JP4557191B2 - Hydraulic silica binder and water / heat resistant solidified body - Google Patents

Description

【０２４３】
［参考例２］
本参考例において、本発明で採択されるシリカ−アルカリ組成物(A) の他の態様として、粉状粘土鉱物(E) とアルカリ塩化合物(F) と水との３成分で調製されるスラリー状の粘土変性組成物(A2)について説明する。
粘土変性組成物(A2)の原料となる粉状粘土鉱物(E) には、天然の粘土鉱物であって層状構造のフィロケイ酸塩である三層構造(2:1層）の２−八面体型モンモリロナイト族の酸性白土(E-1) と、三層構造(2:1層）の３−八面体型タルク族のタルク(E-2) の２種類を選んだ。
各粘土鉱物(E) は、予め110 ℃で乾燥後、粉砕・分級して100 メッシュ篩を全通させた乾燥粉末品を供試料とした。
粉状粘土鉱物(E) の主たる組成成分［乾燥物基準(%) ］と諸物性を表２に併せ表示する。
【０２４４】

【０２４５】
粘土変性組成物(A2)の原料となり、粘土鉱物(E) に反応させるアルカリ塩化合物(F) には、市販の工業薬品から水酸化ナトリウム、炭酸リチウム、炭酸ナトリウム、ホウ酸ナトリウム、ホウ酸カリウム、２号ケイ酸ナトリウム、ケイ酸カリウムの各粉末のアルカリ塩化合物から選んだ。
これらの粘土変性組成物(A2)原料と水の配合割合を表３に併せ表示する。
スラリー状の粘土変性組成物(A2)の調製方法は、上記の天然の粘土鉱物(E) とアルカリ塩(F) とさらに水との３成分を表３に示す配合割合で混和後、常温にて８時間攪拌を行い、アルカリ成分とフェロケイ酸塩との反応・養生を完成させて各供試料とした。
【０２４６】

【０２４７】
［参考例３］
本参考例において、シリカ−アルカリ組成物(A) の他の態様として、緩衝帯形成剤(AT)であるホウ素含有化合物(T) 、結晶成長タネ(AS)であるアルミノケイ酸塩(S) 、硬化調整剤(AJ)であるバリウム塩化合物(J) 、粘度改質剤(AG)であるケイ酸カルシウム(G) ならびにこれら複数の化合物で複合されている各複合組成物（ホウ素複合組成物、タネ複合組成物、バリウム複合組成物、ケイカル複合組成物ならびに複数複合組成物）について説明する。
【０２４８】
本参考例で採択した基本標準組成物(A1)ならびに粘土変性組成物(A2)には、前記参考例１ならびに参考例２において調製した試料番号A1-2、A1-4、A1-5、A2-1ならびにA2-5のシリカ−アルカリ組成物(A) から選んだ。
本参考例の複合組成物に採択した緩衝帯形成剤(AT)のアルカリ溶液に可溶性のホウ素含有化合物(T) としては、市販試薬のホウ酸ソーダ粉末［Na₂B₄O₇・10H₂O (TS)］ならびにホウ酸カリウム粉末［K₂B₄O₇・8H₂O (TP)］から選んだ。
本参考例の複合組成物に採択した結晶の成長タネ(AS)のアルミノケイ酸塩(S) としては、Al／Si原子比が4.2 で、環員数が８で、２次粒径が20μ以下の粉末である合成ゼオライトＡ(SS)を選んだ。
【０２４９】
本参考例の複合組成物に採択した硬化調整剤(AJ)のバリウム塩化合物(J) としては、下記に示す調製法で調製された簡易型ケイ酸バリウム(JS)を選んだ。
ケイ酸バリウム(JS)の調製原料として、酸性白土の酸処理品［水澤化学製の商品名シルジホナイト：主成分(%) SiO₂ 93.0、 Al₂O₃ 1.5、 Fe₂O₃ 0.3、 MgO 0.3、 CaO 0.2、 Ig.Loss 3.7］と工業薬品である結晶性水酸化バリウム［Ba(OH)₂ ］を選んだ。ケイ酸バリウム(JS)の調製方法は、上記の両原料をSiO₂/BaOのモル比で 1.0になるよう均質混合し、ついで200 ℃×60分間乾燥した後、乾燥品をハンマー衝撃型粉砕機を用いて粉砕し、200 メッシュパスの粉末にして供試料とした。
ここに調製された簡易型ケイ酸バリウムは、Ｘ線回析によりケイ酸バリウムを主成分とすることが同定された。また、ここに調製された簡易型ケイ酸バリウムのアルカリ溶液への可溶分(Ba⁺⁺)は、下記に示す方法により測定した結果、800 mg/lの値であった。なお、他のバリウム塩化合物におけるアルカリ溶液への可溶分(Ba⁺⁺)は、市販試薬の粉末水酸化バリウム［Ba(OH)₂ ］では7300mg/lの値であり、粉末酸化バリウム［BaO ］では15000 mg/lの値であった。
【０２５０】
「バリウム塩化合物のアルカリ溶液への可溶分」の測定方法：
粉状バリウム塩化合物試料10 gを25℃の１規定苛性ソーダ溶液 100 ml 中に10分間撹拌分散させた後、試料溶液を濾別して回収した溶液中のバリウムイオンを定量分析し、採取試料中のバリウム元素全量を基準(100) とする１規定苛性ソーダ溶液中に溶出したバリウムイオン(Ba⁺⁺)量(mg/l)を求めて算出した。
【０２５１】
本参考例の粘度改質剤(AG)に採択したケイ酸カルシウム(G) としては、天然産のウオラストナイト鉱物で粒径が10μ以下の微粉末ケイ酸カルシウム(GW)、ならびに合成の粒径が10μ以下の微粉末ケイ酸カルシウム(GS)から選んだ。
以上の内容と配合割合を表４に併せ表示する。
【０２５２】

