JP2011026151A - Solidifying agent and solidification method using the solidifying agent - Google Patents
Solidifying agent and solidification method using the solidifying agent Download PDFInfo
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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
- C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0006—Alkali metal or inorganic ammonium compounds
- C04B2103/0007—K
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00517—Coating or impregnation materials for masonry
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
Abstract
Description
本発明は、珪酸ナトリウムを含有する固化剤及びその固化剤を用いた固化方法に関するものである。 The present invention relates to a solidifying agent containing sodium silicate and a solidifying method using the solidifying agent.
従来より、構造物の壁や柱などの建造や道路や崖などの補強などの広い範囲で固化剤が使用されている。 Conventionally, solidifying agents have been used in a wide range such as construction of structures such as walls and pillars and reinforcement of roads and cliffs.
この固化剤としては、コンクリートに代表されるように、水を加えて固化させるものであり、施工の際に石や砂などの骨材を混入させて固化させるようにしている。 As this solidifying agent, as represented by concrete, water is added and solidified, and aggregates such as stone and sand are mixed and solidified at the time of construction.
そして、近年では、固化剤として、飛灰と珪酸ナトリウムと水とを混合した固化剤が開発されている（たとえば、特許文献１参照。）。 And in recent years, the solidification agent which mixed fly ash, sodium silicate, and water as a solidification agent is developed (for example, refer patent document 1).
ところが、特許文献１に開示されている飛灰と珪酸ナトリウムと水とを混合した固化剤では、重金属が溶出するために重金属を基準値以上含む飛灰の処理には利用することができないものであった。 However, the solidifying agent mixed with fly ash, sodium silicate, and water disclosed in Patent Document 1 cannot be used for the treatment of fly ash containing heavy metals above a reference value because heavy metals are eluted. there were.
また、特許文献１に開示されている固化剤では、飛灰と珪酸ナトリウムと水とを混合して固化する際にジオポリマーとなって還元反応が生じ、水素ガスが発生し、その水素ガスによって固化後の固化体の内部に空隙が生成されてしまい、その空隙によって強度や密度が低下していた。 Further, the solidifying agent disclosed in Patent Document 1, the reduction reaction becomes geopolymer occurs when solidified by mixing fly ash and sodium silicate and water, hydrogen gas is generated, by the hydrogen gas Voids were generated inside the solidified body after solidification, and the strength and density were reduced by the voids.
そこで、請求項１に係る本発明では、固化剤において、珪酸ナトリウムと消石灰とミョウバンとを含有することにした。 Therefore, in the present invention according to claim 1, the solidifying agent contains sodium silicate, slaked lime, and alum.
また、請求項２に係る本発明では、前記請求項１に係る本発明にいおいて、セルロースを添加することにした。 In the present invention according to claim 2, cellulose is added in the present invention according to claim 1.
また、請求項３に係る本発明では、前記請求項１又は請求項２に係る本発明において、多硫化カルシウムを添加することにした。 In the present invention according to claim 3, calcium polysulfide is added in the present invention according to claim 1 or claim 2.
また、請求項４に係る本発明では、前記請求項１〜請求項３のいずれかに係る本発明において、無水石膏又は半水石膏を添加することにした。 In the present invention according to claim 4, anhydrous gypsum or hemihydrate gypsum is added in the present invention according to any one of claims 1 to 3.
また、請求項５に係る本発明では、前記請求項１〜請求項４のいずれかに係る固化剤に加水して液体状とした。 In the present invention according to claim 5, the solidifying agent according to any one of claims 1 to 4 is added to form a liquid.
また、請求項６に係る本発明では、固化方法において、前記請求項１〜請求項４のいずれかに係る固化剤に加水して液体状とし、この液体を乾燥させて所定形状に固化させることにした。 Further, in the present invention according to claim 6, that the solidifying process, hydrolysis to a liquid in the solidification agent according to any one of the claims 1 to 4, to solidify the liquid is dried into a predetermined shape I made it.
