JP4357954B2 - Flocculating precipitant for refractory castable waste liquid treatment - Google Patents
Flocculating precipitant for refractory castable waste liquid treatment Download PDFInfo
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Description
本発明は、耐火キャスタブル廃液処理用凝集沈澱剤に関し、特に、ベントナイト，硫酸アルミニウム，リン酸ナトリウムの３者を組み合わせた耐火キャスタブル廃液処理用凝集沈澱剤に関する。 The present invention relates to a flocculating precipitant for treating a refractory castable waste liquid, and more particularly to a flocculating precipitant for treating a refractory castable waste liquid that combines bentonite, aluminum sulfate, and sodium phosphate.
耐火キャスタブルの廃液［例えば、耐火キャスタブル製造用ミキサーや練り受け箱(トロ箱)など、または、スコップやその他の治具など、に付着したキャスタブルを洗浄する際に発生する廃液］は、耐火キャスタブルの種類によって異なるが、緑色や黒色など、いずれも着色しており、そのままで廃棄することができない。そこで、該廃液の処理が必要となり、従来から、廃液中の固形分を濾過分離する方法や廃液に凝集沈澱剤を添加する方法などが採用されている。 Refractory castable waste liquids (for example, waste liquids that are generated when cleaning castables that adhere to refractory castable mixers, kneading bins (toro boxes), scoops, other jigs, etc.) Depending on the type, both green and black are colored and cannot be discarded as they are. Therefore, treatment of the waste liquid is required, and conventionally, a method of filtering and separating solids in the waste liquid, a method of adding a coagulating precipitant to the waste liquid, and the like have been adopted.
一般に、凝集沈澱剤としては、ベントナイト，硫酸アルミニウム，リン酸ナトリウムなどが知られており、夫々単独で使用されている。
このうち、特に、ベントナイトは、水中で高度に膨潤し、様々な物質を吸収する性質を有することから、廃水処理用の凝集沈澱剤として従来から広く使用されており、例えば、特許文献１(特開平7−24443号公報)には、吸着性能に優れ、廃水処理用に好適な“高濃度ベントナイトスラリー組成物”を提供することを目的として、「ベントナイトとアルカリ金属塩と水の重量比が“1：0.02〜0.2：0.8〜3.0”の範囲にあるベントナイトスラリー組成物」が提案されている。
In general, bentonite, aluminum sulfate, sodium phosphate, and the like are known as coagulating precipitants, and each is used alone.
Among these, in particular, bentonite has been widely used as a coagulating precipitation agent for wastewater treatment because it has a property of being highly swollen in water and absorbing various substances. (Kaihei 7-24443) has an adsorbing performance and is suitable for wastewater treatment with the purpose of providing a “high concentration bentonite slurry composition”, wherein the weight ratio of bentonite, alkali metal salt and water is “ A bentonite slurry composition in the range of 1: 0.02 to 0.2: 0.8 to 3.0 "has been proposed.
また、特許文献２(特開平11−276807号公報)には、「石膏、硫酸アルミニウム、リン酸水素ナトリウム、炭酸ソーダ、アルキル酸ソーダ及びアクリル酸ソーダとアクリルアミドの共重合物を、重量比で“65〜75：10〜20：0.5〜1.5：7〜13：0.5〜1.5：2〜5”の割合で混合し、無機材料が95重量％以上を占める凝集剤」が提案されている。
さらに、特許文献３(特許第3413394号公報)には、光学研磨用酸化セリウム研磨剤廃液を無公害化処理すると共に、該廃液からの“酸化セリウムの回収”を意図して、「酸化セリウム研磨剤廃液中にアルカリ成分を添加してｐＨ7〜11に調整し、研磨剤廃液のゼータ電位を−25〜−70ｍＶに変化させた後、酸化セリウム成分(及びその他の固形分)を分離処理すること」が提案されている。
Patent Document 2 (Japanese Patent Application Laid-Open No. 11-276807) describes “gypsum, aluminum sulfate, sodium hydrogen phosphate, sodium carbonate, sodium alkylate, and a copolymer of sodium acrylate and acrylamide in a weight ratio” 65-75: 10-20: 0.5-1.5: 7-13: 0.5-1.5: 2-5 ", a flocculant in which the inorganic material accounts for 95% by weight or more" has been proposed.
Further, in Patent Document 3 (Japanese Patent No. 3413394), the cerium oxide abrasive waste liquid for optical polishing is treated to be non-polluting and “cerium oxide polishing” is intended for “recovering cerium oxide” from the waste liquid. After adjusting the pH to 7-11 by adding an alkaline component to the waste agent liquid and changing the zeta potential of the abrasive waste liquid to -25 to -70 mV, the cerium oxide component (and other solids) is separated. Is proposed.
