JP2005232341A - Treatment agent of hexavalent chromium-containing soil - Google Patents

Treatment agent of hexavalent chromium-containing soil Download PDF

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JP2005232341A
JP2005232341A JP2004043974A JP2004043974A JP2005232341A JP 2005232341 A JP2005232341 A JP 2005232341A JP 2004043974 A JP2004043974 A JP 2004043974A JP 2004043974 A JP2004043974 A JP 2004043974A JP 2005232341 A JP2005232341 A JP 2005232341A
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Takataro Mizuta
登太郎 水田
Minoru Takano
穣 高野
Masahiro Yota
真宏 要田
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/16—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a contaminated soil remediation agent and a lasting stabilization agent which recover soil functions by mixing them with such soils as a soft soil with a high water content or a slimy sludge to improve and maintain the pH of the soils to be neutral and to reduce hexavalent chromium remaining in the soils to trivalent chromium stable in the nature and to create an environment in which the chromium does not return to hexavalent chromium by re-oxidation. <P>SOLUTION: The treatment agent for hexavalent chromium soil comprises mixing 90 pts.wt. of portland cement, 200 pts.wt. of calcium sulfate (anhydrous gypsum), 3.6 pts.wt. of aluminum sulfate, 1.0-2.0 pts.wt. of a polymer coagulant, 15-150 pts.wt. of sodium bisulfite and 1-15 pts.wt. of protein with 700 pts.wt. of at least one kind selected from the group consisting of paper sludge, flyash, zeolite, bagasse and fired laterite. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、ペーパースラッジ灰、フライアッシュ灰、ゼオライトの持つ二大成分ニ酸化珪素と酸化アルミニウムに着目し、水和化合物、高分子凝集剤との結合によって、土粒子と団粒化を瞬時に且つ大量に行わせて六価クロムの逃避を制限し、しかる後に、混合されている重亜硫酸ソーダと蛋白質により土壌に含有する六価クロムの汚染処理と処理後の土壌の安定化を図ることを特徴とする技術に関する。 The present invention pays attention to the two major components silicon dioxide and aluminum oxide possessed by paper sludge ash, fly ash ash, and zeolite, and by combining with hydrated compounds and polymer flocculants, soil particles and aggregates are instantly formed. In addition, the escape of hexavalent chromium is restricted in a large amount, and then the hexavalent chromium contained in the soil is contaminated with the mixed sodium bisulfite and protein and the soil is stabilized after treatment. It relates to the featured technology.

従来、工事現場、災害現場にて発生する高含水汚泥や養豚場にて発生する畜産汚泥などは、セメント系固化剤、石灰系固化剤、高分子系固化剤などを利用して土壌機能を回復、改良されている。例えば、干拓現場では土壌固化剤として強アルカリ性のセメント系が使用され、土壌固化に長時間を要している。また石灰系のフライアッシュ灰は、印刷物等に含まれる顔料などから六価クロムや鉛などが溶出するおそれのある土壌固化剤であり、固化時には高温で発熱する。更に、高分子系は弱酸性を示し、いずれの土壌固化剤も未処理での利用には限界がある。
Conventionally, high water content sludge generated at construction sites and disaster sites, and livestock sludge generated at pig farms have been restored to soil function using cement-based solidifying agents, lime-based solidifying agents, polymeric solidifying agents, etc. Has been improved. For example, at the reclamation site, a strongly alkaline cement system is used as a soil solidifying agent, and it takes a long time to solidify the soil. Lime-based fly ash ash is a soil-solidifying agent that may elute hexavalent chromium, lead, etc. from pigments contained in printed matter and the like, and generates heat at a high temperature when solidified. Furthermore, the polymer system shows weak acidity, and there is a limit to the use of any soil-solidifying agent untreated.