また、請求項７に係る本発明では、固化方法において、前記請求項１〜請求項４のいずれかに係る固化剤に加水して液体状とし、この液体を構造物の表面に塗布して固化させることにした。 Further, in the present invention according to claim 7, in solidification process, hydrolysis to a liquid in the solidification agent according to any one of the claims 1 to 4, and coating the liquid on the surface of the structure solidifies Decided to let.
そして、本発明では、高強度に固化させることができるとともに、重金属やフッ化物やホウ素化合物の溶出を抑制することができる。 And in this invention, while being able to solidify with high intensity | strength, elution of a heavy metal, a fluoride, and a boron compound can be suppressed.
本発明では、珪酸ナトリウムと消石灰とミョウバンとを混合し、必要に応じて、水やセルロースや多硫化カルシウムや無水石膏又は半水石膏を添加して、固化剤を生成し、この固化剤を所定形状に固化させたり既存の構造物の表面に塗布して固化させるものである。 In the present invention, sodium silicate, slaked lime, and alum are mixed, and if necessary, water, cellulose, calcium polysulfide, anhydrous gypsum, or hemihydrate gypsum is added to produce a solidifying agent. It is solidified into a shape or applied to the surface of an existing structure to be solidified.
ここで、ミョウバンとは、１価の陽イオン（M+）の硫酸塩（M+ 2(SO4)）と３価の金属イオン（M3+）の硫酸塩（M3+ 2(SO4)3）の複塩の総称をいい、M+M3+(SO4)2・12H2OやM+ 2(SO4)M3+ 2(SO4)3・24H2Oなどで表される結晶水を含む構造体のものをいう。なお、ミョウバンと同等の構造や物性を有するミョウバン類似の構造体の物質も含まれる。特に好適なミョウバンとしては硫酸アルミニウム（Al2(SO4)3）を含有するミョウバン（K2(SO4)Al2(SO4)324H20）である。 Here, alum is a monovalent cation (M + ) sulfate (M + 2 (SO 4 )) and a trivalent metal ion (M 3+ ) sulfate (M 3+ 2 (SO 4). 3 ) This is a generic name for the double salt of M + M 3+ (SO 4 ) 2 · 12H 2 O or M + 2 (SO 4 ) M 3+ 2 (SO 4 ) 3 · 24H 2 O A structure containing crystal water. In addition, the substance of the structure similar to alum which has the structure and physical property equivalent to alum is also contained. A particularly suitable alum is alum (K 2 (SO 4 ) Al 2 (SO 4 ) 3 24H 2 0) containing aluminum sulfate (Al 2 (SO 4 ) 3 ).
また、珪酸ナトリウムと消石灰とミョウバンとの混合比率は、適宜調整できるものであるが、たとえば、重量比で珪酸ナトリウム２０：消石灰６０：ミョウバン２０として固化剤を生成する。なお、珪酸ナトリウムと消石灰とミョウバンとの混合比率は全体を１００重量部とした場合に、珪酸ナトリウム、消石灰、ミョウバンそれぞれが０．１重量部以上であれば固化剤として機能するが、望ましくは珪酸ナトリウムが２０±５重量部、消石灰が６０±１０重量部、ミョウバンが２０±５重量部となる重量比で混合する。 The mixing ratio of sodium silicate, slaked lime, and alum can be adjusted as appropriate. For example, the solidifying agent is produced as sodium silicate 20: slaked lime 60: alum 20 by weight ratio. In addition, when the mixing ratio of sodium silicate, slaked lime, and alum is 100 parts by weight as a whole, the sodium silicate, slaked lime, and alum each function as a solidifying agent if the amount is 0.1 parts by weight or more. Sodium is mixed at a weight ratio of 20 ± 5 parts by weight, slaked lime is 60 ± 10 parts by weight, and alum is 20 ± 5 parts by weight.
