JP2002154862A - Hardenable composition and hardened body - Google Patents
Hardenable composition and hardened bodyInfo
- Publication number
- JP2002154862A JP2002154862A JP2000347660A JP2000347660A JP2002154862A JP 2002154862 A JP2002154862 A JP 2002154862A JP 2000347660 A JP2000347660 A JP 2000347660A JP 2000347660 A JP2000347660 A JP 2000347660A JP 2002154862 A JP2002154862 A JP 2002154862A
- Authority
- JP
- Japan
- Prior art keywords
- slag
- curable composition
- weight
- cured product
- water glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Classifications
-
- 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石炭ガス化スラグ
を含有し、耐酸性と施工性に優れた硬化性組成物及びそ
の硬化体に関する。The present invention relates to a curable composition containing coal gasification slag and having excellent acid resistance and workability, and a cured product thereof.
【０００２】[0002]
【従来の技術】従来、耐酸コンクリートとしては、高炉
水滓スラグ粉末にアルカリ金属塩等を刺激剤として加え
て硬化させたアルカリスラグコンクリートが知られてい
る。ここで用いられる高炉水滓スラグは、銑鉄製造工程
で得られ、通常ＣａＯ／ＳｉＯ 2のモル比が１．３以上
であるといわれている。また、斯かる高炉水滓スラグ粉
末と水ガラスを用いたコンクリートは、硬化体中に酸に
弱い遊離のＣａ（ＯＨ） 2が全く生成されないために、
普通セメントコンクリートに比べて耐酸性が強いと言わ
れている。しかしながら、水ガラスと高炉スラグを用い
ると、高炉スラグはＣａＯの含有量が多いため硬化体中
にはシリカゲルの他にＣ−Ｓ−Ｈ（ＣａＯ−ＳｉＯ2−
Ｈ2Ｏ）ゲルも多量に生成し、このＣ−Ｓ−Ｈゲルは、
酸には弱いため結果として耐酸性はさほど大きくなら
ず、また硫酸はＣ−Ｓ−Ｈゲルと反応し、石膏のような
膨張性物質を生成するため、硬化体が膨張応力によって
破壊されることがあった。2. Description of the Related Art Conventionally, acid-resistant concrete has been used in blast furnaces.
Add alkali metal salt, etc. as a stimulant to the slag slag powder
Hardened alkaline slag concrete is known
You. The blast furnace slag used here is used in the pig iron manufacturing process.
And usually CaO / SiO TwoMolar ratio of 1.3 or more
It is said to be. In addition, such blast furnace slag slag powder
Concrete using powder and water glass can
Weak free Ca (OH) TwoIs not generated at all,
It is said that it has higher acid resistance than ordinary cement concrete
Have been. However, using water glass and blast furnace slag
Then, the blast furnace slag contains a large amount of CaO,
In addition to silica gel, CSH (CaO-SiOTwo−
HTwoO) A large amount of gel is also formed, and this CSH gel is
If acid resistance is so large as a result, it is weak to acid
And sulfuric acid reacts with the CSH gel, like gypsum
In order to generate an intumescent substance, the cured body is
Sometimes destroyed.
【０００３】そこで、下水汚泥焼却物やゴミ焼却物等の
廃棄物の非結晶溶融スラグ粉末（ＣａＯ／ＳｉＯ2のモ
ル比が０．１〜１．２）、水ガラス及び骨材を含有する
セメント組成物が優れた耐酸性を有するものとして考案
されたが（特開平１０−２１８６４４号公報）、このよ
うなセメント組成物を用いたモルタル等は、粘性は高い
が流動性もあるため、壁面、天井部に施工すると流れ落
ちる場合がある。また薄く塗り付けることができても、
硬化後に著しいひび割れが発生する等、寸法安定性と施
工性の点で必ずしも充分ではなかった。[0003] Therefore, non-crystalline molten slag powder (molar ratio of CaO / SiO 2 of 0.1 to 1.2) of waste such as incineration of sewage sludge and incineration of garbage, cement containing water glass and aggregates Although the composition was devised as having excellent acid resistance (Japanese Patent Application Laid-Open No. 10-218644), mortar and the like using such a cement composition have high viscosity but high fluidity. When installed on the ceiling, it may run off. Also, even if you can apply it thinly,
It was not always sufficient in terms of dimensional stability and workability, such as occurrence of remarkable cracks after curing.
【０００４】斯かる状況の下、本発明者らは、廃棄物溶
融スラグ等を包含するＣａＯ／ＳｉＯ2のモル比が０．
１〜１．２である溶融スラグ粉末と水ガラスとアルミナ
セメントのそれぞれを一定割合で含有する硬化性組成物
を用いると、施工性がよく、優れた耐酸性を有する硬化
体が得られることを見出し、先に特許出願した（特願２
０００−３４８２６）。[0004] Under such circumstances, the present inventors have found that the molar ratio of CaO / SiO 2 including waste molten slag and the like is 0.1%.
When a curable composition containing a fixed ratio of each of molten slag powder, water glass, and alumina cement of 1 to 1.2 is used, workability is good, and a cured product having excellent acid resistance can be obtained. Heading, and filed a patent application earlier (Japanese Patent Application No.
000-34826).
【０００５】しかし、下水汚泥やゴミ等の廃棄物溶融ス
ラグは厚生省の「一般廃棄物の溶融固化物の再生利用に
関する指針」における目標値を満足する場合が多いが、
多くの重金属が含まれるため、使用上環境面を考慮した
対策の必要があるとともに、ゴミ溶融スラグには金属ア
ルミが含まれるケースが多く、金属アルミが珪酸アルカ
リと反応して発生する水素ガスが硬化体の膨張を引き起
こすなどの問題があり、更に下水スラグについては、そ
の国内総排出量は平成８年度において４万トンにすぎ
ず、供給面においても問題を残していた。また、廃棄物
溶融スラグはその発生量が少ないため、多量のスラグを
集めた場合、ＣａＯ／ＳｉＯ2の量比のばらつきが大き
くなる。[0005] However, waste molten slag such as sewage sludge and garbage often satisfies the target value in the “Guidelines for Recycling of Molten Solidified Solid Waste” by the Ministry of Health and Welfare.