なお、表５中において、各略記号は下記の通りである。
(A1)：基本標準組成物、 (A2)：粘土変性組成物、 (T) ：ホウ素含有化合物
(S) ：アルミノケイ酸塩、(J) ：バリウム塩化合物、(G) ：ケイ酸カルシウム
【０２５３】
［参考例４］
本参考例において、本発明で採択されるアルミン酸塩組成物(B) であるアルミノ粉体(B1)ならびに前駆体組成物(B2)について説明する。
アルミノ粉体(B1)としては、市販工業薬品の中から組成式(2) で示される粉状のアルカリ土類金属のアルミン酸塩を選んだ。
また、前駆体組成物(B2)としては、組成式(6) で示される水酸化アルミニウム(BH)とアルカリ土類金属のケイ酸塩(BC)とを原料として均質混合調製された粉状のアルミン酸塩の前駆体化合物(B2)を選んだ。このときのアルカリ土類金属のケイ酸塩(BC)としては、3CaO・SiO₂ のケイ酸カルシウム(BC-3CS)や2CaO・SiO₂ のケイ酸カルシウム(BC-2CS)、さらにケイ酸マグネシウム(BC-2MS)］を選んだ。
以上の内容、主成分、比表面積と配合割合を表５に併せ表示する。
【０２５４】

【０２５５】
［参考例５］
本参考例において、アルミン酸塩組成物(B) の他の態様である廃棄物粉体(B3)ならびにセメント粉体(B4)について説明する。
廃棄物粉体(B3)としては、フライアッシュ、高炉スラッグ、生ゴミ焼却灰の産業廃棄物類より選んだ。また、セメント粉体(B4)は、JIS 規格品のポルトランドセメントとアルミナセメントより選んだ。
セメント粉体(B4)としては、市販のポルトランドセメントならびにアルミナセメントを選んだ。
以上のの内容と配合割合を表６に併せ表示する。
【０２５６】

【０２５７】
［参考例６］
本実施例において、アルミン酸塩組成物の(B) の他の態様である比表面積の大きいアルミン酸塩の軽量粉体(BL)が含浸溶液(AP)を用いて改質されている改質組成物(B5)、もしくはリンのオキシ酸含有粉体(BP)がカルシウム塩を用いて前処理されている前処理組成物(B6)について説明する。
【０２５８】
軽量粉体(BL)としては、産業廃棄物であるペーパースラッジの焼却灰（ＰＳ焼却灰：BL-P）、粘土鉱物であるモンモリロナイト(BL-M)、普賢岳の火山灰(BL-V)を選んだ。含浸改質剤である含浸溶液(AP)としては、参考例１で選んだ液状組成物(A3)の３号ケイ酸ナトリウム(A3-2)を選んだ。
改質組成物(B5)の調製方法は、下記の仕様で行った。各軽量粉体(BL)90重量部に対しケイ酸ナトリウム(A3-2)の含浸溶液(AP)10重量部と水30重量部とを加え、全体が濡れた状態を維持して混和せしめた後、60ないし80℃で乾燥し、粉末状態の改質組成物(B5-1)、(B5-2)ならびに(B5-3)を調製した。
【０２５９】