この固化剤は、加水して型枠内に流し込んで成形してもよく、高温（６０℃）下で１日間の強制乾燥、または、常温下で７日間の自然乾燥により固化させることができる。また、粒状に固化させるには、容器内で固化させたものを固化後に粒状に細砕してもよく、固化前に粒状に成形してから固化させてもよく、転動造粒やプレス成形や真空成形などを利用してもよい。なお、固化剤は、珪酸ナトリウムと消石灰とミョウバンとを混合し、必要に応じて、セルロースや多硫化カルシウムや無水石膏又は半水石膏を添加した粒体や粉体であり、また、これらに加水して、水溶液化したものや泥状としたものも含まれる。 This solidifying agent may be molded by pouring water into a mold, and can be solidified by forced drying for 1 day at a high temperature (60 ° C.) or by natural drying for 7 days at room temperature. Moreover, in order to solidify into granular form, the solidified substance in the container may be crushed into granular form after solidifying, or may be formed into granular form before solidifying and then solidified. Or vacuum forming may be used. The solidifying agent is a granule or powder obtained by mixing sodium silicate, slaked lime, and alum, and adding cellulose, calcium polysulfide, anhydrous gypsum, or hemihydrate gypsum as necessary. And what was made into aqueous solution and the thing made into mud are also included.
このように、ミョウバン（たとえば、硫酸アルミニウム（Al2(SO4)3を含有するミョウバン（K2(SO4)Al2(SO4)324H20））と水とを混合すると、ミョウバンに含有される硫酸金属（たとえば、硫酸アルミニウム）は優れた凝集力を有しているため、固化剤の固化を促進させることができる。 Thus, when alum (for example, alum containing Al 2 (SO 4 ) 3 (K 2 (SO 4 ) Al 2 (SO 4 ) 3 24H 2 0)) and water is mixed with alum, Since the contained metal sulfate (for example, aluminum sulfate) has an excellent cohesive force, the solidification of the solidifying agent can be promoted.
また、珪酸化合物が含有する場合には、その珪酸化合物を構成する珪酸イオンがミョウバンに含有される硫酸金属（たとえば、硫酸アルミニウム）を構成する金属イオン（たとえば、アルミニウムイオン）と強く結合する。 Further, when the silicate compound is contained, the silicate ions constituting the silicate compound are strongly bonded to the metal ions (for example, aluminum ions) constituting the metal sulfate (for example, aluminum sulfate) contained in the alum.
また、水分子は、含有される珪酸イオン及びミョウバンに含有される金属イオン（たとえば、アルミニウムイオン）と水素結合される。 Further, the water molecules are hydrogen-bonded to the contained silicate ions and metal ions (for example, aluminum ions) contained in alum.
このように、ミョウバンに含有される硫酸金属（たとえば、硫酸アルミニウム）の凝集力や結合性を利用して固化体を生成することができる。 In this way, a solidified body can be generated by utilizing the cohesive strength and binding properties of metal sulfate (for example, aluminum sulfate) contained in alum.
さらに、飛灰に含有されるフッ化物イオンは、飛灰に含有される消石灰と反応して難溶性のフッ化カルシウムを生成するとともに、ミョウバンに含有される金属イオン（たとえば、アルミニウムイオン）を反応して安定なフッ化物（たとえば、フッ化アルミニウム）を生成し、これらの安定なフッ化カルシウムやフッ化アルミニウムなどのフッ化物がミョウバンの凝集力や結合性によって固化体に安定に取り込まれ、これにより、フッ化物イオンの可溶化や溶出が抑制される。 Furthermore, fluoride ions contained in fly ash react with slaked lime contained in fly ash to produce sparingly soluble calcium fluoride and react with metal ions (eg, aluminum ions) contained in alum. To produce stable fluorides (for example, aluminum fluoride), and these stable fluorides such as calcium fluoride and aluminum fluoride are stably taken into the solidified body by the cohesive strength and binding properties of alum. This suppresses solubilization and elution of fluoride ions.