Because it contains a lot of heavy metals, it is necessary to take measures in consideration of the environment in terms of use.In addition, in many cases, molten slag contains metallic aluminum, and hydrogen gas generated by the reaction of metallic aluminum with alkali silicate is generated. There were problems such as the expansion of the cured product, and sewage slag had a total domestic emission of only 40,000 tons in fiscal 1996, leaving problems in supply. Further, since the amount of waste molten slag generated is small, when a large amount of slag is collected, variation in the CaO / SiO 2 ratio becomes large.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、耐酸性、施工性に優れると共に、安定供給でき且つ
環境面でも安全な硬化性組成物及び硬化体を提供するこ
とにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a curable composition and a cured product which are excellent in acid resistance and workability, can be supplied stably, and are environmentally safe.
【０００７】[0007]
【課題を解決するための手段】斯かる実情に鑑み本発明
者らは、更に検討した結果、石炭ガス化複合発電により
生じる石炭ガス化スラグ粉末が、ＣａＯ／ＳｉＯ2比の
ばらつきが小さく、重金属含有量も少なく、且つ安定供
給でき、これと水ガラス及びアルミナセメントのそれぞ
れを一定割合で配合した組成物を用いることにより、優
れた耐酸性と施工性を有する硬化体を安定的且つ効率的
に製造できることを見出し、本発明を完成した。In view of such circumstances, the present inventors have further studied and found that coal gasification slag powder produced by the integrated coal gasification combined cycle has a small variation in CaO / SiO 2 ratio and heavy metal. The content is small and can be supplied stably, and by using a composition in which this is mixed with water glass and alumina cement at a fixed ratio, a cured product having excellent acid resistance and workability can be stably and efficiently produced. They found that they could be manufactured and completed the present invention.
【０００８】すなわち、本発明は、（Ａ）石炭ガス化ス
ラグ粉末１０〜８５重量％、（Ｂ）水ガラスを固形分で
５〜４０重量％及び（Ｃ）アルミナセメント５〜７０重
量％を含有する硬化性組成物を提供するものである。That is, the present invention comprises (A) 10 to 85% by weight of coal gasification slag powder, (B) 5 to 40% by weight of water glass in solid content and (C) 5 to 70% by weight of alumina cement. To provide a curable composition.
【０００９】また、本発明はこの硬化性組成物と水とを
混合し、養生することにより得られる硬化体を提供する
ものである。The present invention also provides a cured product obtained by mixing the curable composition with water and curing.
【００１０】[0010]
【発明の実施の形態】本発明で用いる（Ａ）成分の石炭
ガス化スラグ粉末は、石炭ガス化複合発電において、石
炭ガス化炉内から発生したものを粉砕したものである。
つまり、ガス化炉内において、微粉炭は約１５００℃の
高温でガス化し、その時灰分は溶融され溶融したスラグ
となる。このスラグは炉底の冷却ホッパに落下し、急速
に冷却され、ガラス質の急冷スラグとなる。ここで、ス
ラグのＣａＯ／ＳｉＯ2量比は、石炭の種類や産地によ
って大きく異なってくるが、石炭ガス化の際には、ガス
化効率を上げるために石炭灰分の溶融温度を下げる必要
があり、融点降下剤（フラックス）として石灰石が添加
される。それ故、できたスラグのＣａＯ／ＳｉＯ2比の
ばらつきは炭種が異なっても小さくなる。このようにし
て得られたスラグに含まれるＣａＯ／ＳｉＯ2のモル比
は、０．１〜２．０である。このモル比が０．１０未満
であると組成物の反応性が低く、十分所期強度を発現す
る耐久性のある硬化体が得られず、一方、このモル比が
１．２〜０．１の範囲の石炭ガス化スラグを用いれば、
特にＣａＯ／ＳｉＯ2比を調整することなく耐久性と耐
酸性を持つ硬化体を得ることができる。更に石炭ガス化
スラグに含まれる重金属は少なく（例：Pb＝50ppm以
下）、環境面においても好ましいことから、当該石炭ガ
ス化スラグは好適な材料といえる。BEST MODE FOR CARRYING OUT THE INVENTION The coal gasification slag powder of the component (A) used in the present invention is obtained by pulverizing powder generated from inside a coal gasification furnace in the integrated coal gasification combined cycle.
That is, in the gasification furnace, the pulverized coal is gasified at a high temperature of about 1500 ° C., and at that time, the ash is melted to become molten slag. This slag falls into a cooling hopper at the bottom of the furnace, is rapidly cooled, and becomes vitreous quenched slag. Here, the CaO / SiO 2 ratio of the slag varies greatly depending on the type of coal and the place of production. However, during coal gasification, it is necessary to lower the melting temperature of the coal ash in order to increase the gasification efficiency. Limestone is added as a melting point depressant (flux). Therefore, the variation in the CaO / SiO 2 ratio of the resulting slag is small even if the coal type is different. The molar ratio of CaO / SiO 2 contained in the slag obtained in this way is 0.1 to 2.0. If this molar ratio is less than 0.10, the reactivity of the composition is low, and a durable cured product exhibiting sufficient intended strength cannot be obtained, while the molar ratio is 1.2 to 0.1. Using coal gasification slag in the range of
Particularly, a cured product having durability and acid resistance can be obtained without adjusting the CaO / SiO 2 ratio. Furthermore, the coal gasification slag is a suitable material because the coal gasification slag contains a small amount of heavy metals (eg, Pb = 50 ppm or less) and is environmentally preferable.