【０２６０】
リンのオキシ酸含有粉体(BP)としては、産業廃棄物である某都市下水道汚泥の焼却灰(BP-U)を選んだ。前処理剤であるカルシウム塩(GC)としては、工業薬品として市販されている消石灰を選んだ。
前処理組成物(B6)の調製は下記の仕様で行った。リンのオキシ酸含有粉体(BP)70重量部に対し消石灰のカルシウム塩(GC)30重量部と水40重量部とを加え、全体が濡れた状態を維持して良く混和せしめた後、60ないし80℃で乾燥し、粉末状態の前処理組成物(B6-1)を調製した。
以上、軽量粉体(BL)およびリンのオキシ酸含有粉体(BP)を原料として、それぞれ含浸改質された改質組成物(B5)もしくは前処理された前処理組成物(B6)の主たる組成ならびに比表面積を表７に併せ表示する。
【０２６１】
［参考例７］
本実施例において、アルミン酸塩組成物(B) の他の態様である有機化合物(BC)を含有している有機含有組成物(B7)について説明する。
有機化合物(BC)を含有している有機含有組成物(B7)としては、産業廃棄物であるペーパースラッジの含水ケーキの乾燥品(B7-1)と油脂類の脱色精製で副生した廃白土(B7-2)と焼酎製造で副生する発酵残渣(B7-2)の３種類を選んだ。
これら主たる組成ならびに比表面積を表８に併せ表示する。
【０２６２】

【０２６３】
［参考例８］
本実施例において、アルミン酸塩組成物(B) の他の態様である炭素含有組成物(B8)について説明する。
炭素含有組成物(B8)としては、製紙業界から排出されるパルプ類を含有しているペーパースラッジケーキを原料にして、このペーパースラッジケーキを乾留工程に付して調製された炭素ーアルミナーシリカ複合体［ペーパースラッジ乾留品(B8-1)］、ならびに油脂精製業界から副生される廃油を含有している廃白土を原料にして、この廃白土を乾留工程に付して調製された炭素ーアルミナーシリカ複合体［廃白土乾留品(B8-2)］の２種類を選んだ。
これら主たる組成ならびに比表面積を表９に併せ表示する。
【０２６４】

【０２６５】
［参考例９］
本実施例において、アルミン酸塩組成物(B) の他の態様である数種のアルミン酸塩組成物(B) を２種以上組み合わせて混合された多機能組成物(B9)について説明する。
多機能組成物(B9)としては、８種類のアルミン酸塩組成物(B) ［アルミノ粉体(B1)；前駆体組成物(B2)；廃棄物粉体(B3)；セメント粉体(B4)；改質組成物(B5)；前処理組成物(B6)；有機含有組成物(B7)；炭素含有組成物(B8)］より表10に示される混合割合で混合複合させて５種類の多機能組成物を選んだ。
これら多機能組成物(B9)の主たる成分組成を表10に併せ表示する。
【０２６６】

【０２６７】
［参考例10］
本参考例において、本実施例で採択した粉粒体の添加素材(K) である抗微生物剤(KZ)、機能性素材(KF)、細骨材(KM)ならびに再利用材(KR)について説明する。
抗微生物剤(KZ)としては、前記の組成式(7) で表される粉状の１価または２価 の銅もしくは亜鉛のオキシ酸塩化合物を市販試薬の中から選んだ。さらに銅のキレート化合物ならびに複合抗微生物剤は、市販品より選んだ。
【０２６８】
機能性素材(KF)としては、市販の工業薬品、試薬、特注品の顔料、活性剤、着色剤、充填剤、機能性付与剤から選んだ。
細骨材(KM)としては、代表して天然骨材である川砂より選んだ。
再利用材(KR)としては、廃棄された陶磁器等の破砕・分級品ならびに廃棄ガラス瓶等の破砕・分級品、さらに生ゴミ等の焼却灰を1200℃以上の高温で熔融してスラッグ化した顆粒状スラッグの３種類を選んだ。
以上の各添加素材(K) の代表的な性状等を表11に併せ表示する。
【０２６９】