また、飛灰に含有されるホウ素化合物も、飛灰に含有される消石灰とミョウバンに含有される金属イオン（たとえば、アルミニウムイオン）とで生成された水酸化物（たとえば、水酸化アルミニウム）との反応によって固化体に安定に取り込まれ、これにより、ホウ素化合物の可溶化や溶出が抑制される。 Moreover, the boron compound contained in the fly ash is also composed of hydroxide (eg, aluminum hydroxide) generated from slaked lime contained in the fly ash and metal ions (eg, aluminum ions) contained in alum. By the reaction, it is stably taken into the solidified body, thereby suppressing the solubilization and elution of the boron compound.
さらに、固化剤に消石灰を含んでいるために、水を混合して固化する際にポリマーとなって還元反応が生じるが、珪酸とアルミニウムの水素結合体を形成するために水素が消費され、固化後の固化体の内部に空隙が生成されてしまうのを防止することができ、固化体の強度や密度を良好なものとすることができる。 Furthermore, because it contains a hydrated lime solidifying agent, but the reduction is a polymer in solidified by mixing water reaction occurs, hydrogen is consumed to form hydrogen bonds of silicate and aluminum, solidification It is possible to prevent voids from being generated in the solidified body later, and to improve the strength and density of the solidified body.
以上に説明したように、本発明では、高強度に固化させることができるとともに、飛灰に含有される重金属やフッ化物やホウ素化合物の溶出を抑制することができる。 As described above, in the present invention, it is possible to solidify the high strength, it is possible to suppress the elution of heavy metals and fluoride and boron compound contained in the fly ash.
上記固化剤は、固化させることで、防草用途、冷却用途、充填用途、発泡用途、漁礁用途、人口石材用途、緑化用途、断熱材用途、耐火材用途、防蟻用途、舗装用途、法面保護用途、アスベスト等の廃棄物安定固化用途など多岐にわたって有効に利用することができる。 By solidifying the above solidifying agent, herbicidal use, cooling use, filling use, foaming use, fishing reef use, artificial stone material use, greening use, heat insulation material use, fireproofing use use, ant proof use use, pavement use, slope It can be effectively used in a wide variety of applications, such as protective use and stable stabilization and solidification use of asbestos.
また、上記固化剤は、珪酸ナトリウム、消石灰のいずれか又は両方を含有する物質があれば、その物質を原料として不足する珪酸ナトリウム又は消石灰とミョウバンとを添加して生成することもできる。 In addition, if there is a substance containing either or both of sodium silicate and slaked lime, the solidifying agent can be generated by adding sodium silicate or slaked lime and alum which are insufficient as a raw material.
ここで、消石灰中のカルシウムの混合比率は適宜設定することができるが、強度の増大や長期の安定性を目的とする場合には、混合比率を１重量％以上５重量％未満とし、軽量化を目的とする場合には、混合比率を５重量％以上１５重量％未満とし、多孔質体に成形する場合には、混合比率を１５重量％以上２０重量％未満とする。 Here, it is possible to set the mixing ratio of calcium in the slaked lime is needed, for the purpose of increase and long-term stability of strength, the mixing ratio is less than 1 wt% to 5 wt%, weight Is intended to be 5 wt% or more and less than 15 wt%, and when forming into a porous body, the mixing ratio is 15 wt% or more and less than 20 wt%.
また、上記固化剤に重金属固定剤として多硫化カルシウム溶液を１重量％程度添加することで、重金属の溶出を防止することができる。 Moreover, elution of heavy metals can be prevented by adding about 1% by weight of a calcium polysulfide solution as a heavy metal fixing agent to the solidifying agent.