一方、土壌改良剤の利用方法については、例えば、特許文献１には高含水軟弱土壌改良用団粒状固化剤が提案されている。これは、「大量に廃棄物として発生するフライアッシュ灰やペーパースラッヂ灰などの焼却灰を再利用し、含水量の多い軟弱土やヘドロ状汚泥を植物の植生に好ましい団粒状の土壌環境に改良するとともに、植物生体系に有害なセメントの使用量を極力抑制して、これまで以上に土壌強度を高めることができる。」ことを旨とする土壌改良剤が提供されている。
しかし、上記手段における土壌改良とは、軟弱土等の水分を瞬時に吸収して土壌強度を高めることであり、更に植生に好ましい土壌品質に改良することを言うが、自然環境を破壊する土壌汚染材料六価クロムについては言及されるに至っていない。従って一般の土壌改良剤では、六価クロムが処理されないまま放置されることになり、永久的な土壌の汚染処理剤になり得ないものである。
On the other hand, with respect to the method of using the soil conditioner, for example, Patent Document 1 proposes a granular solidifying agent for improving water content and soft soil. This is because “incineration ash such as fly ash ash and paper sludge ash generated as a large amount of waste is reused, and soft soil and sludge sludge with high water content are improved to a granular soil environment favorable for plant vegetation. In addition, a soil conditioner that has the effect of "suppressing the amount of cement harmful to plant biological systems as much as possible and increasing the soil strength more than ever has been provided."
However, soil improvement in the above means is to instantaneously absorb moisture such as soft soil and increase soil strength, and further to improve soil quality preferable for vegetation, but soil contamination that destroys the natural environment The material hexavalent chromium has not been mentioned. Therefore, in a general soil conditioner, hexavalent chromium is left untreated, and cannot be a permanent soil contamination treatment agent.

更に、土壌の六価クロム処理方法は従来、洗浄法と抽出法の併用であり、処理土を搬出しないで土壌の再利用を行うことはできない高価な処理方法となっている。特に、処理後の大量の水処理方法に難点があり、高含水比土壌処理技術の必要性が待たれる方法となっている。
特願2001-169024号 Furthermore, the hexavalent chromium treatment method of soil is conventionally a combination of a cleaning method and an extraction method, and is an expensive treatment method in which the soil cannot be reused without removing the treated soil. In particular, there is a difficulty in a large amount of water treatment method after treatment, and the need for high water content soil treatment technology is awaited.
Japanese Patent Application No. 2001-169024

そこで本発明は、含水量の多い軟弱土やヘドロ状汚泥などの土壌に混合してｐＨを中性に改質維持し、該土壌に残存する六価クロムを自然界において安定な三価クロムに還元して、再び六価クロムに酸化変換できない場を形成することにより土壌機能を回復する土壌汚染処理剤および長期的な安定剤を提供するものである。 Therefore, the present invention mixes with soil such as soft soil and sludge sludge having a high water content to maintain the pH neutrally, and reduces the hexavalent chromium remaining in the soil to trivalent chromium which is stable in nature. Thus, the present invention provides a soil contamination treating agent and a long-term stabilizer that restore soil function by forming a field that cannot be oxidized and converted again to hexavalent chromium.

上記目的を達成するために、請求項１記載の含有六価クロム土壌の処理剤は、ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分７００重量部に対して、ポルトランドセメント９０重量部、硫酸カルシウム（無水石膏）２００重量部、硫酸バンド３.６重量部、高分子凝集剤１．０〜２．０重量部、重亜硫酸ソーダ１５〜１５０重量部、蛋白質１〜１５重量部を混合することを特徴とする。 In order to achieve the above object, the treatment agent for hexavalent chromium soil according to claim 1 includes at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and red clay. Portland cement 90 parts by weight, calcium sulfate (anhydrite) 200 parts by weight, sulfate band 3.6 parts by weight, polymer flocculant 1.0-2.0 parts by weight, sodium bisulfite 15 -150 parts by weight and 1-15 parts by weight of protein are mixed.

請求項２記載の含有六価クロム土壌の処理剤は、ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分が汚泥水を包括し、該汚泥水中の六価クロムを自然界において安定な三価クロムに還元するために重亜硫酸ソーダを添加することを特徴とする。 The treatment agent for hexavalent chromium soil according to claim 2, wherein the component containing at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and red earth baked product includes sludge water, In order to reduce hexavalent chromium in the sludge water to trivalent chromium which is stable in nature, sodium bisulfite is added.