【０２７０】
以下、本実施例で採用する物性評価の試験方法を下記に示す。
なお、シリカ系バインダーの評価は、バインダー施工時における作業可能な流動性ないしは可塑性を有する湿式流動体が確保されている時間を可使時間として評価すると共に、硬化体形成時の固化体物性により評価した。
【０２７１】
［物性評価試験方法］
１．湿式流動体の可使時間
30℃に保たれた供試料より調製された湿式流動体（３成分もしくは４成分混和物）供試体を30±2 ℃の恒温槽中に放置して、供試体に外圧を加えた時に変形を生じなくなるまでの時間を測定し、その時間を可使時間として表示した。
【０２７２】
なお、本発明シリカ系バインダーにおけるスラリー状湿式流動体の一般的施工作業可能な粘性限界を、シリカ系バインダー調製10分後の粘性が8,000 cPを越えない範囲とし、一方作業可能な可使時間を1 時間と想定した。したがって、１時間の範囲でシリカ系バインダーの粘性が10,000 cP を越えない粘性を作業性良好な可使粘性を有するシリカ系バインダーとして「合格」とした。但し、本発明シリカ系バインダーを可塑性湿式流動体として盛付や接着・目地等に用いる時は、バインダー粘性が10,000 cP を越えても施工作業性を損なうものではない。
【０２７３】
２．保存棚寿命性
粉状のワンパック品において、供試料を４層からなる紙袋に封じ込め、温度25±5 ℃で関係湿度80±10％に維持された部屋に６ヶ月間保存し、６ヶ月後における保存粉状ワンパック品を湿式流動体に調製した時の可使時間で評価し、この時の可使時間ならびに後述する固化体の一軸圧縮強度に大きな異常変動のない場合を保存棚寿命性「あり」と評価した。
【０２７４】
３．円柱状または顆粒状供試体の調製方法
一軸方向圧縮破壊強度試験評価においては、各供試料から調製された湿式流動体をφ60×90 mm の円筒状の型に注入し、室温（約25℃）で所定時間（28日間）養生固化した円柱状供試体を用いた。
その他の試験評価においては、湿式流動体を、約2 〜6 mmの顆粒状に成型し、室温（約25℃）で所定時間（48時間）養生固化した顆粒状供試体を用いた。
【０２７５】
４．一軸圧縮強度試験
調製した軸圧縮強度測定用円筒型の供試体（n 数＝３）を圧縮強度試験機により一軸方向の圧縮破壊強度試験に付し、その強度を測定し、Kg/cm²で表示した。
なお、本発明の供試体の一軸圧縮強度が28日養生で200 Kg/cm²以上の強度を示す場合を一つの目安として「合格」とした。しかし、固化体の使用目的等によっては、この目安強度値に拘束されるものでない。
【０２７６】
５．固化体強度の評価
顆粒体で調製した固化体の強度は、約5 mm型の顆粒（n 数＝５）を選び、２枚の鉄板の間に挟み、上部に50kgの分銅を静かに載せて、このとき顆粒が「潰れなかった」ときを固化体強度「あり」と評価した。
【０２７７】
６．耐熱性の評価
調製した顆粒状供試体を、650 ℃に保たれた電気オーブン中で24時間暴露し、暴露後の供試体の圧縮強度を確認し、暴露前の圧縮強度に対して暴露後の圧縮強度が60％以上確保されている場合を耐熱性「あり」と評価した。
【０２７８】
７．耐水性の評価
調製した顆粒状供試体を、約20℃に保たれた水中に７日間浸漬放置し、放置後の供試体が浸漬放置前の状態と大差のない顆粒状固化体強度を示す場合を耐水性「あり」とした。
【０２７９】
８．重金属類の水溶出試験
調製した顆粒状供試体を、JIS K 0102の規定に準拠し、環境庁告示第１３号に定める方法により、重金属類の水溶出試験を行った。なお、有害重金属としては６価クロム、カドミニウム、鉛、全シアン、ひ素、総水銀があるが、本実施例ではこれら重金属の代表として鉛元素を選び測定した。結果の表示に際し、水溶出試験における重金属の濃度検出限界以下を「ND」として表示した。
【０２８０】
９．付着力試験