【００１１】また、石炭ガス化スラグは発電規模２５万
Ｋｗにおいて年間約７万トンの排出が見込まれること、
及び石炭ガス化複合発電の発電端効率が５０％程度であ
り、４０％程度の発電端効率である現在の石炭火力発電
（微粉炭燃焼方式）に比べて高効率であり、今後は主流
になると考えられていることより、将来的に安定供給で
きるという利点もある。更に、石炭ガス化スラグは現
在、埋立処分を考えられているが、本発明により、これ
を有効利用する新たな用途を提案し、この結果、更に石
炭ガス化複合発電の経済性を高めることができる。[0011] Further, the coal gasification slag is expected to emit about 70,000 tons annually at a power generation scale of 250,000 Kw.
And the power generation efficiency of the integrated coal gasification combined cycle is about 50%, which is higher than the current coal-fired power generation (pulverized coal combustion method), which has a power generation efficiency of about 40%. There is also an advantage that it can be supplied in a stable manner in the future. Furthermore, although coal gasification slag is currently considered for landfill disposal, the present invention proposes a new use to make effective use of this, and as a result, it is possible to further increase the economics of the integrated coal gasification combined cycle. it can.
【００１２】（Ａ）成分の粉末度は、硬化体の強度発現
性の観点から比表面積で好ましくは、２０００〜１５０
００cm2／ｇ、より好ましくは３０００〜１５０００cm2
／ｇ、特に好ましくは４０００〜１５０００cm2／ｇで
ある。なお、比表面積が１５０００cm2／ｇを超えたも
のでも本発明に好適に使用できるが、粉砕にコストがか
かり経済的でない。一方、これが２０００cm2／ｇ未満
であると、水和活性が乏しく、硬化体の強度が不十分と
なることがある。The fineness of the component (A) is preferably from 2000 to 150 in terms of specific surface area from the viewpoint of developing strength of the cured product.
00 cm 2 / g, more preferably 3000-15000 cm 2
/ G, particularly preferably 4000-15000 cm 2 / g. It should be noted that a material having a specific surface area exceeding 15000 cm 2 / g can be suitably used in the present invention, but the pulverization is costly and not economical. On the other hand, if it is less than 2000 cm 2 / g, the hydration activity is poor and the strength of the cured product may be insufficient.
【００１３】本発明で用いられる水ガラス（Ｂ）は、特
に限定されず市販のものが使用でき、ＪＩＳ規格により
規定される１号、２号、３号の他、各水ガラスメーカー
で製造販売されているＪＩＳ規格外の製品においても使
用が可能であり、それぞれを単体で使用する他、２種類
以上を組み合わせて使用することができる。The water glass (B) used in the present invention is not particularly limited, and a commercially available water glass can be used. In addition to Nos. 1, 2, and 3 specified by JIS standards, the water glass (B) is manufactured and sold by each water glass manufacturer. It can be used in products that do not conform to the JIS standard, and can be used alone or in combination of two or more.
【００１４】水ガラスの使用量は、硬化性組成物中５〜
４０重量％、好ましくは１０〜３０重量％（固形分換
算）である。この量が５重量％未満であると、十分な耐
酸性を有する硬化体が得られず、４０重量％を超えると
粘性が大きくなりすぎ、成形又は作業が困難となること
がある。The amount of water glass used is 5 to 5 in the curable composition.
It is 40% by weight, preferably 10 to 30% by weight (as solid content). If the amount is less than 5% by weight, a cured product having sufficient acid resistance cannot be obtained, and if it exceeds 40% by weight, the viscosity becomes too large, and molding or working may be difficult.
【００１５】本発明に用いられるアルミナセメント
（Ｃ）は、特に限定されず市販のものが使用できるが、
好ましくはＣａＯ・Ａｌ2Ｏ3の含有率が高いものが良
い。例えば、ラファージュ社製「セカール５１ＢＴ
Ｆ」、電気化学工業社製「アルミナセメント１号」等が
好ましい。（Ｃ）の含有量は５〜７０重量％の範囲であ
れば良い。７０重量％を超えると良好な耐酸性を示さな
くなる。また、特に常温養生においては、本発明の硬化
体の収縮量が大きくなる傾向があるので、収縮を低下さ
せるため含有率を５重量％以上にするのが好ましい。The alumina cement (C) used in the present invention is not particularly limited, and a commercially available one can be used.
Preferably, the content of CaO.Al 2 O 3 is high. For example, "Sekar 51BT" manufactured by Lafarge
F "and" Alumina Cement No. 1 "manufactured by Denki Kagaku Kogyo KK are preferred. The content of (C) may be in the range of 5 to 70% by weight. If it exceeds 70% by weight, good acid resistance is not exhibited. In addition, particularly at room temperature curing, since the amount of shrinkage of the cured product of the present invention tends to increase, the content is preferably set to 5% by weight or more to reduce shrinkage.
【００１６】本発明の硬化性組成物には、必要により高
炉スラグ、転炉スラグ、脱リンスラグ、脱ケイスラグ及
び脱硫スラグから選ばれる１種又は２種以上の結合材
（Ｄ）を配合することができる。本発明に用いられる結
合材（Ｄ）は、特に限定されず市販のものが使用できる
が、粉末度が比表面積で４０００cm2／ｇ以上のものが
好ましい。結合材の含有率は１〜３０重量％の範囲であ
れば良いが、好ましい範囲としては５〜２０重量％であ
る。石炭ガス化スラグ粉末（Ａ）を結合材（Ｄ）と併用
することにより、常温養生において良好な強度発現性を
持つ硬化体が得られる。結合材（Ｄ）の含有率を増加す
ることにより早強性が得られるが、同時に含有率が３０
重量％を超えると耐酸性が低下する傾向にある。このた
め結合材（Ｄ）の含有率を使用する石炭ガス化スラグ粉
末（Ａ）のＣａＯ／ＳｉＯ2モル比に合わせて調整する
ことにより耐酸性の良好な硬化体を得られる。石炭ガス
化スラグ粉末（Ａ）と結合材（Ｄ）の混合物のＣａＯ／
ＳｉＯ2モル比が１．２０以下、好ましくは０．８０以
下、より好ましくは０．６０以下が耐酸性の点から好ま
しい範囲である。また、アルミナセメント（Ｃ）と結合
材（Ｄ）の合計は６〜７５重量％とすることが好まし
い。The curable composition of the present invention may optionally contain one or more binders (D) selected from blast furnace slag, converter slag, dephosphorized slag, desilicated slag, and desulfurized slag. it can. The binder (D) used in the present invention is not particularly limited, and a commercially available binder can be used. However, a binder having a specific surface area of 4000 cm 2 / g or more is preferable. The content of the binder may be in the range of 1 to 30% by weight, but is preferably in the range of 5 to 20% by weight. By using the coal gasified slag powder (A) in combination with the binder (D), a cured product having good strength development at room temperature curing can be obtained. The early strength can be obtained by increasing the content of the binder (D), but at the same time, the content is 30%.