この重金属固定剤としては、公知のものを利用することもできるが、飛灰を原料とした重金属固定剤を利用することで、廃棄物としての飛灰を有効に利用することができ、廃棄物の減量化を図ることができる。 As the heavy metal fixatives, can also be utilized a known, the use of the heavy metal fixatives in which the fly ash as a raw material, it is possible to effectively utilize the fly ash as waste, waste Can be reduced.
たとえば、飛灰（炭種;マッセルブルグ５０％、ドレイトン５０％の混焼により発生したもので、アルカリ度ｐＨ１３．５）を用い、飛灰２０重量部、硫黄２０重量部、水１００重量部の配合比とし、まず、飛灰２０重量部と水１００重量部を反応缶に入れ、上蓋を閉じ、混合機を作動させて１０分程度混合する。 For example, fly ash (coal species; Masseruburugu 50%, which was generated by Drayton 50% co-firing, alkalinity pH 13.5) using the fly ash 20 parts by weight sulfur 20 parts by weight, the formulation of 100 parts by weight of water First, 20 parts by weight of fly ash and 100 parts by weight of water are placed in a reaction can, the upper lid is closed, and the mixer is operated to mix for about 10 minutes.
次に、安全弁を設定し上限反応圧力として排気圧を約１０ｋｇ／ｃｍ２にセットし、炉体冷却排水バルブ及び冷却バルブを開放するとともに冷却水入口バルブを開放して通水する。 Next, a safety valve is set, the exhaust pressure is set to about 10 kg / cm 2 as the upper limit reaction pressure, the furnace body cooling drain valve and the cooling valve are opened, and the cooling water inlet valve is opened to allow water to flow.
次に、反応中の蒸発を抑えるために、エアーコンプレッサーによる加圧によって２．５ｋｇ／ｃｍ２程度の予圧をかける。 Next, in order to suppress evaporation during the reaction, a preload of about 2.5 kg / cm 2 is applied by pressurization with an air compressor.
次に、バーナに点火して、圧力計と温度計とを確認し、混合しながら昇温する。この時に、圧力は１０ｋｇ／ｃｍ２以下とし、温度計の表示が１１０℃に達してから、約３０分間混合反応させる。 Next, the burner is ignited, the pressure gauge and the thermometer are confirmed, and the temperature is raised while mixing. At this time, the pressure is set to 10 kg / cm 2 or less, and after the thermometer display reaches 110 ° C., the mixture is reacted for about 30 minutes.
次に、バーナを停止し、圧力計が下降するまで放置し、安定したら排気弁により最終残圧を完全に排出し、大気圧と同化させる。 Next, the burner is stopped and left until the pressure gauge is lowered. When the pressure gauge is stabilized, the final residual pressure is completely discharged by the exhaust valve and assimilated with the atmospheric pressure.
次に、混合機を停止させ、排出バルブを開放して、沈澱物及び液体を排出して、これらを回収する。 Next, the mixer is stopped, the discharge valve is opened, the precipitate and liquid are discharged, and these are collected.
次に、回収物を冷却し、沈澱分離し薬液と沈澱物を得る。ここでは、薬液１３０重量部と沈澱物20重量部を得ることができた。 Next, the recovered product is cooled and separated by precipitation to obtain a chemical solution and a precipitate. Here, 130 parts by weight of the chemical solution and 20 parts by weight of the precipitate were obtained.
また、回収された薬液は、多硫化カルシウムを含有しており、液比重が１．２ｇ／ｃｃで黄緑色のｐＨ１０の液体であった。 The recovered chemical solution contained calcium polysulfide and was a yellow-green liquid with a liquid specific gravity of 1.2 g / cc and a pH of 10.
また、原料とし焼却場飛灰ｐＨ１３．５を用いたところ、多硫化カルシウムを含有した液比重が１．１５ｇ／ｃｃの茶色のｐＨ１１の液体を得た。 In addition, when using the incineration fly ash pH13.5 as a raw material, liquid density containing a calcium polysulfide got pH11 liquid brown 1.15 g / cc.
