JP2014062164A - Treatment agent - Google Patents
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- JP2014062164A JP2014062164A JP2012207082A JP2012207082A JP2014062164A JP 2014062164 A JP2014062164 A JP 2014062164A JP 2012207082 A JP2012207082 A JP 2012207082A JP 2012207082 A JP2012207082 A JP 2012207082A JP 2014062164 A JP2014062164 A JP 2014062164A
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Abstract
Description
本発明は、処理剤に関するものであり、特に、重金属の固定化処理に適する処理剤に関するものである。 The present invention relates to a treatment agent, and particularly to a treatment agent suitable for heavy metal immobilization treatment.
従来より、産業廃棄物や都市ごみなどは、焼却処理された後に埋立処分されている。 Conventionally, industrial waste and municipal waste have been incinerated after being incinerated.
そして、焼却処理により発生する焼却灰や飛灰などには、人体等に有害な重金属が含まれているために、埋立処分した焼却灰や飛灰などから重金属が溶出しないように重金属の固定化処理を行っている（たとえば、特許文献１参照。）。 Incineration ash and fly ash generated by incineration contain heavy metals that are harmful to the human body, etc., so that heavy metals are fixed so that heavy metals do not elute from landfilled incineration ash or fly ash. Processing is performed (for example, see Patent Document 1).
本発明者は、重金属の固定化処理に適した処理剤を鋭意研究し、本発明を成すに至った。 The inventor diligently studied a treatment agent suitable for the heavy metal immobilization treatment, and reached the present invention.
すなわち、請求項１に係る本発明では、硫黄の高分子陰イオン（ＳＸ ｍ−（ｘ、ｍは整数。））と粒子状の硫黄を含有する水溶液を主成分とすることを特徴とする処理剤を提供する。
That is, the present invention according to
また、請求項２に係る本発明では、硫黄の高分子陰イオン（ＳＸ ｍ−（ｘ、ｍは整数。））を含有する水溶液であり、処理時に硫黄の高分子陰イオンから硫黄の陰イオン（Ｓ２−）と固体（Ｓ）が生成されることを特徴とする処理剤を提供する。
Further, the present invention according to
本発明に係る処理剤は、硫黄の高分子陰イオンと粒子状の硫黄を含有する水溶液を主成分としており、硫黄の高分子陰イオンの作用によって、重金属の固定化処理を行うことができる。 The treatment agent according to the present invention is mainly composed of an aqueous solution containing a sulfur polymer anion and particulate sulfur, and the heavy metal can be fixed by the action of the sulfur polymer anion.
この処理剤は、アスベストの結晶の層間で硫黄の陰イオンの酸化反応（分解反応）が進んでアスベストの繊維を分解することができるとともに、固体分の硫黄に吸着されて沈殿分離することもできる。 This treatment agent is capable of decomposing asbestos fibers by proceeding with an oxidation reaction (decomposition reaction) of sulfur anions between the layers of asbestos crystals, and is also adsorbed by solid sulfur and separated by precipitation. .
そのため、本発明に係る処理剤は、重金属の固定処理を行う処理剤として有効であるとともに、アスベストの分解処理を行う処理剤としても有効である。 Therefore, the treatment agent according to the present invention is effective as a treatment agent for fixing heavy metals, and is also effective as a treatment agent for decomposing asbestos.
本発明に係る処理剤は、硫黄の高分子陰イオン（ＳＸ ｍ−（ｘ、ｍは整数。））と粒子状の硫黄を含有する水溶液を主成分とする。 The treatment agent according to the present invention is mainly composed of an aqueous solution containing sulfur polymer anions (S x m- (x and m are integers)) and particulate sulfur.
製造方法は、特に限定されないが、たとえば下記に説明するようにして製造することができる。 Although a manufacturing method is not specifically limited, For example, it can manufacture as explained below.
まず、硫黄１０重量部とアルカリ水１００重量部とを反応容器に投入し、上蓋を閉じ、混合機で約１０分間混合する。なお、ここでは、アルカリ水として消石灰の水溶液を用いている。 First, 10 parts by weight of sulfur and 100 parts by weight of alkaline water are put into a reaction vessel, the upper lid is closed, and the mixture is mixed for about 10 minutes with a mixer. Here, a slaked lime aqueous solution is used as the alkaline water.
次に、反応容器の上蓋を開け、反応容器に中性又は陰性の界面活性剤５重量部を投入する。ここで、中性の界面活性剤としては、ノニオン性界面活性剤を使用し、陰性の界面活性剤としては、アニオン性界面活性剤を使用することができる。 Next, the upper lid of the reaction vessel is opened, and 5 parts by weight of a neutral or negative surfactant is put into the reaction vessel. Here, a nonionic surfactant can be used as the neutral surfactant, and an anionic surfactant can be used as the negative surfactant.