JIS K 6852記載の方法に準拠して、基材鋼板と厚さ0.5 mmのアスベスト板を30×25cmの長方形に試験板に切断し、鋼板との接着面に当たる部分は240 番の練磨紙を用いて金属光沢が出るまで磨き上げ、ついでトリクロルエチレンで表面をきれいに洗浄して乾燥する。
ついで調製された供試料のシリカ系バインダーを、長方形アスベスト試験板の25×25cm面積の上に約2 mm厚に塗布し、その上に長方形鋼板の試験片の25×25cm面積を対応させる状態で接着させ、このとき接着されていない 5×25cm部分が相互に反対部分で一直線上に耳状ではみ出すようにセットする。
接着セットされた試験片を、約20℃の室温に７日間放置後、圧縮破壊試験機を用いて、試験片の耳状部分を立てて剪断破壊力を加重強度(Kg/cm²)で測定して付着力を評価した。
【０２８１】
10．処理水の抗菌効果試験とpH測定
▲１▼大腸菌混入温水の浄化試験
菌液の作成：滅菌精製水1,100 ccに大腸菌(E.c.-3)の栄養としてＮＢ培地（ブイヨン）を1/50濃度（試験標準濃度の10倍）を加え、27℃、16時間振盪培養した大腸菌を最終1/10,000となるように添加、pH７に調整する。
処理水作成：上記大腸菌液 150ccを三角フラスコに分注後密栓してブランク液(BL)とする。上記大腸菌液に所定量濃度（1g/150ccと0.5g/150ccの２水準）の供試料を投入し、密栓して試験処理水とする。
試験条件 ：試験処理水を４０℃、恒温槽中で所定時間(72 時間 )培養して菌数を測定する。
▲２▼処理水のpH測定
上記の試験処理水（1g/150cc濃度）のpHをpHメターで測定する。
【０２８２】
［実施例１］
本実施例において、各種の液状シリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) からなる２成分混合組成物(CD)、さらに必要に応じて加えられる添加素材(K) からなる３成分混合組成物(CT)に水が加えられて調製される湿式流動体の３成分混和物(WT)または４成分混和物(WQ)である水硬性シリカ系バインダー（試料番号C シリーズ）、さらにこの水硬性シリカ系バインダーを用いて硬化させた固化体について説明する。
【０２８３】
水硬性シリカ系バインダーを構成するシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) 、さらに添加素材(K) を表12に示す各種類で選び、これらと水を表12に示す配合割合で均質混和して各水硬性シリカ系バインダーを調製した。
調製した水硬性シリカ系バインダーは可使時間を測定し、一方供試体調製方法に準拠してそれぞれ供試体を作成し、耐熱性ならびに耐水性を評価し、また28日養生後の一軸圧縮強度を測定し、さらに重金属類の水溶出試験を鉛で行い、それらの結果を表13に併せ表示する。
【０２８４】
なお、本実施例における効果を明確にするために４種類の比較例を用意した。
常温における不焼成で形成される固化体として、ポルトランドセメント(H-C1)、(H-C2)と酸硬化型の水ガラス系バインダー(H-S1)、(H-S2)を選んだ。これらの供試体について上記と同様の評価試験を行いその結果を表13に併せ表示する。
ポルトランドセメント系の供試体はつぎの調製法により調製した。表12に示す市販のポルトランドセメントと川砂の場合(H-C1)、生ゴミの焼却灰の場合(H-C2)の２種類をそれぞれ配合・混練してセメントモルタルとした後、所定の円筒型枠（φ60×90mm) に流し込み、常温で28日養生して供試体とした。
【０２８５】
水ガラス系バインダーの供試体はつぎの調製法により調製した。(H-S1)の酸硬化型では表10に示す配合割合で市販JIS ３号品の液状水ガラスと酸硬化剤のリン酸アルミ二ウムの配合の場合(H-S1)、および３号品の液状水ガラスに本発明のアルミン酸塩組成物(B) に代えて水酸化アルミニウムを配合した場合(H-S2)をそれぞれ水を加えて配合・混練してモルタル状とした後、所定の型枠（φ60×90 mm)に流し込み、常温で28日養生して供試体とした。
【０２８６】