このようにして生成した液体、さらには沈殿物を重金属固定剤として用いることができる。 The liquid thus produced, and further the precipitate, can be used as a heavy metal fixing agent.
また、上記固化剤に廃棄処理された紙やダンボールなどのセルロースを含有する廃棄物を混合することもできる。 In addition, waste containing cellulose such as paper and cardboard, which has been disposed of in the solidifying agent, can be mixed.
このように、セルロースを混合した場合には、固化剤の固化が進行する途中において伸縮性を向上させることができ、固化途中でのクラックの防止を図ることができるとともに成形を容易なものとすることができ、また、固化後に微生物の坦体などとなる空洞を形成させることができる。 Thus, when cellulose is mixed, stretchability can be improved in the course of solidification of the solidifying agent, cracks can be prevented during solidification, and molding can be facilitated. It is also possible to form a cavity that becomes a carrier of microorganisms after solidification.
すなわち、固化剤の固化が進行する初期の吸水膨張と乾燥時の収縮に対してセルロースが有効なテンション材として機能する。これは、通常の有機繊維では無機の結合物との接合性が悪いが、固化剤が水酸基を含むシリカ体であるためにセルロースが橋体を構成して初期の結合性に優れ、乾燥時にはセルロースが含有する水分の脱水のほうが遅く進み、セルロースの結合性によってクラックを防止することができる。また、セルロースには導水材として水分の外部への排出を促す働きがあり、一般的に見られる表面の水分のみが蒸散して内面と表面とで水バランスが図れず残留ストレスとなる現象の発生を防止しながら乾燥することになる。さらに、乾燥後にはセルロースの脱水（収縮）によって固化体の内部に空洞が形成される。この空洞は、微生物の良好な担体として或いは種子の宿体として有効に利用することができる。なお、空洞は、カルシウムや珪酸ナトリウムやミョウバンなどの水溶液を含浸させることで閉塞することもできる。 That is, cellulose functions as an effective tension material for the initial water absorption expansion and solidification shrinkage when solidification of the solidifying agent proceeds. This is because ordinary organic fibers have poor bondability with inorganic binders, but since the solidifying agent is a silica body containing a hydroxyl group, cellulose constitutes a bridge body and has excellent initial binding properties. The dehydration of water contained in the water advances more slowly, and cracks can be prevented by the binding properties of cellulose. Cellulose also has a function to promote the discharge of moisture to the outside as a water-conducting material. Only the moisture on the surface, which is generally seen, evaporates, causing a phenomenon of residual stress that cannot balance the water between the inner surface and the surface. Drying while preventing. Furthermore, after drying, a cavity is formed inside the solidified body due to dehydration (shrinkage) of cellulose. This cavity can be effectively used as a good carrier for microorganisms or as a seed accommodation. The cavity can be closed by impregnating with an aqueous solution such as calcium, sodium silicate, or alum.
また、上記固化剤に無水石膏（無水硫酸カルシウムCaSO4）又は半水石膏（硫酸カルシウム・1/2水和物CaSO4・1/2H2O）を添加してもよい。 Further, anhydrous gypsum (anhydrous calcium sulfate CaSO 4 ) or hemihydrate gypsum (calcium sulfate · 1/2 hydrate CaSO 4 · 1 / 2H 2 O) may be added to the solidifying agent.
このように、無水石膏や半水石膏を添加することで、これら無水石膏や半水石膏が水和反応により二水石膏（硫酸カルシウム・2水和物CaSO4・2H2O）となって固化することになり、固化の促進を図ることができる。 In this way, by adding anhydrous gypsum and hemihydrate gypsum, these anhydrous gypsum and hemihydrate gypsum solidify into dihydrate gypsum (calcium sulfate dihydrate CaSO 4 2H 2 O) by hydration reaction. Thus, solidification can be promoted.
さらに、上記固化剤に骨材を混入させて固化するようにしてもよい。 Furthermore, you may make it solidify by mixing an aggregate with the said solidification agent.