When the content is more than 10% by weight, acid resistance tends to decrease. Therefore, by adjusting the content of the binder (D) according to the CaO / SiO 2 molar ratio of the coal gasified slag powder (A), a cured product having good acid resistance can be obtained. CaO / of mixture of coal gasification slag powder (A) and binder (D)
A SiO 2 molar ratio of 1.20 or less, preferably 0.80 or less, more preferably 0.60 or less is a preferable range from the viewpoint of acid resistance. Further, the total of the alumina cement (C) and the binder (D) is preferably 6 to 75% by weight.
【００１７】また、本発明の硬化性組成物には、更に、
アルカリ金属塩類（Ｅ）を添加することができる。本発
明で用いられるアルカリ金属塩類（Ｅ）は、メタ珪酸ソ
ーダ、オルソ珪酸ソーダ、粉末珪酸ソーダ１号、水酸化
ナトリウム、水酸化カリウム、水酸化リチウム等が挙げ
られるが、メタ珪酸ソーダ、オルソ珪酸ソーダ、水酸化
ナトリウムが好ましい。これらは水ガラス（Ｂ）中の−
Ｓｉ−Ｏ−Ｓｉ−の鎖をアルカリによって切断すること
により、粘性を低下させ、モルタル、コンクリートとし
て使用した際の作業性の改善を行う他、アルカリの添加
により溶融スラグを刺激し硬化を促進する働きがある。
アルカリ金属塩類はそれぞれを単体で使用するほか、２
種類以上を組み合わせて使用することができる。これら
アルカリ金属塩類は、１〜１５重量％添加することが好
ましく、特に１〜７重量％添加することが好ましい。ア
ルカリ金属塩類を１５重量％を超えて添加した場合、強
度増進の効果は得られるが、粘性低下の効果は増進せ
ず、特にアルカリ度の高いものを過剰に添加した場合、
硬化体表面に白華を生じることがあり好ましくない。The curable composition of the present invention further comprises:
Alkali metal salts (E) can be added. Examples of the alkali metal salts (E) used in the present invention include sodium metasilicate, sodium orthosilicate, powdered sodium silicate No. 1, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Among them, sodium metasilicate and orthosilicate Soda and sodium hydroxide are preferred. These are-in water glass (B).
By cutting the Si-O-Si- chains with alkali, the viscosity is reduced and the workability when used as mortar and concrete is improved. In addition, the addition of alkali stimulates molten slag to promote hardening. There is work.
Each of the alkali metal salts is used alone,
More than one type can be used in combination. These alkali metal salts are preferably added in an amount of 1 to 15% by weight, particularly preferably 1 to 7% by weight. When the alkali metal salt is added in excess of 15% by weight, the effect of increasing the strength can be obtained, but the effect of lowering the viscosity is not increased, especially when an alkali having a high alkalinity is added excessively.
Unevenness may occur on the surface of the cured product, which is not preferable.
【００１８】本発明の硬化性組成物に、結合材（Ｄ）及
びアルカリ金属塩類（Ｅ）を共に添加する場合、
（Ｃ）、（Ｄ）及び（Ｅ）成分の合計は、組成物中１１
〜７５重量％とすることが好ましい。When both the binder (D) and the alkali metal salt (E) are added to the curable composition of the present invention,
The sum of the components (C), (D) and (E) is 11 in the composition.
It is preferable to set it to 75% by weight.
【００１９】本発明の硬化性組成物は、更に骨材（Ｆ）
を含有せしめることができる。骨材の配合割合は、硬化
性組成物（骨材を含まない）に対して、３０〜３００重
量％とすることができる。骨材としては、耐酸性を有す
るものであれば特に限定されないが、種類としては、例
えば石英質岩石、安山岩、玄武岩、陶磁器破砕物等が挙
げられる。細骨材としては、３〜８号珪砂、珪石粉及び
これらと同等の粒度、粒径を有する川砂、海砂、砕砂が
好ましく、粗骨材は用途に応じた粒径の砂利、砕石が好
ましい。細骨材の配合割合は上記の通りであるが、粗骨
材の配合割合は、５０〜３００重量％とすることが好ま
しい。なお、骨材の配合割合は３００重量％を超えても
硬化体の耐酸性は得られるが、強度低下と施工性の悪化
を招くため好ましくない。一方、骨材の配合割合が３０
重量％未満では、骨材を配合する意義が少ない。The curable composition of the present invention further comprises an aggregate (F)
Can be contained. The mixing ratio of the aggregate can be 30 to 300% by weight based on the curable composition (not including the aggregate). The aggregate is not particularly limited as long as it has acid resistance. Examples of the kind include quartz rock, andesite, basalt, crushed ceramics, and the like. As the fine aggregate, river sand, sea sand, and crushed sand having the same particle size and particle size as those of silica sand, silica powder, and silica powder of No. 3 to 8 are preferable, and the coarse aggregate is preferably gravel or crushed stone having a particle size according to the application. . Although the mixing ratio of the fine aggregate is as described above, the mixing ratio of the coarse aggregate is preferably 50 to 300% by weight. Although the acid resistance of the cured product can be obtained even when the mixing ratio of the aggregate exceeds 300% by weight, it is not preferable because the strength is reduced and the workability is deteriorated. On the other hand, when the mixing ratio of the aggregate is 30
If the amount is less than% by weight, there is little significance in mixing the aggregate.