請求項３記載の含有六価クロム土壌の処理剤は、ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分が汚泥水を包括し、自然界において安定な三価クロムに還元した後に、再び六価クロムに酸化されないで三価クロムを保持するために蛋白質を添加することを特徴とする。 The treatment agent for hexavalent chromium soil according to claim 3, wherein the component containing at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and red soil baked product includes sludge water, After reducing to trivalent chromium which is stable in nature, a protein is added to retain trivalent chromium without being oxidized again to hexavalent chromium.

本発明は、含有六価クロム土壌の処理剤は、ペーパースラッヂ灰、フライアッシュ灰、ゼオライトに共通して存在するニ酸化珪素と酸化アルミニウムを含む粉状焼却灰や天然資源を原料とするので、水和化鉱物との結合によって、含水量の多い軟弱土やヘドロ状汚泥など土壌の水分を多量に保水して植物の植生などに好ましい団粒状の土壌環境に瞬時に改良固化することができる。更に、畜産汚泥の水分を保水するので、水分中に溶解している臭気元を離脱気化させて消臭することができる。そして汚泥水に残存する六価クロムを三価に還元して、再び六価に戻らない土壌に固化することができる。また粉状焼却灰は大量の製紙スラッジを焼却した灰分であるので、産業廃棄物の有効利用ができる。 In the present invention, since the processing agent for the hexavalent chromium soil contains paper slag ash, fly ash ash, powdered incineration ash containing silicon dioxide and aluminum oxide, which are commonly present in zeolite, and natural resources, By combining with hydrated minerals, a large amount of water in the soil, such as soft soil with a high water content or sludge-like sludge, can be retained and instantly improved and solidified into a granular soil environment favorable for plant vegetation and the like. Furthermore, since the water content of the livestock sludge is retained, the odor source dissolved in the water can be removed and vaporized for deodorization. The hexavalent chromium remaining in the sludge water can be reduced to trivalent and solidified in the soil that does not return to hexavalent again. Further, since the powdered incineration ash is ash obtained by incinerating a large amount of papermaking sludge, industrial waste can be effectively used.

この発明の実施の形態を、表１、表２、表３、表４に基づいて説明する。その冒頭に、本発明の原料であるペーパースラッヂ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物について説明する。
ペーパースラッヂ灰、フライアッシュ灰は大量の産業廃棄物として排出され、ペーパースラッヂ灰は製紙スラッジの焼却処分灰であり、フライアッシュ灰は石炭の燃焼残灰である。特に、石灰系のフライアッシュ灰は、印刷物等に含まれる顔料などから六価クロムや鉛などが溶出するおそれのある土壌固化剤となり、固化時には高温で発熱する。またゼオライトは天然資源で、単独あるいは混合灰として土壌安定固化剤の原料に用いられる。バガスは砂糖きびの炭化物を主原料とした表面積の極めて大きな活性炭に相当して、吸水量が多大である。最後に赤土の焼成物は、赤土を焼成して多孔質体にしたものをいう。 Embodiments of the present invention will be described with reference to Table 1, Table 2, Table 3, and Table 4. At the beginning, the fired product of paper sludge ash, fly ash ash, zeolite, bagasse, and red clay, which are raw materials of the present invention, will be described.
Paper sludge ash and fly ash ash are discharged as a large amount of industrial waste. Paper sludge ash is incineration disposal ash of papermaking sludge, and fly ash ash is combustion residue ash of coal. In particular, lime-based fly ash ash serves as a soil solidifying agent that may elute hexavalent chromium, lead, and the like from pigments contained in printed matter and the like, and generates heat at a high temperature during solidification. Zeolite is a natural resource and is used alone or as a mixed ash as a raw material for soil stabilization and solidification agents. Bagasse is equivalent to activated carbon with a very large surface area made of sugar cane carbide, and has a large water absorption. Finally, the fired product of red clay refers to a product obtained by firing red soil into a porous body.