この骨材としては、公知のものを利用することもできるが、飛灰を原料とした骨材を利用することで、廃棄物としての飛灰を有効に利用することができ、廃棄物の減量化を図ることができる。 As the aggregate, may also be used known ones, the use of the aggregate in which the fly ash as a raw material, it is possible to effectively utilize the fly ash as waste, waste reduction Can be achieved.
たとえば、飛灰と珪酸ナトリウムと水とを混合し、その後、吸水性を有する状態となるように粒状に固化させて骨材を製造することができる。 For example, fly ash, sodium silicate, and water can be mixed and then solidified into a granular form so as to have water absorption, thereby producing an aggregate.
ここで、飛灰と珪酸ナトリウムと水との混合比率は、適宜調整できるものであるが、たとえば、重量比で飛灰１００：珪酸ナトリウム２：水５０として製造することができる。 Here, the mixing ratio of the fly ash and sodium silicate and water, although it can appropriately adjusted, for example, fly ash 100 in a weight ratio of: sodium silicate 2: can be produced as water 50.
また、飛灰と珪酸ナトリウムと水との混合においては、飛灰と珪酸ナトリウム溶液を混合するようにしてもよい。 Moreover, you may make it mix a fly ash and a sodium silicate solution in mixing of fly ash, sodium silicate, and water.
また、固化は、吸水性を有する状態となるように適宜調整できるものであるが、たとえば、高温（６０℃）下で１日間の強制乾燥、または、常温下で７日間の自然乾燥により吸水性を有する状態で固化させることができる。 Further, solidification, but those that can be appropriately adjusted so as to be in a state of having a water-absorbing, for example, a high temperature (60 ° C.) forced drying for one day under, or absorbent by natural drying at room temperature for 7 days It can be solidified in the state which has.
また、粒状に固化させるには、容器内で固化させたものを固化後に粒状に細砕してもよく、固化前に粒状に成形してから固化させてもよく、転動造粒やプレス成形や真空成形などを利用してもよい。 Moreover, in order to solidify into granular form, the solidified substance in the container may be crushed into granular form after solidifying, or may be formed into granular form before solidifying and then solidified. Or vacuum forming may be used.
以上に説明したようにして骨材を製造することができ、製造された骨材は、数十％（たとえば、３０％）の吸水性を有している。 The aggregate can be manufactured as described above, and the manufactured aggregate has a water absorption of several tens% (for example, 30%).
そのため、建造物の建造や補強などにおいて特開平８−３０１６３９号公報に開示されているように飛灰と珪酸ナトリウムと水とを混合した固化剤を用いて固化を行うときに、上記骨材を固化剤に混入することで、固化剤の高流動性を保ちながら施工時に加えた水が骨材に吸水されることになり、固化や養生に要する時間を短くすることができ、施工期間を短期化させることができる。なお、上記の吸水性を有する骨材だけを使用することで減水効果が増大し軽量化を図ることができるが、軽量化が不要で増強化や全体の収縮を防止するなどの目的や施工コストの引下げなどを図るために石や砂などの一般的な骨材を混入させてもよい。 Therefore, when solidifying using a solidifying agent in which fly ash, sodium silicate, and water are mixed as disclosed in JP-A-8-301039 in the construction or reinforcement of a building, the above-mentioned aggregate is used. By mixing in the solidifying agent, the water added during construction while keeping the high fluidity of the solidifying agent will be absorbed by the aggregate, shortening the time required for solidification and curing, and shortening the construction period It can be made. The use of only the above-mentioned aggregates having water absorption can increase the water-reducing effect and reduce the weight, but the purpose and construction cost such as increasing the weight and preventing overall shrinkage are unnecessary. General aggregates such as stone and sand may be mixed in order to lower the size of the steel.
