特許文献１の処理方法では、溶融温度が１３５０〜１４００℃と高温であること、アルカリ金属、アルカリ土類金属、ケイ酸塩化合物などの多種の成分を混合する必要があるため高温に耐える処理装置を必要とすること、薬剤の投入や混合などの複雑な工程を行わなければ飛灰を固化することができないことなどの問題がある。
【０００６】
したがって、本発明は、このような従来の問題点に鑑み、ホウ素含有廃棄物を簡便に処理してホウ素の溶出を低減させることができるホウ素含有廃棄物の処理方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究した結果、ホウ素酸化物を含むホウ素含有廃棄物とケイ素酸化物を含むケイ素含有物を同じ系に存在させて３００℃より高く且つ１０００℃以下の温度、好ましくは５００〜１０００℃の温度、さらに好ましくは７００〜９００℃の温度で加熱することにより、ホウ素酸化物とケイ素酸化物とを融合させ、その融合物を冷却することにより、ホウ素の溶出を低減できる融合物を生成することができることを見出し、本発明を完成するに至った。ここで、「融合」とは、両方が溶けあってもよいし、一方が溶融して他方の未溶融物に付着する形態でもよい。具体的には、溶融したホウ素酸化物がケイ素酸化物に付着した形態が最も好ましい。ケイ素酸化物の方が機械的強度が高いため、融合物の取り扱いが容易になり、２次汚染を防止できるからである。
【０００８】
すなわち、本発明によるホウ素含有廃棄物の処理方法は、ホウ素酸化物を含むホウ素含有廃棄物とケイ素酸化物を含むケイ素含有物とが存在する系を３００℃より高く且つ１０００℃以下の温度、好ましくは５００〜１０００℃の温度、さらに好ましくは７００〜９００℃の温度で加熱してホウ素酸化物とケイ素酸化物の融合物を形成することを特徴とする。
【０００９】
このホウ素含有廃棄物の処理方法において、ホウ素酸化物を含むホウ素含有廃棄物とケイ素酸化物を含むケイ素含有物とが存在する系は、１重量部のホウ素酸化物に対して好ましくは１０重量部以上、さらに好ましくは４０重量部以上のケイ素酸化物を含む系である。また、ケイ素含有物がケイ素酸化物を含む土壌であるのが好ましい。
【００１０】
【発明の実施の形態】
本発明によるホウ素含有廃棄物の処理方法の実施の形態は、ホウ素酸化物を含むホウ素含有廃棄物とケイ素酸化物を含むケイ素含有物とが存在する系を３００℃より高く且つ１０００℃以下の温度、好ましくは５００〜１０００℃の温度、さらに好ましくは７００〜９００℃の温度で加熱してホウ素酸化物とケイ素酸化物の融合物を形成することを特徴とする。
【００１１】
本明細書中において、ホウ素含有廃棄物とは、ホウ素成分を含む物品、一般廃棄物、産業廃棄物、汚染された土壌などであり、常温で固形のものが好ましく、液状であっても、特に加熱処理において障害となる排ガスや有害化合物が生成しなければ問題ない。特に、ホウ素が酸化されているＢ２Ｏ３などになっている物が含まれているものがよい。例えば、電子基板類を焼却処理することにより得られる飛灰やホウ砂のなどが挙げられる。
【００１２】
本明細書中において、ケイ素含有物とは、ケイ素成分を含む物品や廃棄物などであり、常温で固形物であればよい。その形態は、顆粒、粒状または砂状であることが好ましく、１つの大きさがより細かい物がよい。例えば、ケイ素酸化物を含む土壌、通常の産業廃棄物として扱える廃土、汚染物を含有する汚染土壌などが挙げられる。
【００１３】
ホウ素酸化物を含むホウ素含有廃棄物とケイ素酸化物を含むケイ素含有物は、それぞれ別個に加熱処理装置、すなわち炉に投入してもよいが、炉に投入する前に混合してもよい。ホウ素含有廃棄物とケイ素含有物を混合する装置としては、市販のブレンダー装置を使用すればよい。
【００１４】
炉に投入するケイ素酸化物の量は、ホウ素酸化物１重量部に対して、好ましくは１０重量部以上、さらに好ましくは４０重量部以上である。加熱処理時にケイ素酸化物の量がホウ素酸化物よりも多い方が、加熱処理後の取扱いを投入時と同様な設備により行うことが可能になり、簡易であるためである。
【００１５】
このようにケイ素酸化物の量をホウ素酸化物の量よりも圧倒的に多くするのは、加熱処理時にホウ素酸化物が先に溶解して液状になってケイ素酸化物に付着するか、溶解して液状になったホウ素酸化物にケイ素酸化物が付着して、ホウ素酸化物の溶解した液がケイ素酸化物の界面で局部的に融合してガラス質を形成し、この間にも他のケイ素酸化物がホウ素酸化物に付着して顆粒状の凝集体を形成し、この凝集体が冷却後においてホウ素酸化物を包み込む形態になり、ホウ素の溶出を抑制するのに好適な形態になると考えられるからである。また、この凝集体の大きさは、ケイ素酸化物の大きさの数倍程度であり、加熱処理後の取扱いなどを損なうことはない。
【００１６】
また、ケイ素酸化物を多量に投入することにより、ホウ素酸化物の周辺に多量のケイ素酸化物を存在させることができるとともに、ケイ素酸化物によりホウ素酸化物の周辺を覆うことにより、ホウ素酸化物の周囲の雰囲気を制御することができ、ホウ素などの揮発を抑制することもできるため、ホウ素酸化物の処理を確実に行うことが可能になる。
【００１７】