凝集沈澱剤としては、前記したように、一般に、硫酸アルミニウム，ベントナイト，リン酸ナトリウムなどが知られており、夫々単独で使用されている。このうち、耐火キャスタブルの前記廃液の処理用凝集沈澱剤として、硫酸アルミニウムを使用しても、透明な上澄み液を得るには２〜３日の静置が必要である。また、ベントナイトを添加しても、ベントナイトの分散液で茶色の上澄み液となり、２日以上経過しても透明にならず、濁ったままである。さらに、各種のリン酸ナトリウムを添加しても、分散効果が働き、凝集沈澱せず、透明な上澄み液が得られ難い、という問題があった。 As described above, as described above, aluminum sulfate, bentonite, sodium phosphate, and the like are generally known as the coagulating and precipitating agent, and each is used alone. Among these, even when aluminum sulfate is used as the coagulating precipitant for treating the waste liquid of the refractory castable, it is necessary to stand for 2 to 3 days in order to obtain a transparent supernatant. Moreover, even if bentonite is added, it becomes a brown supernatant with a dispersion of bentonite, and it does not become transparent even after 2 days or more and remains cloudy. Further, even when various sodium phosphates are added, there is a problem that a dispersion effect works, aggregation does not occur, and it is difficult to obtain a transparent supernatant.
本発明者等は、上記問題点に鑑み鋭意研究を重ねた結果、耐火キャスタブルの廃液処理用凝集沈澱剤として、各々単独では凝集沈澱効果が生じない“ベントナイト，硫酸アルミニウム，リン酸ナトリウム”の３者を組み合わせることにより、凝集沈殿が短時間（数分で沈殿が目視でき、数１０分で略沈澱し、３〜６時間でほぼ透明な上澄み液が得られる）で進行することを見出して、本発明を完成したものである。 As a result of intensive research in view of the above-mentioned problems, the present inventors, as a coagulating precipitation agent for waste solution treatment of refractory castable, each of “bentonite, aluminum sulfate, sodium phosphate” 3 which does not produce an aggregation precipitation effect alone. By combining the above, it was found that the coagulation precipitation proceeds in a short time (precipitation can be visually observed in several minutes, almost precipitation in several tens of minutes, and almost transparent supernatant is obtained in 3 to 6 hours), The present invention has been completed.
すなわち、本発明が解決しようとする課題は、耐火キャスタブルの廃液（洗浄廃液）中の“固形分”が素早く凝集沈殿し、該廃液の“上澄み液の透明化”が迅速に進行する「耐火キャスタブルの廃液処理用凝集沈殿剤」を提供することにある。 That is, the problem to be solved by the present invention is that the “solid content” in the refractory castable waste liquid (cleaning waste liquid) quickly agglomerates and precipitates, and the “clearing of the supernatant liquid” proceeds rapidly. It is to provide a coagulating precipitation agent for waste liquid treatment.
上記課題を解決するための手段として、本発明に係る耐火キャスタブル廃液処理用凝集沈殿剤は、「ベントナイト、硫酸アルミニウムおよびリン酸ナトリウムを配合してなること(請求項１)」を特徴とし、「前記ベントナイトと硫酸アルミニウムとの配合比(重量比)が粉末換算で９：１〜３：７であり、前記ベントナイトとリン酸ナトリウムとの配合比(重量比)が粉末換算で９９：１〜７０：３０であること(請求項２)」を特徴とする。 As a means for solving the above-mentioned problems, the aggregated precipitant for treating a refractory castable waste liquid according to the present invention is characterized by comprising "bentonite, aluminum sulfate and sodium phosphate (Claim 1)". The blending ratio (weight ratio) of the bentonite and aluminum sulfate is 9: 1 to 3: 7 in terms of powder, and the blending ratio (weight ratio) of the bentonite and sodium phosphate is 99: 1 to 70 in terms of powder. : 30 (Claim 2) ".