次に、土壌汚染の原因の一つであるクロムについて更に詳細に説明する。
クロムは通常三価および六価のイオンとして自然界に存在する。そしてクロムは生体にとって必要なものであるが、逆に六価のクロムは強い毒性を持ち、発ガン性物質であることが知られている。工業的には、メッキや塗料、印刷インク、プラスチックス、絵具やクレヨン、磁気テープなどに広く用いられている。その生産工場の廃液等には、多量の六価クロムを含有しており、土壌汚染を引き起こしている。もちろん、国及び地方の行政府は排出基準を定めてその規制を行っているが、技術的にあるいは化学的に決定的な解決手段を持たないのが現状である。 Next, chromium that is one of the causes of soil contamination will be described in more detail.
Chromium usually exists in nature as trivalent and hexavalent ions. Chromium is necessary for living organisms. On the other hand, hexavalent chromium is known to have strong toxicity and to be a carcinogenic substance. Industrially, it is widely used for plating, paint, printing ink, plastics, paint, crayon, magnetic tape, and the like. The waste liquid of the production plant contains a large amount of hexavalent chromium, causing soil contamination. Of course, national and local governments set emission standards and regulate them, but there are currently no technically or chemically definitive solutions.

さて、含有六価クロム土壌の汚染処理方法について説明する。
六価クロムを処理する方法として、自然界において汚染性のない三価クロムに還元する方法を利用する。六価クロムは水に溶解し易い性質を利用して、六価クロムが溶出した水に還元剤を投入し撹拌する。この時に還元反応が起こり、結晶水を持った錯体として三価の化合物となる。因みに、該還元剤としては、塩化第一鉄、硫酸第一鉄、亜硫酸ソーダ、重亜硫酸ソーダ、チオールやチオエーテルなどの含硫黄化合物があり、そのうち重亜硫酸ソーダを用いるのが望ましい。表１で六価クロムの還元反応について検証する。
六価クロム化合物はクロム酸塩と重クロム酸塩で、この塩は還元によって安定な６配位の錯体を作り、三価クロム化合物となる。該三価クロム化合物は錯塩であり、塩の水溶液や結晶水を含む結晶においては、水分子がCr3+イオンに配位し、ヘキサアクアクロムイオン〔Cr(H2O)6〕3+ などの錯イオンを作って安定化していることが多い。 Now, a method for treating the contaminated hexavalent chromium soil will be described.
As a method of treating hexavalent chromium, a method of reducing to trivalent chromium which is not polluted in nature is used. Utilizing the property that hexavalent chromium is easily dissolved in water, a reducing agent is added to the water from which hexavalent chromium is eluted and stirred. At this time, a reduction reaction occurs, and a trivalent compound is formed as a complex having crystal water. Incidentally, as the reducing agent, there are sulfur-containing compounds such as ferrous chloride, ferrous sulfate, sodium sulfite, sodium bisulfite, thiol and thioether, among which sodium bisulfite is preferably used. Table 1 verifies the reduction reaction of hexavalent chromium.
Hexavalent chromium compounds are chromate and dichromate, and this salt forms a stable six-coordinate complex by reduction, and becomes a trivalent chromium compound. The trivalent chromium compound is a complex salt, and in a crystal containing an aqueous solution of salt or water of crystallization, water molecules coordinate to Cr 3+ ions, hexaaqua chromium ions [Cr (H 2 O) 6 ] 3+, etc. It is often stabilized by making complex ions.

Figure 2005232341
Figure 2005232341

しかしながら、この安定した三価クロムであっても、強アルカリ性溶液の存在下では比較的酸化され易く、Na2Cr2O4など亜クロム酸塩となって溶解し、毒性を持った六価クロムになる。また、完全に還元された三価クロムであっても、空気との接触によって酸化され、六価に戻ることもある。 However, even this stable trivalent chromium is relatively easily oxidized in the presence of a strong alkaline solution, dissolves as a chromite such as Na 2 Cr 2 O 4 , and is a toxic hexavalent chromium. become. Even trivalent chromium that has been completely reduced may be oxidized by contact with air to return to hexavalent.