加熱処理における加熱温度は、３００℃より高く且つ１０００℃以下の温度にすればよいが、ホウ素酸化物とケイ素酸化物の共晶温度である４５０℃付近の温度以上であることが好ましく、９００℃以下の温度であることが好ましい。ホウ素酸化物を確実に溶解してケイ素酸化物と反応させるためである。また、１０００℃より高い温度では、土壌の成分によって異なるが、土壌が溶解し始める可能性があり、融合物が大きくなり、後工程の取扱いが悪くなるので、１０００℃より高い温度にするのは好ましくない。また、前述したようなホウ素酸化物を包み込むような形態なるか否かが明確でなく、この形態を形成するためには、５００〜１０００℃の温度に加熱するのが好ましく、７００〜９００℃の温度に加熱するのがさらに好ましい。さらに、加熱時間は、ホウ素酸化物とケイ素酸化物の配合比や、反応の進行状況などによって、適宜設定することができる。
【００１８】
加熱処理によってホウ素酸化物とケイ素酸化物の融合物が形成された後、放置冷却する。この冷却は、水冷によって行ってもよいし、大気中に放置して冷却することによって行ってもよい。
【００１９】
融合物からのホウ素の溶出試験については、環境庁告示第４６号に記載された溶出試験方法に従って測定などを行う。融合物が大きい場合には、測定データの精度を上げるために、融合物を２ｍｍ以下に粉砕して溶出試験を行えばよい。
【００２０】
【実施例】
以下、本発明によるホウ素含有廃棄物の処理方法の実施例について詳細に説明する。
【００２１】
［実施例１］
８重量％のホウ素を含有するホウ砂５重量％と、２８重量％のケイ素を含有する土壌９５重量％とを混合して、大気中において９００℃に加熱して、２０分間加熱処理を行った。この加熱処理終了後に、融合物を炉から取り出して、そのまま放置して冷却させて固化させた。
【００２２】
この冷却後の融合物を２ｍｍ程度の粒径に粉砕し、環境庁告示第４６号に従ってホウ素の溶出試験を行った。その結果、ホウ素の溶出値は１０ｍｇ／Ｌであり、溶出率は３％であった。なお、上記の加熱処理後の融合物中のホウ素の含有量は３８２０ｍｇ／ｋｇであった。この溶出試験の結果から、本実施例のホウ素含有廃棄物の処理方法によって、ホウ素の溶出を抑制して、ホウ素による２次汚染を抑制することが可能であることがわかる。
【００２３】
［実施例２］
加熱温度を７００℃とした以外は、実施例１と同様の処理および試験を行ったところ、ホウ素の溶出値は５４ｍｇ／Ｌであり、溶出率は１７％であった。なお、上記の加熱処理後の融合物中のホウ素の含有量は３１９０ｍｇ／ｋｇであった。
【００２４】
［実施例３］
加熱温度を５００℃とした以外は、実施例１と同様の処理および試験を行ったところ、ホウ素の溶出値は２００ｍｇ／Ｌであり、溶出率は５８％であった。なお、上記の加熱処理後の融合物中のホウ素の含有量は３４５０ｍｇ／ｋｇであった。
【００２５】
［比較例１］
加熱温度を３００℃とした以外は、実施例１と同様の処理および試験を行ったところ、ホウ素の溶出値は３６０ｍｇ／Ｌであり、溶出率は１００％であった。なお、上記の加熱処理後の融合物中のホウ素の含有量は３５２０ｍｇ／ｋｇであった。
【００２６】
［比較例２］
実施例１と同じホウ砂と土壌の混合物について、実施例１の加熱処理を行わずに、そのまま実施例１と同様の溶出試験を行った。その結果、ホウ素の溶出値は８０ｍｇ／Ｌであり、溶出率は１００％であった。なお、上記の加熱処理後の融合物中のホウ素の含有量は４１００ｍｇ／ｋｇであった。
【００２７】
これらの実施例１〜３および比較例１〜２の結果を表１にまとめて示す。
【００２８】
【表１】
これらの結果から、ホウ素の溶出を抑えるためには、１０００℃以下でより高い温度で加熱処理を行うのが好ましいことがわかる。特に、実施例で使用したホウ砂の融点は８７８℃であるので、この融点に近い温度以上で加熱処理を行えば、ホウ素とケイ素がホウ珪酸ガラスを形成してホウ素の溶出が抑えられると考えられる。
【００３０】
【発明の効果】
上述したように、本発明によれば、ホウ素の溶出のおそれがある廃棄物でも、簡便な方法でホウ素の溶出を抑制することができ、また、土壌などの自然資源をそのまま利用することができるので、特別な薬剤も必要せず、そのような薬剤の製造および使用による２次汚染などの発生もない。したがって、本発明によるホウ素含有廃棄物の処理方法は、極めて地球環境にやさしい処理方法である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for treating a boron-containing waste, and in particular, to reduce the elution of boron before discarding a treated product obtained by applying an oxidation heat treatment such as incineration to an article containing a boron component as a boron-containing waste. The present invention relates to a boron-containing waste treatment method for treating boron-containing waste.
[0002]
[Prior art]