【００２０】本発明の硬化性組成物は、適量な水を加え
て練り混ぜることで左官モルタル、グラウト材、裏込め
材、耐酸性コンクリートとすることができる。更に、８
号珪砂及び又は珪石粉と比表面積８０００〜１２０００
cm2／ｇの溶融スラグ粉末を配合し適量の水を加えれ
ば、地盤注入材として使用することもできる。The curable composition of the present invention can be made into plaster mortar, grout material, backfill material, and acid-resistant concrete by adding an appropriate amount of water and mixing. In addition, 8
No. silica sand and / or silica powder and specific surface area 8000 to 12000
If melted slag powder of cm 2 / g is blended and an appropriate amount of water is added, it can be used as a ground injection material.
【００２１】本発明の硬化性組成物を左官モルタル、グ
ラウト材、裏込め材等として使用する場合、施工方法は
鏝塗り、吹付け、ポンプ圧送、流し込み等がある。養生
方法は、通常寒冷期を除き施工現場の環境温度で行われ
る。寒冷期には、施工後凍害を避けるため加温養生を取
ることがある。耐酸性コンクリートとして使用する場合
は、施工量によりポンプ圧送、流し込み等がある。養生
方法は、施工現場の環境温度で通常行われ、寒冷期には
加温養生を取ることがある。When the curable composition of the present invention is used as a plaster mortar, a grout material, a backfill material, etc., the method of application includes troweling, spraying, pumping, pouring and the like. The curing method is usually performed at the environmental temperature of the construction site except during the cold season. During the cold season, heating and curing may be applied after construction to avoid frost damage. When used as acid-resistant concrete, there are pumping and pouring depending on the construction volume. The curing method is usually performed at the environmental temperature of the construction site, and may be heated in a cold season.
【００２２】本発明の硬化性組成物は、蒸気養生を行う
ことによりコンクリート製品とすることができる。養生
温度は４０℃〜９０℃で２時間以上行うのが好ましく、
温度は特に５０℃〜８０℃、更に６５℃〜８０℃が好ま
しく、時間は特に２〜８時間、更に２〜５時間が好まし
い。養生時間はこれ以上の時間とすることもできるが、
製造上、製造時間が長くなりコストが大きくなるため好
ましくない。また養生温度も同様にこれ以上上昇するこ
とも可能だが製造コストが大きくなるため好ましくな
い。The curable composition of the present invention can be made into a concrete product by steam curing. Curing temperature is preferably performed at 40 ° C to 90 ° C for 2 hours or more,
The temperature is particularly preferably 50 ° C to 80 ° C, more preferably 65 ° C to 80 ° C, and the time is particularly preferably 2 to 8 hours, more preferably 2 to 5 hours. The curing time can be longer, but
It is not preferable because the manufacturing time is long and the cost is high in manufacturing. Similarly, the curing temperature can be increased further, but this is not preferable because the production cost increases.
【００２３】本発明の硬化性組成物をコンクリート製品
とする際の成形方法は特に限定されず、例えば遠心力成
形、振動成形、流し込み成形、加圧成形、押し出し成
形、即時脱型成形等の従来用いられている方法のいずれ
をも用いることができる。The method of molding the curable composition of the present invention into a concrete product is not particularly limited. For example, conventional molding methods such as centrifugal force molding, vibration molding, cast molding, pressure molding, extrusion molding, and immediate demolding are available. Any of the methods used can be used.
【００２４】本発明の硬化性組成物をコンクリート製品
とする際の用途としては、特に限定されないが、例えば
管、側溝、マンホール、ボックスカルバート、共同溝、
セグメント、ブロック、漁礁、平板、ます、擁壁、貯留
槽、すて型枠、フリューム等の製品とすることができ
る。また、これらの製品において、耐酸性を必要とする
構成部材の一部、又は全てに本発明の硬化性組成物を適
用することができる。例えば、下水道に使用される管の
場合、管内面で硫黄酸化細菌により硫酸が生成すること
により腐食され、外面の土壌からの腐食は少ないため、
内面に硬化性組成物を用い、外面に普通コンクリートを
使用するのも有効である。また、強酸性温泉地などの場
合、酸性土壌であるため、製品外面に腐食環境があり、
この場合外面に硬化性組成物を適用するのが有効であ
る。内外面全てに腐食環境がある場合、製品の全ての硬
化性組成物で製造することが有効である。The use of the curable composition of the present invention as a concrete product is not particularly limited. For example, pipes, gutters, manholes, box culverts, joint grooves,
It can be a product such as a segment, a block, a reef, a flat plate, a square, a retaining wall, a storage tank, a plaster form, and a flume. Further, in these products, the curable composition of the present invention can be applied to part or all of the constituent members requiring acid resistance. For example, in the case of pipes used for sewage, corrosion is caused by the generation of sulfuric acid by sulfur oxidizing bacteria on the inner surface of the pipe, and corrosion from the soil on the outer surface is small,
It is also effective to use a curable composition for the inner surface and use ordinary concrete for the outer surface. Also, in the case of strong acid hot springs, etc., because of the acidic soil, there is a corrosive environment on the outer surface of the product,
In this case, it is effective to apply the curable composition to the outer surface. When there is a corrosive environment on all inner and outer surfaces, it is effective to manufacture with all curable compositions of the product.