このように、ベントナイト，硫酸アルミニウム，リン酸ナトリウムの３者を組み合わせることにより、各々単独添加では得られない凝集・沈殿効果、すなわち、耐火キャスタブルの廃液（洗浄廃液）中の“固形分”が素早く凝集して沈殿する効果が生じ、その結果、該廃液の“上澄み液の透明化”が迅速に進行する効果［耐火キャスタブルの種類によって異なるが、一般に、数分で沈殿が目視でき、数１０分で略沈澱し、３〜６時間でほぼ透明な上澄み液が得られる効果］を奏する。
このメカニズムについては、未だ明らかではないけれども、耐火キャスタブル廃液中の固形分を、硫酸アルミニウムが凝集させ、ベントナイトが吸収し、一方、リン酸ナトリウムは、ベントナイトの分散を行われるためであると推察される。
In this way, by combining the three of bentonite, aluminum sulfate, and sodium phosphate, the agglomeration / precipitation effect that cannot be obtained by adding each of them alone, that is, the “solid content” in the refractory castable waste liquid (cleaning waste liquid) can be quickly obtained. The effect of agglomerating and precipitating occurs, and as a result, the effect of “clearing the supernatant liquid” of the waste liquid proceeds rapidly [varies depending on the type of refractory castable, but in general, precipitation can be visually observed in several minutes, and several tens of minutes The effect that the substantially clear supernatant liquid can be obtained in 3 to 6 hours].
Although it is not yet clear about this mechanism, it is presumed that the solid content in the refractory castable waste liquid is agglomerated by aluminum sulfate and absorbed by bentonite, while sodium phosphate disperses bentonite. The
以下、本発明を実施するための最良の形態について説明すると、本発明で使用するベントナイトとしては、市販品粉末を任意に使用することができる。それを例示すれば、ベントナイト５号，ベントナイト８号などを挙げることができる。 Hereinafter, the best mode for carrying out the present invention will be described. As the bentonite used in the present invention, commercially available powders can be arbitrarily used. Examples thereof include bentonite No. 5, bentonite No. 8, and the like.
本発明で使用する硫酸アルミニウムとしては、液状，粉末状の何れでも使用可能であるが、粉末での使用が製造上好ましい。
また、本発明で使用するリン酸ナトリウムとしては、酸性メタリン酸ナトリウム，リン酸６ナトリウム，リン酸２ナトリウム，リン酸３ナトリウム，ピロリン酸ナトリウム，トリポリリン酸ナトリウム，テトラポリリン酸ナトリウム，ペンタポリリン酸ナトリウム，ヘキサメタリン酸ナトリウムなどを任意に使用することができる。そして、該リン酸ナトリウムも、液状，粉末状の何れでも良いが、粉末での使用が製造上好ましい。
The aluminum sulfate used in the present invention can be used in either liquid or powder form, but use in powder is preferred for production.
The sodium phosphate used in the present invention includes sodium metaphosphate, 6 sodium phosphate, 2 sodium phosphate, 3 sodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium pentapolyphosphate. , Sodium hexametaphosphate and the like can be arbitrarily used. The sodium phosphate may be either liquid or powder, but the use in powder is preferable for production.
本発明において、ベントナイトと硫酸アルミニウムとの配合比(重量比)は、粉末換算で９：１〜３：７が好ましく、より好ましくは８：２〜６：４である。また、ベントナイトとリン酸ナトリウムとの配合比(重量比)は、粉末換算で９９：１〜７０：３０が好ましく、より好ましくは９５：５〜８０：２０である。
ベントナイトと硫酸アルミニウムとの配合比が９：１〜３：７の範囲外では、本発明で意図する凝集・沈殿効果が得られ難く、また、ベントナイトとリン酸ナトリウムとの配合比が９９：１〜７０：３０の範囲外でも、同じく本発明で意図する凝集・沈殿効果が得られ難いので、いずれも好ましくない。
In the present invention, the blending ratio (weight ratio) of bentonite and aluminum sulfate is preferably 9: 1 to 3: 7, more preferably 8: 2 to 6: 4, in terms of powder. Further, the blending ratio (weight ratio) of bentonite and sodium phosphate is preferably 99: 1 to 70:30, more preferably 95: 5 to 80:20 in terms of powder.
When the blending ratio of bentonite and aluminum sulfate is outside the range of 9: 1 to 3: 7, it is difficult to obtain the aggregation / precipitation effect intended in the present invention, and the blending ratio of bentonite and sodium phosphate is 99: 1. Even outside the range of ˜70: 30, it is difficult to obtain the aggregation / precipitation effect which is also intended in the present invention.
次に、本発明に係る耐火キャスタブル廃液処理用凝集沈澱剤の使用方法について説明すると、特に限定するものではないが、該廃液に“ベントナイト，硫酸アルミニウム，リン酸ナトリウム”の粉末を投入する。そして、この投入と同時に充分に攪拌し、その後静置する。 Next, the method of using the aggregated precipitant for treating refractory castable waste liquid according to the present invention will be described. Although not particularly limited, powder of “bentonite, aluminum sulfate, sodium phosphate” is charged into the waste liquid. And it stirs simultaneously with this addition, and leaves still after that.