そこで、自然界において毒性がなく比較的安定な三価クロムを保持するために、蛋白質のラセン状立体構造に着目した。該ラセン状立体構造体の中に錯体三価クロムを取り込み、三価クロムが強アルカリや空気と接触することを遮断して酸化を起こさせないような分子鋳型的な包括機能を利用する。
包括機能を強く発揮する蛋白質は繊維状蛋白質であるが、特にαヘリクス構造やβシートのケラチンよりも、三重ラセン立体構造を持つコラーゲンを利用する方が包括効果が大きい。三価クロムイオンは蛋白質と結合する作用が強く、繊維状蛋白質であるコラーゲン繊維に結合して水に不溶な三価クロムとなる。このような機構に沿って、三価クロムは蛋白質のポリペプチド鎖およびその立体構造内に取り込まれる。一方、蛋白質の特性である疎水結合やファンデルワールス力によって強アルカリや空気との嫌気性条件を与えられ、更に水素結合やＳ−Ｓ結合を多く持っている蛋白質は表面変性を受け難い性質により、外部との酸化を断ち、内部の三価クロムを保護することとなる。
三価クロムの固定方法として、蛋白質成分とりわけコラーゲンが効果的であることが分かったが、タンパク質に有機酸を併用することも可能である。併用可能な有機酸は、例えばグルコン酸、乳酸、マレイン酸、酢酸、スルファミン酸などである。更には、カゼイン、ゼラチン、卵白など蛋白質食品も使用可能である。カゼイン、ゼラチン、卵白に三価のクロムイオンが結合すると水に不溶性になるが、六価クロムにはこの作用はない。 Therefore, in order to retain trivalent chromium which is not toxic in nature and is relatively stable, we focused on the helical structure of the protein. The complex trivalent chromium is incorporated into the helical three-dimensional structure, and a molecular template-like comprehensive function that prevents the trivalent chromium from coming into contact with a strong alkali or air to cause oxidation is utilized.
A protein that exerts a strong global function is a fibrous protein. However, the use of collagen having a triple helix structure is more effective than α-helical structure or β-sheet keratin. Trivalent chromium ions have a strong effect of binding to proteins, and bind to collagen fibers, which are fibrous proteins, to form trivalent chromium that is insoluble in water. Along this mechanism, trivalent chromium is incorporated into the polypeptide chain of the protein and its conformation. On the other hand, proteins that have anaerobic conditions with strong alkali and air due to hydrophobic bonds and van der Waals forces, which are the characteristics of proteins, and proteins that have many hydrogen bonds and SS bonds are less susceptible to surface modification. This will cut off external oxidation and protect the internal trivalent chromium.
As a method for fixing trivalent chromium, protein components, particularly collagen, have been found to be effective, but it is also possible to use an organic acid in combination with the protein. Examples of organic acids that can be used in combination include gluconic acid, lactic acid, maleic acid, acetic acid, sulfamic acid, and the like. Furthermore, protein foods such as casein, gelatin, and egg white can also be used. When trivalent chromium ions bind to casein, gelatin, and egg white, they become insoluble in water, but hexavalent chromium does not have this effect.

そこで該フライアッシュ灰、ゼオライト、バガス、赤土の焼成物を原料とし、水和化鉱物や高分子凝集剤に汚染処理剤および安定剤を配して水の吸着量を増大すると共に、土壌の六価クロム汚染を処理して土壌の安定固化を図る配合構成を行った。含有六価クロム土壌の処理剤の組成を表２に示す。水和化鉱物および凝集剤は、ペーパースラッジ灰、フライアッシュ灰、ゼオライトと水の界面において水和反応を起こして水和物を形成し、汚泥など軟弱土からの吸水を促進する。粉状焼却灰および天然資源の有効利用と汚泥の安定固化への機能回復を果す。 Therefore, using the burned product of fly ash ash, zeolite, bagasse, and red clay as raw materials, the amount of water adsorbed is increased by adding a pollution treatment agent and a stabilizer to the hydrated mineral and polymer flocculant, and the soil six. The compound composition which treated valent chromium contamination and stabilized solidification was performed. Table 2 shows the composition of the treatment agent for the hexavalent chromium soil contained. Hydrated minerals and flocculants cause hydration to form hydrates at the interface between paper sludge ash, fly ash ash, zeolite and water, and promote water absorption from soft soil such as sludge. Effective use of powdered incineration ash and natural resources and functional recovery to stable solidification of sludge.