次に、反応容器の上蓋を閉じ、混合機で約１０分間混合する。その際に、反応容器に高周波振動機で振動を加えてもよい。 Next, the upper lid of the reaction vessel is closed, and mixing is performed for about 10 minutes with a mixer. At that time, the reaction vessel may be vibrated with a high-frequency vibrator.
次に、反応容器を加熱装置で加熱し、反応容器の内部圧力が２．５Kg/cm2以下、内部温度が９０℃以上となるようにする。反応容器の内部温度が１１０℃に達してから約３０分間放置して、反応容器の内部で混合反応させる。 Next, the reaction vessel is heated with a heating device so that the internal pressure of the reaction vessel is 2.5 kg / cm 2 or less and the internal temperature is 90 ° C. or more. After the internal temperature of the reaction vessel reaches 110 ° C., the reaction vessel is left to stand for about 30 minutes to cause a mixing reaction inside the reaction vessel.
その後、加熱を停止するとともに、内部圧力が低下するまで放置し、安定したら排気を行って内部圧力を大気圧とし、上蓋を開ける。 After that, the heating is stopped and the system is left until the internal pressure decreases. When the internal pressure is stabilized, the exhaust is performed to bring the internal pressure to atmospheric pressure, and the upper cover is opened.
これにより、反応容器には、液体状の薬液９０重量部と固体状の沈殿物１０重量部とが得られる。このようにして得られた薬液について調べたところ、薬液は、硫黄の高分子陰イオン（ＳＸ ｍ−（ｘ、ｍは整数。））と粒子状の硫黄を含有する水溶液であることがわかった。 As a result, 90 parts by weight of liquid chemical solution and 10 parts by weight of solid precipitate are obtained in the reaction vessel. When the chemical solution thus obtained was examined, it was found that the chemical solution was an aqueous solution containing sulfur polymer anions (S X m- (x and m are integers)) and particulate sulfur. It was.
通常であれば、消石灰と硫黄と水とを反応させた場合、多硫化カルシウムの水溶液が生成されると考えられるが、上記薬液についてＸＡＮＥＳ（Ｘ−ｒａｙ Ａｂｓｏｒｐｔｉｏｎ Ｎｅａｒ Ｅｄｇｅ Ｓｔｒｕｃｔｕｒｅ：Ｘ線吸収端近傍構造）法によりＸＡＮＥＳスペクトルを測定したところ、固体の硫黄と近似することがわかった。 Normally, when slaked lime, sulfur, and water are reacted, an aqueous solution of calcium polysulfide is considered to be produced. However, the XANES (X-ray Absorption Near Edge Structure: X-ray absorption edge vicinity structure of the above chemical solution is considered. ) Method to measure the XANES spectrum, it was found to approximate solid sulfur.
すなわち、上記薬液のＸＡＮＥＳスペクトル（蛍光収量）は、図１（ａ）に示すように、２４７１．３eVに主ピークを有し、２４７９．５eVにブロードピークを有している。なお、２４６９．５eVに小さな立ち上がりが検出された。 That is, the XANES spectrum (fluorescence yield) of the chemical solution has a main peak at 2471.3 eV and a broad peak at 2479.5 eV, as shown in FIG. A small rising edge was detected at 2469.5 eV.
これに対して、固体の硫黄のＸＡＮＥＳスペクトル（電子収量）は、図１（ｂ）に示すように、ほぼ同じく２４７１．３eVに主ピークを有し、２４７８．４eVにブロードピークを有している。 On the other hand, the XANES spectrum (electron yield) of solid sulfur has a main peak at 2471.3 eV and a broad peak at 2478.4 eV, as shown in FIG. .
このことから、上記薬液は、水溶液中に多硫化カルシウムではなく固体の硫黄として含有されていることがわかった。また、２４６９．５eVに検出された小さな立ち上がりがＮａ２Ｓの水溶液の２４７０．９eVのピークと近似していることから、一部が硫黄の陰イオン（たとえば、Ｓ２−）の酸化状態として含有されていることがわかる。 From this, it was found that the chemical solution was contained in the aqueous solution not as calcium polysulfide but as solid sulfur. Moreover, since the small rising edge detected at 2469.5 eV approximates the peak of 2470.9 eV of the aqueous solution of Na 2 S, a part of it is contained as an oxidation state of sulfur anion (for example, S 2− ). You can see that
そして、硫黄が水に不溶であるのに上記薬液が透明な溶液であり、ゼータ電位を測定したところ−９３．３９mVと非常に大きく、また、粒子径を測定したところ約８μｍと非常に大きいことから、この水溶液には硫黄が高分子陰イオン（ＳＸ ｍ−（ｘ、ｍは整数。）、たとえば、Ｓ２−）の状態で存在しており、硫黄のポリマー分子に負電荷が非局在化した構造で存在していると考えられる。 Although the above chemical solution is a transparent solution even though sulfur is insoluble in water, the zeta potential was measured to be very large as -93.39 mV, and the particle size was measured to be very large as about 8 μm. In this aqueous solution, sulfur exists in the state of a polymer anion (S X m- (x, m is an integer), for example, S 2− ), and the sulfur polymer molecule has no negative charge. It is considered that it exists in a naturalized structure.