この凝集沈澱剤の耐火キャスタブル廃液に対する添加量は、廃液中に分散している固形分の濃度や、該固形分の種類（耐火キャスタブルの差に伴う固形分の種類）などにより異なるが、その目安は、廃液１リットルに対し４グラムが標準である。この添加量で期待する効果が得られない場合は、追加増量することができる。なお、この２段投入による弊害は特にない。 The amount of this coagulant-precipitating agent added to the refractory castable waste liquid varies depending on the concentration of the solids dispersed in the waste liquid and the type of the solids (the type of solids associated with the difference in the refractory castables). Is 4 grams per liter of waste liquid. When the expected effect cannot be obtained with this addition amount, it can be increased additionally. There is no particular adverse effect caused by the two-stage charging.
次に、本発明の実施例を比較例と共に挙げ、本発明を具体的に説明するが、本発明は、以下の実施例に限定されるものではない。 Next, although the Example of this invention is given with a comparative example and this invention is demonstrated concretely, this invention is not limited to a following example.
（実施例，比較例１〜３）
表１に示す配合の凝集沈殿剤（実施例，比較例１〜３）を製造した。
得られた凝集沈殿剤をキャスタブル(ＣＳＴ−Ａ７１６：品川白煉瓦社製の商品名)の洗浄廃液(緑色廃液)に添加し、その効果を調査した。すなわち、上記洗浄廃液１リットルに対し、実施例，比較例１〜３の凝集沈殿剤とも各４ｇ添加し、凝集・沈澱効果を比較した。
(Example, Comparative Examples 1-3)
Aggregation precipitation agents (Examples and Comparative Examples 1 to 3) having the formulations shown in Table 1 were produced.
The obtained coagulating precipitant was added to the cleaning waste liquid (green waste liquid) of castable (CST-A716: trade name manufactured by Shinagawa White Brick Co., Ltd.), and the effect was investigated. That is, 4 g of each of the coagulating precipitants of Examples and Comparative Examples 1 to 3 was added to 1 liter of the washing waste liquid, and the coagulation / precipitation effects were compared.
実施例の凝集沈殿剤では、数分後にフロックが形成し、沈降して行く様子が目視できた。そして、上澄み液は、３０分後に半透明となり、５時間後に透明になった。
一方、比較例１および比較例３の凝集沈殿剤では、２日以上経過しても上澄み液が透明にならず、濁ったままであった。また、比較例２の凝集沈殿剤では、１日経過後では上澄み液が透明とならず、２日目以降で初めて透明になった。
In the coagulating precipitant of the example, flocs were formed after a few minutes, and the state of sedimentation was visible. The supernatant liquid became translucent after 30 minutes and became transparent after 5 hours.
On the other hand, in the aggregated precipitants of Comparative Example 1 and Comparative Example 3, the supernatant liquid did not become transparent and remained cloudy even after 2 days or more. Moreover, in the coagulating precipitation agent of Comparative Example 2, the supernatant liquid was not transparent after 1 day, and became transparent only after the second day.
キャスタブルの洗浄廃液として、上記ＣＳＴ−Ａ７１６の洗浄廃液(緑色廃液)以外に、ＨＦＣ−Ｎ５５(品川白煉瓦社製の商品名)の洗浄廃液(白色廃液)およびＣＳＴ−Ａ８９７(同社製の商品名)の洗浄廃液(黒色廃液)に対しても、上記と同様にして、その効果を調査した。その結果は、前記と同様であった。 As castable cleaning waste liquid, in addition to the above-mentioned CST-A716 cleaning waste liquid (green waste liquid), cleaning waste liquid (white waste liquid) of HFC-N55 (product name manufactured by Shinagawa Shira brick) and CST-A897 (trade name manufactured by the same company) The cleaning waste liquid (black waste liquid) was also investigated in the same manner as described above. The result was the same as above.
本発明は、以上詳記したとおり、耐火キャスタブル廃液処理用の凝集沈殿剤として、ベントナイト，硫酸アルミニウム，リン酸ナトリウムの３者を組み合わせたことを特徴とし、これにより、各単独添加では得られない凝集・沈殿効果が得られる。すなわち、耐火キャスタブルの廃液（洗浄廃液）中の“固形分”が素早く凝集して沈殿する効果が生じ、その結果、該廃液の“上澄み液の透明化”が迅速に進行する効果を奏する。 As described in detail above, the present invention is characterized by combining three of bentonite, aluminum sulfate, and sodium phosphate as a coagulating precipitation agent for the treatment of refractory castable waste liquid. Aggregation and precipitation effect can be obtained. That is, the “solid content” in the refractory castable waste liquid (cleaning waste liquid) quickly agglomerates and precipitates, and as a result, the “clearing of the supernatant liquid” of the waste liquid proceeds quickly.
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