Figure 2005232341
Figure 2005232341

更に、各組成の機能について説明する。
多孔質を保持しているペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物は汚泥中の水分を吸収し、土壌安定固化剤を構成する水和化鉱物と反応して、水和反応を起こす。水和化鉱物の一つ目、ポルトランドセメントまたは早強セメントは、水を吸収して含まれる骨材とともに固化する性質がある。水和化鉱物のニつ目、無水石膏は、水和反応により吸水固化して土質の強度を上げ、硫酸バンドの凝集力を助ける効果がある。三つ目は硫酸バンドで、ｐＨを下げ、汚泥水分に溶出する溶存汚濁物質を吸着固定する。そして四つ目が必要に応じて用いるメタクリル酸エステルで、硫酸バンドと無水石膏との組合せで凝集力を増強し、また改良土のひび割れを防止する効果がある。五つ目が高分子凝集剤で、フロックを形成して水の脱水分離を促進し、水分吸着能を高く急速に保持する効果がある。 Furthermore, the function of each composition is demonstrated.
Paper sludge ash, fly ash ash, zeolite, bagasse, and red clay fired products that retain porosity absorb water in the sludge and react with the hydrated minerals that constitute the soil-stabilizing solidifying agent to hydrate. Cause a reaction. The first hydrated mineral, Portland cement or early strength cement, has the property of absorbing water and solidifying with the contained aggregate. The second hydrated mineral, gypsum, has the effect of solidifying water by hydration reaction to increase the strength of the soil and helping the cohesive strength of the sulfate band. The third is a sulfuric acid band that lowers the pH and adsorbs and fixes dissolved pollutants that elute into sludge moisture. The fourth is a methacrylic acid ester used as necessary, and has the effect of enhancing the cohesive force and preventing cracking of the improved soil by the combination of sulfuric acid band and anhydrous gypsum. The fifth is a polymer flocculant, which has the effect of forming flocs to promote water dehydration and separation, and maintaining high moisture adsorption capacity rapidly.

その結果、多孔質を保持しているペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物は汚泥中の水分を吸収し、土壌安定固化剤を構成する水和化鉱物によって水和反応を起こし、土粒子を包囲しながら迅速に固化し団粒化していく。また、該ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物は多孔質であるので、その孔表面に有機質、重金属、臭気などを短時間に付着吸収して離脱させないで、団粒体を形成する。そこで、該水和化鉱物に高分子凝集剤を添加して吸水量を増加させ、土粒子の固化団粒化を促進する。
ここにおいて吸収された汚泥水が六価クロムを含有した汚染水である場合、汚染処理剤である重亜硫酸ソーダと化学反応を起こし、毒性のない三価クロムに還元する。この三価クロムは、強アルカリ性水溶液や空気に曝されると再び六価クロムに酸化されてしまう。この酸化を起こさせないために、処理安定剤として蛋白質、特にコラーゲンを添加して、コラーゲンの持つ三価クロムとの強い反応性に鑑み、三価クロムの包括、安定性を形成する。 As a result, the paper sludge ash, fly ash ash, zeolite, bagasse, and red clay baked products that retain the porous structure absorb moisture in the sludge and hydrate by the hydrated minerals that constitute the soil stabilization solidifying agent. And quickly solidifies and aggregates while surrounding the soil particles. In addition, the paper sludge ash, fly ash ash, zeolite, bagasse, red clay baked product is porous, so that organic particles, heavy metals, odors, etc. adhere to the surface of the pores in a short period of time and do not leave them. Form the body. Therefore, a polymer flocculant is added to the hydrated mineral to increase the amount of water absorption and promote solidification of the soil particles.
When the absorbed sludge water is contaminated water containing hexavalent chromium, it causes a chemical reaction with sodium bisulfite, which is a contamination treatment agent, and is reduced to non-toxic trivalent chromium. When this trivalent chromium is exposed to a strong alkaline aqueous solution or air, it is oxidized again to hexavalent chromium. In order not to cause this oxidation, a protein, particularly collagen, is added as a treatment stabilizer, and the inclusion and stability of trivalent chromium is formed in view of the strong reactivity of the collagen with trivalent chromium.