また、骨材としては、廃石綿、廃アスベスト分解物、廃石膏等の廃半水化物、鉄鋼スラグ等の金属廃棄物、おがくず等の木材廃棄物などを添加してもよい。 Further, as aggregate, waste asbestos, waste asbestos decomposition products, waste hemihydrate such as waste gypsum, metal waste such as steel slag, wood waste such as sawdust may be added.
また、上記固化剤には、メッキ廃液や生コンクリート洗浄液等の廃液、卵白や魚油等の食品廃液、オレンジ等の食品残渣物、家畜糞などを混合させてもよい。 The solidifying agent may be mixed with waste liquid such as plating waste liquid or fresh concrete cleaning liquid, food waste liquid such as egg white or fish oil, food residue such as orange, livestock dung, and the like.
上記固化剤の具体的な実施例としては、飛灰100重量部に対してに消石灰を５〜40重量部とセルロースを１〜５重量部を添加して10分程度ドライミキシングする一方、水30〜60重量部と多硫化カルシウム溶液0.5〜５重量部とを10分程度混合し、これらを混合したものにミョウバン0.2〜５重量部添加するとともに、珪酸ナトリウムを0.2〜５重量部添加して15分程度混合して固化剤を生成し、この固化剤を型枠内に流し込んで固化させたり、構造物の表面にコテで塗布して固化させることができる。 Specific examples of the solidification agent, while about 10 minutes dry mixing with the addition of 1 to 5 parts by weight of 5 to 40 parts by weight of cellulose hydrated lime with respect to fly ash 100 parts by weight of water 30 -60 parts by weight and 0.5-5 parts by weight of calcium polysulfide solution are mixed for about 10 minutes, 0.2 to 5 parts by weight of alum is added to the mixture, and 0.2 to 5 parts by weight of sodium silicate is added. A solidifying agent is produced by mixing for about a minute, and this solidifying agent can be poured into a mold and solidified, or can be solidified by applying it to the surface of a structure with a trowel.
特に、耐熱性が要求される場合には、飛灰に窒化灰（窒素酸化物や窒化金属等の窒素原子を含んだ灰、たとえば高温燃焼により炭化物を含んだ飛灰など）を５〜40重量部混入させてもよい。この場合には、成型時や塗布時等の固化時にガス化発泡してスポンジ状の断面を有する比重0.3〜1.0程度の軽量な耐火層を形成させることができ、高い耐火性を発揮させることができ、高温バルブや配管の保温材としても利用することができる。なお、水の混合比率を60〜150重量部程度まで増大させても自然発泡した後に固化させることができる。 In particular, when heat resistance is required, (ash containing nitrogen atom of the nitrogen oxide, metal nitride, for example fly ash, etc. that contain carbides by high-temperature combustion) ash nitride fly ash 5 to 40 weight It may be mixed. In this case, it is possible to form a lightweight fire-resistant layer having a specific gravity of about 0.3 to 1.0 having a sponge-like cross section by gasifying and foaming at the time of solidification such as molding or application, and exhibiting high fire resistance It can also be used as a heat insulating material for high temperature valves and pipes. Even if the mixing ratio of water is increased to about 60 to 150 parts by weight, it can be solidified after spontaneous foaming.
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| JP2013231696A (en) * | 2012-05-01 | 2013-11-14 | Sanai Fujita | Immobilizing agent and immobilizing method for radioactive waste |
| JP2015081265A (en) * | 2013-10-21 | 2015-04-27 | 株式会社土地改良センター | Heavy metal-coating solidifying agent |
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| JPH11293246A (en) * | 1998-02-16 | 1999-10-26 | Mitsui Chem Inc | Suspension-type grout and soil improvement therewith |
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| JP2013231696A (en) * | 2012-05-01 | 2013-11-14 | Sanai Fujita | Immobilizing agent and immobilizing method for radioactive waste |
| JP2015081265A (en) * | 2013-10-21 | 2015-04-27 | 株式会社土地改良センター | Heavy metal-coating solidifying agent |
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