【００２５】[0025]
【実施例】次に実施例を挙げて本発明を更に詳細に説明
するが、本発明はこれに何ら限定されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
【００２６】配合例 表１に、使用した石炭ガス化スラグのＣａＯ／ＳｉＯ2
モル比を示す。尚、石炭ガス化スラグは、試料１及び２
については表１に示す組成のＡスラグを、試料３及び４
については組成のＢスラグを用いた。Formulation Example Table 1 shows the CaO / SiO 2 of the coal gasification slag used.
Shows the molar ratio. In addition, coal gasification slag was used for samples 1 and 2.
For A, slag having the composition shown in Table 1 was used for Samples 3 and 4.
About the B slag of a composition was used.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】実施例１（耐酸性試験） 表２に示す配合割合で、パウダー部（石炭ガス化スラグ
粉末、高炉スラグ粉末、アルミナセメント）、水ガラス
部（水ガラス１号、水ガラス３号、メタ珪酸ソーダ粉
末）、骨材（ＪＩＳ標準砂（ＪＩＳ Ｒ５２０１準拠
品）及び水ガラス中の水分を考慮した水を添加して水分
の合計を調整し（試料１〜４）、ＪＩＳ Ｒ５２０１に
準じて混練した後、直径５０mm×高さ１００mm円柱型枠
に流し込み、ＪＩＳ Ｒ５２０１に記載の振動成形装置
にて振動二層詰め成形後、１日で脱型し、８０℃８時間
蒸気養生し（昇降湿条件２０℃／ｈｒ、９０％ＲＨ）、
本発明の硬化体１〜４を得た。比較として、普通ポルト
ランドセメントを同様に成形、養生し、硬化体とした
（比較品１）。この硬化体を２０℃で１０重量％硫酸溶
液に浸漬し、３日後、７日後、１１日後、１４日後、２
１日後及び２８日後の重量変化（重量減少率（％））を
測定した。結果を表３及び図１に示す。Example 1 (Acid resistance test) Powder parts (coal gasification slag powder, blast furnace slag powder, alumina cement), water glass parts (water glass No. 1, water glass No. 3, Sodium metasilicate powder), aggregate (JIS standard sand (JIS R5201 compliant)) and water in consideration of the water in the water glass were added to adjust the total water content (samples 1 to 4), and according to JIS R5201. After kneading, the mixture is poured into a cylindrical form having a diameter of 50 mm and a height of 100 mm, and is molded in two layers by a vibration molding apparatus described in JIS R5201. Conditions: 20 ° C./hr, 90% RH),
The cured products 1 to 4 of the present invention were obtained. For comparison, ordinary Portland cement was similarly molded and cured to obtain a cured product (Comparative product 1). This cured product was immersed in a 10% by weight sulfuric acid solution at 20 ° C., and after 3 days, 7 days, 11 days, 14 days,
The weight change (weight reduction rate (%)) after 1 day and 28 days was measured. The results are shown in Table 3 and FIG.
【００３０】[0030]
【表３】 [Table 3]
【００３１】硫酸溶液に２８日間浸漬した場合、比較品
１の普通セメント硬化体では約３９％の重量減少を示
し、溶液に溶解してしまった。これに対し、本発明の硬
化体１〜４は高々約２％の重量減少とあまり変化せず、
また外観も変化せず、高い耐酸性を示した。When immersed in a sulfuric acid solution for 28 days, the cured ordinary cement of Comparative Example 1 showed a weight loss of about 39% and was dissolved in the solution. In contrast, the cured products 1 to 4 of the present invention did not change much with a weight loss of at most about 2%,
The appearance did not change, indicating high acid resistance.
【００３２】実施例２（耐酸性試験） 表２に示す配合割合で、パウダー部（石炭ガス化スラグ
粉末、高炉スラグ粉末、アルミナセメント）、水ガラス
部（水ガラス１号、水ガラス３号、メタ珪酸ソーダ粉
末）、骨材（ＪＩＳ標準砂（ＪＩＳ Ｒ５２０１準拠
品）及び水ガラス中の水分を考慮した水を添加して水分
の合計を調整し（試料１〜４）、ＪＩＳ Ｒ５２０１に
準じて混練した後、直径５０mm×高さ１００mm円柱型枠
に流し込み、ＪＩＳ Ｒ５２０１に記載の振動成形装置
にて振動二層詰め成形後、１日湿空（２０℃−９０％Ｒ
Ｈ）で養生し、脱型後、２０℃で１４日間水中養生し、
本発明の硬化体５〜８を得た。比較として、普通ポルト
ランドセメントを同様に成形、養生し、硬化体とした
（比較品２）。この硬化体を２０℃で１０重量％硫酸溶
液に浸漬し、３日後、７日後、１１日後、１４日後、２
１日後及び２８日後の重量変化（重量減少率（％））を
測定した。結果を表４及び図２に示す。Example 2 (Acid resistance test) Powder parts (coal gasification slag powder, blast furnace slag powder, alumina cement), water glass parts (water glass No. 1, water glass No. 3, Sodium metasilicate powder), aggregate (JIS standard sand (JIS R5201 compliant)) and water considering water in water glass are added to adjust the total water content (samples 1 to 4), and according to JIS R5201. After kneading, the mixture is poured into a cylindrical form having a diameter of 50 mm and a height of 100 mm, and is subjected to two-layer vibration molding using a vibration molding apparatus described in JIS R5201, and then wet for one day (20 ° C-90% R).
H), after demolding, cured in water at 20 ° C for 14 days,
The cured products 5 to 8 of the present invention were obtained. For comparison, ordinary Portland cement was similarly molded and cured to obtain a cured product (Comparative product 2). This cured product was immersed in a 10% by weight sulfuric acid solution at 20 ° C., and after 3 days, 7 days, 11 days, 14 days,
The weight change (weight reduction rate (%)) after 1 day and 28 days was measured. The results are shown in Table 4 and FIG.