Before disposing of oxidized heat treatment such as incineration to articles containing boron components, for example, fly ash from incineration treatment of general waste or industrial waste, the elution of boron contained in this fly ash It is desired to perform a process for reducing the amount in terms of environmental measures.
[0003]
As a processing method for solidifying such fly ash, elution of metals by mixing and solidifying a processing material composed of a mixture mainly composed of a silicate compound containing an alkali metal and an alkaline earth metal into the fly ash. There is known a method for preventing such a problem (see, for example, Patent Document 1).
[0004]
[Patent Document 1]
JP-A-9-271738 (paragraph 0012)
[0005]
[Problems to be solved by the invention]
However, in the treatment method of Patent Document 1, the melting temperature is as high as 1350 to 1400 ° C., and it is necessary to mix various components such as an alkali metal, an alkaline earth metal, and a silicate compound. There are problems such as the necessity of a processing device and the inability to solidify fly ash unless complicated steps such as charging and mixing of chemicals are performed.
[0006]
Therefore, an object of the present invention is to provide a method for treating a boron-containing waste that can easily treat the boron-containing waste and reduce the elution of boron in view of the conventional problems. .
[0007]
[Means for Solving the Problems]
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that a boron-containing waste containing boron oxide and a silicon-containing material containing silicon oxide were present in the same system and higher than 300 ° C and 1000 ° C. By heating at a temperature below, preferably at a temperature of 500 to 1000 ° C., more preferably at a temperature of 700 to 900 ° C., the boron oxide and the silicon oxide are fused, and It has been found that a fusion product capable of reducing elution of can be produced, and the present invention has been completed. Here, “fusion” may be a form in which both are melted or one is melted and adheres to the other unmelted material. Specifically, a form in which the molten boron oxide adheres to the silicon oxide is most preferable. This is because the silicon oxide has a higher mechanical strength, so that the fusion product can be easily handled and secondary contamination can be prevented.