【０２８７】

【０２８８】
［実施例２］
本実施例において、各種の液状シリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) との２成分混合組成物(CD)に水の加えられて調製される湿式流動体の３成分混和物(WT)である水硬性シリカ系バインダー、さらにこれらの水硬性シリカ系バインダーを用いて顆粒状で硬化させた顆粒体について説明する。
【０２８９】
水硬性シリカ系バインダーを構成するシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) の種類とこれに加える水を含めた配合割合を表14に示す。これら３成分を均質混和して各水硬性シリカ系バインダーを調製した。
調製した水硬性シリカ系バインダーは可使時間を測定した後、前述した顆粒状供試体の調製方法に準拠して顆粒体供試体を作成し、それぞれ耐熱性ならびに耐水性を評価し、また28日養生後の固化体強度を評価し、重金属類の水溶出試験を鉛で行い、それらの結果を表15に併せ表示する。
【０２９０】

【０２９１】

【０２９２】
［実施例３］
本実施例において、液状シリカ−アルカリ組成物(A) と各種のアルミン酸塩組成物(B) との２成分混合組成物(CD)に水の加えられて調製される湿式流動体の３成分混和物(WT)である水硬性シリカ系バインダー、さらにこれらの水硬性シリカ系バインダーを用いて顆粒状で硬化させた顆粒体について説明する。
【０２９３】
水硬性シリカ系バインダーを構成するシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) の種類とこれに加える水を含めた配合割合を表16に示す。これら３成分を均質混和して各水硬性シリカ系バインダーを調製した。
調製した水硬性シリカ系バインダーは可使時間を測定した後、前述した顆粒状供試体の調製方法に準拠して顆粒体供試体を作成し、それぞれ耐熱性ならびに耐水性を評価し、また28日養生後の固化体強度を評価し、重金属類の水溶出試験を鉛で行い、それらの結果を表17に併せ表示する。
【０２９４】

【０２９５】

【０２９６】
［実施例４］
本実施例において、粉状のシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) とで予め混合されている粉状ワンパック品の粉粒体混合組成物(CH)に水が加えて調製される湿式流動体の水硬性シリカ系バインダー、さらにこれらの水硬性シリカ系バインダーを型を用いて加圧成型させた後硬化させた成型体について説明する。
【０２９７】
水硬性シリカ系バインダーを構成する粉状のシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) 、さらに必要に応じて加えられる添加素材(K) の種類とその配合割合を表18に示す。これら２成分もしくは３成分を予め混合機で均質混合して各粉粒体混合組成物(CH)を調製した。ここの調製した各粉粒体混合組成物(CH)は前述した保存棚寿命性を評価して表18に併せ表示する。
【０２９８】
各粉粒体混合組成物(CH)には、水を表18に示す量割合を加え混和して各水硬性シリカ系バインダーを調製した。調製された各水硬性シリカ系バインダーは、可使時間を測定し、一方前述した円柱状供試体調製方法に準拠して円柱状供試体を作成し、耐熱性ならびに耐水性を評価し、また28日養生後の一軸方向圧縮破壊強度試験により固化体強度を評価し、重金属類の水溶出試験を鉛で行い、それらの結果を表19に併せ表示する。
【０２９９】

【０３００】

【０３０１】
［実施例５］
本実施例において、シリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) と添加素材(K) からなる３成分混合組成物(CT)において、添加素材(K) が抗菌性等の機能を有する抗微生物剤(KZ)であり、この３成分混合組成物(CT)に水が加えられる湿式流動体の４成分混和物(WQ)である水硬性シリカ系バインダー、さらにこの水硬性シリカ系バインダーを用いて硬化させた固化体について説明する。
【０３０２】
水硬性シリカ系バインダーを構成するシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) と抗微生物剤(KZ)の種類と、これらに加える水を含めた配合割合を表20に示す。これら４成分を均質混和して４成分混和物(WQ)である各水硬性シリカ系バインダーを調製した。
調製した水硬性シリカ系バインダーは可使時間を測定した後、前述した顆粒状供試体の調製方法に準拠して顆粒体供試体を作成し、それぞれ耐熱性と耐水性を評価し、また28日養生後の固化体強度を評価し、さらに前述した処理水の抗菌効果試験に付して抗微生物性を評価した。これらの結果を表21に併せ表示する。
【０３０３】