以上、含有六価クロム土壌の処理剤における各原料の性質に勘案して、上記混合重量比の範囲で、改良すべき土壌の性質、状態に適するように調合を行なう。その基本となる含有六価クロム土壌への処理剤の実施例を表３に示す。 As described above, in consideration of the properties of each raw material in the treatment agent for the hexavalent chromium soil, the blending is performed so as to be suitable for the properties and conditions of the soil to be improved within the range of the mixing weight ratio. Table 3 shows examples of treatment agents for the basic hexavalent chromium soil.

Figure 2005232341
Figure 2005232341

次に、汚染土壌の処理方法について説明する。
汚染土壌の処理方法として、表３に示す組成表を用いて行う。汚染土壌である検体土を採取し、汚染土壌２００重量部と水３００重量部を撹拌槽に投入し、撹拌した汚染土壌と水の合計重量５００重量部に対して、表３に示した安定のための組成物を１００重量部添加して、再び２分以上撹拌すると加えた水は急速になくなる。採取した汚染土壌を元の場所に戻し、乾燥させる。
その後、乾燥土壌の一部を溶出試験のサンプルとして溶出の有無を確認し、溶出のないことが確認できた後、整地し、汚染土壌の処理を完了する。
以上の汚染土壌の処理方法は標準方法であり、土壌に含まれる六価クロムの含有量により薬剤投入量および撹拌時間は種々異なる。 Next, a method for treating contaminated soil will be described.
As a method for treating contaminated soil, a composition table shown in Table 3 is used. Sample soil, which is contaminated soil, is collected, 200 parts by weight of contaminated soil and 300 parts by weight of water are put into a stirring tank, and the total weight of the agitated contaminated soil and water is 500 parts by weight. When 100 parts by weight of the composition is added and stirred again for 2 minutes or more, the added water rapidly disappears. Return the collected contaminated soil to its original location and dry it.
Thereafter, a part of the dry soil is used as a sample for the dissolution test to confirm the presence or absence of dissolution. After confirming that there is no dissolution, the soil is leveled and the treatment of the contaminated soil is completed.
The above-mentioned treatment method of contaminated soil is a standard method, and the amount of the chemical and the stirring time differ depending on the content of hexavalent chromium contained in the soil.

試験例１Test example 1

六価クロム含有汚染土壌を１Ｌ採取し、六価クロムの溶出試験を行った。試験方法はＪＩＳ Ｋ ０１０２（６５．２．１）に従い、土壌の六価クロム汚染改良前と改良後の六価クロム計量比較を行った。表４にその結果を示す。 1 L of hexavalent chromium-containing contaminated soil was collected and subjected to a hexavalent chromium elution test. The test method was in accordance with JIS K 0102 (65.2.1), and the hexavalent chromium measurement before and after the improvement of soil hexavalent chromium contamination was compared. Table 4 shows the results.

Figure 2005232341
Figure 2005232341

上記の比較にあるように、土壌の汚染改良前は１９０mg/L計量された六価クロムが、表３に示した組成物を添加した後に計量すると該六価クロムは０．０２mg/L以下にまで減少した。その減少度合いは１／１０,０００に達し、含有六価クロム土壌の処理剤の大きさが伺える。   As shown in the above comparison, 190 mg / L of hexavalent chromium was measured before the soil contamination was improved, and when hexavalent chromium was measured after adding the composition shown in Table 3, the hexavalent chromium was reduced to 0.02 mg / L or less. Decreased to. The degree of reduction reaches 1 / 10,000, indicating the size of the treatment agent for the hexavalent chromium soil contained.