[0008]
That is, the method for treating a boron-containing waste according to the present invention is a system in which a boron-containing waste containing boron oxide and a silicon-containing substance containing silicon oxide are present at a temperature higher than 300 ° C. and 1000 ° C. or less, preferably Is characterized by heating at a temperature of 500 to 1000 ° C., more preferably 700 to 900 ° C., to form a fusion product of boron oxide and silicon oxide.
[0009]
In this method for treating boron-containing waste, the system in which the boron-containing waste containing boron oxide and the silicon-containing material containing silicon oxide are present is preferably 10 parts by weight with respect to 1 part by weight of boron oxide. Above, more preferably a system containing at least 40 parts by weight of silicon oxide. Preferably, the silicon-containing material is a soil containing silicon oxide.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
An embodiment of the method for treating a boron-containing waste according to the present invention is a method for treating a system in which a boron-containing waste containing boron oxide and a silicon-containing material containing silicon oxide are present at a temperature higher than 300 ° C and 1000 ° C or less. , Preferably at a temperature of 500 to 1000C, more preferably at a temperature of 700 to 900C to form a fusion of boron oxide and silicon oxide.
[0011]
In the present specification, the boron-containing waste is an article containing a boron component, general waste, industrial waste, contaminated soil, and the like. There is no problem as long as no exhaust gas or harmful compounds that hinder the heat treatment are generated. In particular, it is preferable that a material containing boron-oxidized B 2 O 3 or the like is included. For example, fly ash and borax obtained by incinerating electronic substrates are included.
[0012]
In the present specification, the silicon-containing material is an article or waste containing a silicon component, and may be a solid at room temperature. The form is preferably granules, granules or sand, and one having a smaller size is preferred. Examples include soil containing silicon oxide, waste soil that can be treated as ordinary industrial waste, and contaminated soil containing contaminants.
[0013]
The boron-containing waste containing boron oxide and the silicon-containing material containing silicon oxide may be separately charged into a heat treatment apparatus, that is, a furnace, or may be mixed before being charged into the furnace. As a device for mixing the boron-containing waste and the silicon-containing material, a commercially available blender device may be used.
[0014]
The amount of silicon oxide to be charged into the furnace is preferably at least 10 parts by weight, more preferably at least 40 parts by weight, based on 1 part by weight of boron oxide. This is because, when the amount of silicon oxide is larger than that of boron oxide during the heat treatment, handling after the heat treatment can be performed with the same equipment as at the time of introduction, which is simple.
[0015]
The reason why the amount of silicon oxide is overwhelmingly larger than the amount of boron oxide is that the boron oxide first dissolves during the heat treatment to become a liquid and adhere to the silicon oxide or to dissolve it. The silicon oxide adheres to the boron oxide in a liquid state, and the liquid in which the boron oxide is dissolved locally fuses at the interface of the silicon oxide to form a vitreous material. The substance adheres to the boron oxide to form granular aggregates, and the aggregates become wrapped around the boron oxide after cooling, which is considered to be a suitable form for suppressing the elution of boron. It is. The size of the aggregate is several times the size of the silicon oxide, and does not impair handling after the heat treatment.
[0016]
In addition, by introducing a large amount of silicon oxide, a large amount of silicon oxide can be present around the boron oxide, and by covering the periphery of the boron oxide with the silicon oxide, Since the surrounding atmosphere can be controlled and the volatilization of boron and the like can be suppressed, the treatment of boron oxide can be reliably performed.
[0017]
The heating temperature in the heat treatment may be higher than 300 ° C. and equal to or lower than 1000 ° C., and is preferably equal to or higher than 450 ° C., which is the eutectic temperature of boron oxide and silicon oxide, and 900 ° C. The temperature is preferably as follows. This is because the boron oxide is surely dissolved and reacted with the silicon oxide. At a temperature higher than 1000 ° C., although it depends on the components of the soil, the soil may start to dissolve, the fusion product increases, and the handling of the post-process becomes poor. Not preferred. Further, it is not clear whether or not the above-described form encloses the boron oxide, and in order to form this form, it is preferable to heat to a temperature of 500 to 1000 ° C. It is more preferred to heat to temperature. Further, the heating time can be appropriately set depending on the mixing ratio of the boron oxide and the silicon oxide, the progress of the reaction, and the like.
[0018]
After a fusion of boron oxide and silicon oxide is formed by the heat treatment, the mixture is left to cool. This cooling may be performed by water cooling, or may be performed by leaving it in the air and cooling.