【０３０４】

【０３０５】
［実施例６］
本実施例において、シリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) からなる２成分混合組成物(CD)、さらに必要に応じて加えられる添加素材(K) からなる３成分混合組成物(CT)に水が加えられて調製される湿式流動体の３成分混和物(WT)または４成分混和物(WQ)である水硬性シリカ系バインダー、さらにこの水硬性シリカ系バインダーを用いて硬化させた付着体について説明する。
【０３０６】
水硬性シリカ系バインダーを構成するシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) と、必要に応じて添加素材(K) の種類と、これらに加えられる水を含めた配合割合を表22に示す。これら３成分もしくは４成分を均質混和して３成分混和物(WT)もしくは４成分混和物(WQ)である水硬性シリカ系バインダーを調製した。
【０３０７】
調製した水硬性シリカ系バインダーは可使時間を測定し、前述した付着力試験の評価方法に準拠して鋼板とアスベスト板を基材とし、各バインダーの付着力を剪断破壊力測定により評価した。なお、付着力試験用の試験片を水中に24時間浸漬後に、また250 ℃の乾燥器に24時間暴露後に、それぞれの試験片の剪断破壊力を測定し、それぞれ付着体の耐水性ならびに耐熱性を評価した。それらの結果を表23に併せ表示する。
【０３０８】

【０３０９】

【０３１０】
［実施例８］
本実施例において、液状のシリカ−アルカリ組成物(A) とアルミン酸塩組成物(B) と水との３成分で調製される湿式流動体の水硬性シリカ系バインダーから生成させた顆粒体を原料として、貫通空隙を有する粟おこし状集合硬化体を調製し、不燃性防音材（板）として応用する場合について説明する。
【０３１１】
本実施例で採択した顆粒体は、実施例２で調製した試料No.C-22 ［A7-2: 20部＋B3-1: 80部］の顆粒体で1 ないし5 mmφに整粒された顆粒体を選んだ。
顆粒体を一体化させるバインダーには、実施例２における試料No.C-22 で調製した顆粒体と同質の湿式流動体の水硬性シリカ系バインダーを選んだ。
防音板の製造加工は、整粒された顆粒体100 Kgに約10Kgの水加えて顆粒体表面をぬらした後、湿式流動体の水硬性シリカ系バインダーの15Kgを加え混合し、顆粒体表面にバインダーを均質に行きわたらせ、ついで厚み30mmで300 ×300 mmの型枠に流し込む、常温に少なくとも24時間放置して初期硬度を発現させた後、脱型する。ついで、80℃に1 時間放置して固化を完成させ、防音材板製品とする。
製造された防音材板製品の防音効果を下記表24に示す規格（代表的項目）に従い、JIS A 1416に準拠して測定し、そのた結果を表24に併せ表示する。
【０３１２】