この硫黄の高分子陰イオンは不可逆的に硫黄の陰イオンと固体の硫黄とを生成する。そのため、処理時には、硫黄の高分子陰イオンから硫黄の陰イオンとコロイド状の固体の硫黄とが生成され、硫黄の陰イオンの酸化反応が進んで重金属と結合するとともに固体分の硫黄によって吸着され、沈殿分離することができる。 The sulfur polymer anion irreversibly generates a sulfur anion and solid sulfur. Therefore, during processing, sulfur anions and colloidal solid sulfur are produced from sulfur polymer anions, and the oxidation reaction of sulfur anions proceeds to be combined with heavy metals and adsorbed by solid sulfur. The precipitate can be separated.
なお、処理剤をアスベストに塗布した場合には、アスベストの結晶の層間に硫黄の陰イオンがインターカレートした後に酸化反応（分解反応）が進んでイオン半径が大きな硫酸イオン等になって結晶破壊が起きてアスベストの繊維を分解することができるとともに、固体分の硫黄に吸着されて沈殿分離することもできる。 When the treatment agent is applied to asbestos, sulfur anions intercalate between the asbestos crystal layers, followed by an oxidation reaction (decomposition reaction) that causes sulfate ions with a large ion radius to break the crystal. As a result, the asbestos fibers can be decomposed and can be adsorbed by solid sulfur and separated by precipitation.
そのため、上記薬剤は、重金属の固定処理を行う処理剤として有効であるのみならず、アスベストの分解処理を行う処理剤としても有効である。 Therefore, the said chemical | medical agent is not only effective as a processing agent which performs the fixed process of a heavy metal, but is effective also as a processing agent which performs a decomposition process of asbestos.
なお、上記ＸＡＮＥＳ法では、液体状の薬液の蛍光収量と固体状の硫黄の電子収量を比較しているが、本発明者は、ＸＡＮＥＳ法を用いた場合、液体の蛍光収量と固体の電子収量とがほぼ同じ傾向を示すことや、陽イオンの違いによる影響がないことについて検証を行っており、液体状の薬液の蛍光収量と固体状の硫黄の電子収量とを比較することで薬液の成分を特定しても何ら問題はない。 In the XANES method, the fluorescence yield of the liquid chemical solution and the electron yield of solid sulfur are compared. However, when the XANES method is used, the present inventor has analyzed the fluorescence yield of the liquid and the electron yield of the solid. Are showing the same tendency and are not affected by the difference in cations, comparing the fluorescence yield of liquid chemical and the electron yield of solid sulfur, There is no problem even if it is specified.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5162186A (en) * | 1974-11-29 | 1976-05-29 | Nichireki Chem Ind Co | Odeino shorihoho |
| JPS5959281A (en) * | 1982-09-30 | 1984-04-05 | Kazuhisa Hoshino | Chemical liquid composition for treatment of noxious waste matter and its preparation |
| JP2002086128A (en) * | 2000-09-14 | 2002-03-26 | Shimizu Corp | Method for cleaning contaminated soil |
| JP2004033812A (en) * | 2002-06-28 | 2004-02-05 | Jfe Engineering Kk | Cleaning method of polluted soil or the like and cleaning equipment |
| JP2009209231A (en) * | 2008-03-03 | 2009-09-17 | Koda Tooru | Method for producing polysulfide chemical agent for heavy metal fixation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5162186A (en) * | 1974-11-29 | 1976-05-29 | Nichireki Chem Ind Co | Odeino shorihoho |
| JPS5959281A (en) * | 1982-09-30 | 1984-04-05 | Kazuhisa Hoshino | Chemical liquid composition for treatment of noxious waste matter and its preparation |
| JP2002086128A (en) * | 2000-09-14 | 2002-03-26 | Shimizu Corp | Method for cleaning contaminated soil |
| JP2004033812A (en) * | 2002-06-28 | 2004-02-05 | Jfe Engineering Kk | Cleaning method of polluted soil or the like and cleaning equipment |
| JP2009209231A (en) * | 2008-03-03 | 2009-09-17 | Koda Tooru | Method for producing polysulfide chemical agent for heavy metal fixation |
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