[0019]
As for the dissolution test of boron from the fusion product, measurement is performed according to the dissolution test method described in the Environment Agency Notification No. 46. When the fusion product is large, the dissolution test may be performed by crushing the fusion product to 2 mm or less in order to improve the accuracy of the measurement data.
[0020]
【Example】
Hereinafter, examples of the method for treating boron-containing waste according to the present invention will be described in detail.
[0021]
[Example 1]
5% by weight of borax containing 8% by weight of boron and 95% by weight of soil containing 28% by weight of silicon were mixed, heated to 900 ° C. in the atmosphere, and subjected to a heat treatment for 20 minutes. . After the completion of the heat treatment, the fused product was taken out of the furnace, left as it was, and cooled to solidify.
[0022]
The cooled fusion product was pulverized to a particle size of about 2 mm and subjected to a boron elution test according to the notification of the Environment Agency No. 46. As a result, the elution value of boron was 10 mg / L, and the elution rate was 3%. The content of boron in the fusion product after the above heat treatment was 3820 mg / kg. From the results of the dissolution test, it is understood that the dissolution method of boron can be suppressed and the secondary contamination by boron can be suppressed by the method for treating the boron-containing waste in this example.
[0023]
[Example 2]
When the same treatment and test as in Example 1 were performed except that the heating temperature was 700 ° C., the elution value of boron was 54 mg / L, and the elution rate was 17%. In addition, the content of boron in the fusion product after the above heat treatment was 3190 mg / kg.
[0024]
[Example 3]
The same treatment and test as in Example 1 were carried out except that the heating temperature was 500 ° C., the elution value of boron was 200 mg / L, and the elution rate was 58%. In addition, the content of boron in the fusion product after the above heat treatment was 3450 mg / kg.
[0025]
[Comparative Example 1]
When the same treatment and test as in Example 1 were performed except that the heating temperature was set to 300 ° C., the elution value of boron was 360 mg / L, and the elution rate was 100%. The content of boron in the fusion product after the heat treatment was 3520 mg / kg.
[0026]
[Comparative Example 2]
The same mixture of borax and soil as in Example 1 was subjected to the same dissolution test as in Example 1 without performing the heat treatment of Example 1. As a result, the elution value of boron was 80 mg / L, and the elution rate was 100%. In addition, the content of boron in the fusion product after the heat treatment was 4100 mg / kg.
[0027]
Table 1 collectively shows the results of Examples 1 to 3 and Comparative Examples 1 and 2.
[0028]
[Table 1]
From these results, it can be seen that in order to suppress the elution of boron, it is preferable to perform the heat treatment at 1000 ° C. or lower and at a higher temperature. Particularly, since the melting point of the borax used in the examples is 878 ° C., it is considered that if the heat treatment is performed at a temperature higher than this melting point, boron and silicon form borosilicate glass and the elution of boron is suppressed. Can be
[0030]
【The invention's effect】
As described above, according to the present invention, even in a waste in which boron may be eluted, the elution of boron can be suppressed by a simple method, and natural resources such as soil can be used as it is. Therefore, no special agent is required, and there is no occurrence of secondary contamination due to the production and use of such agent. Therefore, the method for treating boron-containing waste according to the present invention is an extremely environmentally friendly treatment method.
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| JP2020032345A (en) * | 2018-08-29 | 2020-03-05 | Ｊｆｅスチール株式会社 | Method for suppressing elution of boron in boron-including material, and method for production of treatment material for boron elution suppression |
| JP2022096598A (en) * | 2020-12-17 | 2022-06-29 | Ｊｆｅスチール株式会社 | Method of modifying boron-containing substance, and method of manufacturing material for civil engineering and construction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020032345A (en) * | 2018-08-29 | 2020-03-05 | Ｊｆｅスチール株式会社 | Method for suppressing elution of boron in boron-including material, and method for production of treatment material for boron elution suppression |
| JP2022096598A (en) * | 2020-12-17 | 2022-06-29 | Ｊｆｅスチール株式会社 | Method of modifying boron-containing substance, and method of manufacturing material for civil engineering and construction |
| JP7303989B2 (en) | 2020-12-17 | 2023-07-06 | Ｊｆｅスチール株式会社 | Method for modifying boron-containing substance and method for producing civil engineering and construction material |
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