【００３３】[0033]
【表４】 [Table 4]
【００３４】硫酸溶液に２８日間浸漬した場合、比較品
２の普通セメント硬化体では約５６％の重量減少を示
し、溶液に溶解してしまった。これに対し、本発明の硬
化体５〜８は高々約２．６％の重量減少とあまり変化せ
ず、また外観も変化せず、高い耐酸性を示した。When immersed in a sulfuric acid solution for 28 days, the cured ordinary cement of Comparative Example 2 showed a weight loss of about 56% and was dissolved in the solution. On the other hand, the cured products 5 to 8 of the present invention did not change much with a weight loss of at most about 2.6%, did not change appearance, and showed high acid resistance.
【００３５】実施例３（圧縮強度試験） 表２に示す配合割合で、パウダー部（石炭ガス化スラグ
粉末、高炉スラグ粉末、アルミナセメント）、水ガラス
部（水ガラス１号、水ガラス３号、メタ珪酸ソーダ粉
末）、骨材（ＪＩＳ標準砂（ＪＩＳ Ｒ５２０１準拠
品）及び水ガラス中の水分を考慮した水を添加して水分
の合計を調整し（試料１〜４）、ＪＩＳ Ｒ５２０１に
準じて混練した後、直径５０mm×高さ１００mm円柱型枠
に流し込み、ＪＩＳ Ｒ５２０１に記載の振動成形装置
にて振動二層詰め成形後、それぞれ８０℃８時間、２０
℃３日間及び２０℃２８日間の条件で養生を行い、硬化
体９〜２０を得た。比較として、普通ポルトランドセメ
ントを同様に成形し、同様の条件で養生し、硬化体とし
た（比較品３〜５）。それぞれの硬化体について、ＪＩ
Ｓ Ａ１１０８に準拠し、圧縮強度（N/mm2）を測定し
た。結果を表５及び図３に示す。Example 3 (Compression strength test) Powder ratio (coal gasification slag powder, blast furnace slag powder, alumina cement), water glass portion (water glass No. 1, water glass No. 3, Sodium metasilicate powder), aggregate (JIS standard sand (JIS R5201 compliant)) and water in consideration of the water in the water glass were added to adjust the total water content (samples 1 to 4), and according to JIS R5201. After kneading, the mixture was poured into a cylindrical mold having a diameter of 50 mm and a height of 100 mm.
Curing was performed under the conditions of 3 days at 20 ° C and 28 days at 20 ° C to obtain cured products 9 to 20. For comparison, ordinary Portland cement was molded in the same manner, cured under the same conditions to obtain a cured product (Comparative products 3 to 5). For each cured product, JI
Compressive strength (N / mm 2 ) was measured according to SA1108. The results are shown in Table 5 and FIG.
【００３６】[0036]
【表５】 [Table 5]
【００３７】試料１〜４を用いて製造された本発明の硬
化体は、８０℃８時間及び２０℃３日間の養生条件で製
造された場合には、普通セメント硬化体と同等以上の強
度を示した。また、２０℃２８日間の養生条件の場合で
は、普通セメント硬化体より強度は低いが、４０Ｎ／mm
2以上と十分な強度を示した。When the cured product of the present invention produced using Samples 1 to 4 is produced under the curing conditions of 80 ° C. for 8 hours and 20 ° C. for 3 days, the cured product has a strength equal to or higher than that of the ordinary cement cured product. Indicated. Further, under the curing conditions of 20 ° C. for 28 days, the strength is lower than that of the ordinary hardened cement, but 40 N / mm.
It showed sufficient strength of 2 or more.
【００３８】[0038]
【発明の効果】本発明の硬化組成物に用いられる石炭ガ
ス化スラグは、一定のＣａＯ／ＳｉＯ 2比を有し、重金
属含量も少なく、且つ安定供給でき、これを利用するこ
とにより、安定的且つ効率的に優れた耐酸性と施工性を
有する硬化体を製造することができる。また、廃棄物と
して埋め立て処理を考えられている石炭ガス化スラグを
有効利用できることからガス化炉の経済性を高めること
もできる。The coal gas used in the cured composition of the present invention
Slag slag has a constant CaO / SiO TwoHave ratio, heavy gold
Genus content is low and stable supply is possible.
With this, stable and efficient excellent acid resistance and workability
A cured product having the same can be produced. Also, waste and
Coal gasification slag considered for landfill
Improve gasifier economics because they can be used effectively
Can also.
【図面の簡単な説明】[Brief description of the drawings]
【図１】図１は８０℃８時間蒸気養生して得られた硬化
体の耐酸性試験の結果を示す図である。FIG. 1 is a view showing the results of an acid resistance test of a cured product obtained by steam curing at 80 ° C. for 8 hours.
【図２】図２は２０℃１４日間水中養生して得られた硬
化体の耐酸性試験の結果を示す図である。FIG. 2 is a view showing the results of an acid resistance test of a cured product obtained by curing in water at 20 ° C. for 14 days.