本発明は、含水量の多い軟弱土やヘドロ状汚泥を保水し、更には畜産汚泥の水分を保水することによる消臭など汚泥土壌の機能回復に要した後、保水中の土壌汚染材料六価クロムを三価に還元して土壌汚染処理剤に、更に三価から六価に酸化されないよう捕獲する土壌安定固化剤に利用することができる。環境基準に適合し、安全且つ安価で安定した処理法として利用できる。 The present invention retains soft soil and sludge sludge having a high water content, and further requires functional recovery of sludge soil such as deodorization by retaining the moisture of livestock sludge, and then the soil contamination material hexavalent in the water retention It can be used as a soil contamination treatment agent by reducing chromium to trivalent, and further as a soil stabilizing solidifying agent that captures chromium from being oxidized from trivalent to hexavalent. It conforms to environmental standards and can be used as a safe, inexpensive and stable treatment method.

Claims (3)

ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分７００重量部に対して、ポルトランドセメント９０重量部、硫酸カルシウム（無水石膏）２００重量部、硫酸バンド３.６重量部、高分子凝集剤１．０〜２．０重量部、重亜硫酸ソーダ１５〜１５０重量部、蛋白質１〜１５重量部を混合することを特徴とする含有六価クロム土壌の処理剤。 90 parts by weight of Portland cement and 200 parts by weight of calcium sulfate (anhydrous gypsum) with respect to 700 parts by weight of a component containing at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and red clay A mixed hexavalent chromium characterized by mixing 3.6 parts by weight of a sulfuric acid band, 1.0 to 2.0 parts by weight of a polymer flocculant, 15 to 150 parts by weight of sodium bisulfite, and 1 to 15 parts by weight of a protein. Soil treatment agent. ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分が汚泥水を包括し、該汚泥水中の六価クロムを自然界において安定な三価クロムに還元するために重亜硫酸ソーダを添加することを特徴とする請求項１記載の含有六価クロム土壌の処理剤。 Ingredients containing at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and red clay are included in sludge water, and hexavalent chromium in the sludge water is trivalent chromium that is stable in nature. The treatment agent for containing hexavalent chromium soil according to claim 1, wherein sodium bisulfite is added to reduce the amount of sodium hexasulfite. ペーパースラッジ灰、フライアッシュ灰、ゼオライト、バガス、赤土の焼成物から成る群の少なくともいずれか一つを含む成分が汚泥水を包括し、自然界において安定な三価クロムに還元した後に、再び六価クロムに酸化されないで三価クロムを保持するために蛋白質を添加することを特徴とする請求項１記載の含有六価クロム土壌の処理剤。 A component containing at least one of the group consisting of paper sludge ash, fly ash ash, zeolite, bagasse, and reddish baked material contains sludge water, reduced to trivalent chromium, which is stable in nature, and then again hexavalent. The treatment agent for containing hexavalent chromium soil according to claim 1, wherein a protein is added to retain trivalent chromium without being oxidized by chromium.
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JP2013064052A (en) * 2011-09-16 2013-04-11 Dc Co Ltd Soil conditioner
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CN110790474A (en) * 2019-11-14 2020-02-14 济南大学 Treatment agent and method for removing hexavalent chromium in sludge
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JP2010222430A (en) * 2009-03-23 2010-10-07 Daio Paper Corp Soil-improving material and method for producing the same
JP2012201765A (en) * 2011-03-24 2012-10-22 Daiwa House Industry Co Ltd Soil-modifying composition and method for modifying soil
JP2013064052A (en) * 2011-09-16 2013-04-11 Dc Co Ltd Soil conditioner
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CN110790474A (en) * 2019-11-14 2020-02-14 济南大学 Treatment agent and method for removing hexavalent chromium in sludge
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