【図３】図３は圧縮強度試験の結果を示す図である。FIG. 3 is a diagram showing the results of a compressive strength test.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０４Ｂ 18:14 Ｃ０４Ｂ 18:14 Ｆ ） ） Ｚ 111:23 111:23 (72)発明者 犬丸 淳 神奈川県横須賀市長坂２丁目６番１号 財 団法人電力中央研究所横須賀研究所内 (72)発明者 山本 武志 千葉県我孫子市我孫子1646 財団法人電力 中央研究所我孫子研究所内 (72)発明者 松本 匡史 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社内 (72)発明者 石田 泰之 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社内 (72)発明者 鎌田 浩司 千葉県佐倉市大作２丁目４番２号 太平洋 セメント株式会社内 (72)発明者 加藤 将裕 東京都千代田区西神田３丁目８番１号 太 平洋セメント株式会社内 Ｆターム(参考） 4G012 PA09 PA29 PB05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C04B 18:14 C04B 18:14 F)) Z 111: 23 111: 23 (72) Inventor Atsushi Inumaru Kanagawa 2-6-1 Nagasaka, Yokosuka City Inside the Central Research Institute of Electric Power Industry Yokosuka Research Institute (72) Inventor Takeshi Yamamoto 1646 Abiko, Abiko-shi, Chiba Electric Power Central Research Institute Abiko Research Institute (72) Inventor Masafumi Matsumoto Chiba Prefecture 2-4-2, Daisaku, Sakura-shi Taiheiyo Cement Co., Ltd. (72) Inventor Yasuyuki Ishida 2-4-2, Daisaku, Sakura-shi, Chiba Taiheiyo Cement Co., Ltd. (72) Koji Kamada, Daisaku 2 in Sakura-shi, Chiba Chome 4-2 Taiheiyo Cement Co., Ltd. (72) Inventor Masahiro Kato 3-8-1, Nishikanda, Chiyoda-ku, Tokyo Taihei Cement Co., Ltd. in the F-term (reference) 4G012 PA09 PA29 PB05
Claims (6)
重量％、（Ｂ）水ガラスを固形分で５〜４０重量％及び
（Ｃ）アルミナセメント５〜７０重量％を含有する硬化
性組成物。(A) Coal gasification slag powder 10 to 85
A curable composition containing (B) 5 to 40% by weight of water glass in solid content and (C) 5 to 70% by weight of alumina cement.
面積２０００〜１５０００cm2／ｇである請求項１記載
の硬化性組成物。2. The curable composition according to claim 1, wherein the fineness of the coal gasified slag powder is from 2000 to 15000 cm 2 / g in specific surface area.
脱リンスラグ、脱ケイスラグ及び脱硫スラグから選ばれ
る結合材を１〜３０重量％含有する請求項１又は２記載
の硬化性組成物。(D) blast furnace slag, converter slag,
The curable composition according to claim 1, wherein the curable composition contains 1 to 30% by weight of a binder selected from dephosphorized slag, desilicated slag, and desulfurized slag.
５重量％含有する請求項１、２又は３記載の硬化性組成
物。4. The method according to claim 1, wherein (E) the alkali metal salt is 1 to 1
4. The curable composition according to claim 1, which contains 5% by weight.
性組成物に対し、（Ｆ）骨材を３０〜３００重量％含有
せしめた硬化性組成物。5. A curable composition comprising (F) 30 to 300% by weight of the curable composition according to claim 1.
性組成物と水とを混合し、養生することにより得られる
硬化体。6. A cured product obtained by mixing the curable composition according to claim 1 with water and curing.
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| JP4575577B2 JP4575577B2 (en) | 2010-11-04 |
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Cited By (7)
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| JP2004168640A (en) * | 2002-11-07 | 2004-06-17 | Doboku Chishitsu Kk | Water glass for water glass-slag concrete, its manufacturing method, and water glass-slag concrete |
| CN101885599A (en) * | 2009-05-14 | 2010-11-17 | 中冶天工上海十三冶建设有限公司 | Premixed concrete of using coal gangue slag to replace partial natural sands |
| KR101602620B1 (en) * | 2014-09-11 | 2016-03-11 | 경기대학교 산학협력단 | Manufacturing method of geopolymer having high strength by using coal gasification slag |
| KR101611592B1 (en) * | 2014-07-16 | 2016-04-12 | 주식회사 효석 | concrete compound using slag of coal gasifier and manufacturing method thereof |
| CN111079219A (en) * | 2019-12-18 | 2020-04-28 | 太原理工大学 | Method for determining resistance of residual coal pillar passing support of residual mining face |
| CN112125589A (en) * | 2020-09-27 | 2020-12-25 | 武汉理工大学 | Coal gasification slag full-component pervious concrete |
| CN114014687A (en) * | 2021-11-11 | 2022-02-08 | 河南心连心化学工业集团股份有限公司 | Aerated concrete block prepared from gasified ash and slag and preparation method thereof |
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| CN106082884B (en) * | 2016-06-12 | 2019-05-31 | 南京大学 | A kind of insulating light wall slab and preparation process containing solid waste cinder |
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| JPH10218644A (en) * | 1997-02-05 | 1998-08-18 | Chichibu Onoda Cement Corp | Acid resistant cement composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004168640A (en) * | 2002-11-07 | 2004-06-17 | Doboku Chishitsu Kk | Water glass for water glass-slag concrete, its manufacturing method, and water glass-slag concrete |
| JP4677181B2 (en) * | 2002-11-07 | 2011-04-27 | 土木地質株式会社 | Water glass for water glass slag concrete, method for producing the same, and water glass slag concrete |
| CN101885599A (en) * | 2009-05-14 | 2010-11-17 | 中冶天工上海十三冶建设有限公司 | Premixed concrete of using coal gangue slag to replace partial natural sands |
| KR101611592B1 (en) * | 2014-07-16 | 2016-04-12 | 주식회사 효석 | concrete compound using slag of coal gasifier and manufacturing method thereof |
| KR101602620B1 (en) * | 2014-09-11 | 2016-03-11 | 경기대학교 산학협력단 | Manufacturing method of geopolymer having high strength by using coal gasification slag |
| CN111079219A (en) * | 2019-12-18 | 2020-04-28 | 太原理工大学 | Method for determining resistance of residual coal pillar passing support of residual mining face |
| CN111079219B (en) * | 2019-12-18 | 2023-06-27 | 太原理工大学 | Method for determining residual coal pillar support resistance of residual mining working face |
| CN112125589A (en) * | 2020-09-27 | 2020-12-25 | 武汉理工大学 | Coal gasification slag full-component pervious concrete |
| CN114014687A (en) * | 2021-11-11 | 2022-02-08 | 河南心连心化学工业集团股份有限公司 | Aerated concrete block prepared from gasified ash and slag and preparation method thereof |
| CN114014687B (en) * | 2021-11-11 | 2022-10-18 | 河南心连心化学工业集团股份有限公司 | Aerated concrete block prepared from gasified ash and slag and preparation method thereof |
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