【０３１３】
【発明の効果】
本発明によれば、不焼成で製造できる耐水・耐熱性で重金属類の封じ込め可能な無機質固化体を固定体、成型体、付着体、顆粒体、集合硬化体として供給することができる。したがって、大量エネルギーを用いることなく省エネで無機質固化体の製造が可能となり、しかも有害物質を含有する産業廃棄物等の処理処分とリサイクル再利用を可能にすることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydraulic silica-based binder and a water / heat resistant solidified body, and more specifically, a silica-alkali composition, an aluminate composition, water, and an additive material added as necessary. A fixed silica, a molded body, and a composite body composed of an aluminosilicate and a silica polymer produced by releasing the hydraulic silica binder at least at room temperature, as a cured body, The present invention relates to an adherent, a granule, a heated granule, and an aggregate hardened body. In particular, when the adopted aluminate composition is a waste, the present invention relates to a technology that contributes to the recycling and reuse of waste without giving a burden to global warming.
[0002]
[Prior art]
Conventionally, water-resistant and heat-resistant inorganic products generally include so-called ceramic bodies produced by a melting or sintering method represented by tiles, tiles, sanitary ware, glass and the like. However, nowadays, there is a strong demand for carbon dioxide emission regulations related to the depletion of petroleum and the global warming, and products manufactured by melting or sintering methods using firing energy tend to be avoided. Under these circumstances, research on producing non-fired inorganic products has been actively conducted.
[0003]
There are three types of hydraulic solidification materials listed below as solidification binder materials selected for the production of inorganic products without firing.
(1) A cementing material by hydration reaction of hydraulic minerals, mainly calcium salts, as seen in plaster and cement.
(2) An alumina sol binder material obtained by alkali neutralization of aluminum sulfate as seen in sulfuric acid bands.
(3) A siloxane-bonded silica-based binder material formed by polymerization of silanol groups as seen in the acid neutralization reaction of alkali silicates such as water glass.
[0004]
Concrete is a cementing material, and this concrete is used in the field of construction and civil engineering by adding aggregate and water to cement powder and kneading to form a hydrated product of calcium-based minerals. It is widely used in the field of processing cement-based concrete secondary products, and is widely used in JIS.
[0005]
The hardening mechanism of cement is described as a solid matrix formed by hydrated compounds such as calcium silicate hydrate and ettringite produced by a hydration reaction. Therefore, concrete is a solidified body that forms a matrix with a hydrate consisting mainly of calcium compounds, has no resistance to acids, and dehydration occurs under heating conditions, causing the solidified matrix to break down and form a solidified body. Thus, a so-called acid-resistant and heat-resistant solidified body cannot be secured.
[0006]
Furthermore, when various aggregates are solidified using cement, when the organic components such as saccharides and phosphate components coexist in the aggregate, these saccharides and phosphate components are converted to cement mineral calcium salts. Since it digests, the solidified solid body formed here cannot be expected to have a strong solidified body property.
[0007]
As an alumina sol-based binder material, a binder effect of an alumina sol produced by neutralizing an acidic compound such as aluminum sulfate with an alkali is expected. However, since the neutralization reaction at this time proceeds very quickly, it is difficult to control this neutralization reaction according to the working time, and it is difficult to secure the so-called work working time. far cry.
[0008]
As the silica-based binder material, an alkali silicate containing a silanol group typified by water glass is generally used. Application as a binder is achieved by adding an acidic curing agent to the water-soluble alkali silicate and forming a polymer composed of polysiloxane bonds by acid neutralization of the alkali silicate.
[0009]
The liquid alkali silicate typified by this water glass is inexpensive and has a binding form mainly composed of siloxane bonds (-Si-O-), so that it can be used in construction and civil engineering fields. It has been used for a long time for silica gel production raw materials, production of solidified bodies requiring acid resistance and heat resistance, and coating agents and adhesives.
[0010]
The alkali silicate curing mechanism includes an air-drying type, a hydraulic type, and a reactive type. In general, the reactive type is applied. This reaction type is a type in which a curing agent is added to an alkali silicate to cause a dealkalization reaction, and a silanol group is dehydrated and condensed to form a polymer having a polysiloxane (—O—Si—O—) bond.
[0011]
Silica-based binders made from alkali silicate, which is currently commercialized, are generally composed of three components that use liquid water glass as a paste, select an acidic compound as a curing agent, and add aggregates such as fillers. ing. Therefore, at the time of construction, the three components are once mixed and kneaded on site to prepare a paste or mortar.
However, various problems remain in this silica-based binder. For example, a silica-based binder using alkali silicate as a raw material has a poor balance between on-site workability and expression of various physical properties of the produced solidified body. That is, if emphasis is placed on workability, the physical properties of the produced solidified body are poor, and if the physical properties of the produced solidified material are accelerated, the workability is poor.
[0012]
Moreover, in the silica-type binder which uses these alkali silicates as a raw material, in the solidified body formed by carrying out normal temperature construction, generally it remains as a water-soluble alkali salt in the produced solidified body. Therefore, the alkali salt prevents the water resistance of the solidified body, and the solidified body cannot be used outdoors exposed to rainwater. Moreover, the water-soluble alkali salt remaining in the solidified body reacts with carbon dioxide in the air to generate alkali carbonate, so that the so-called whitening phenomenon is unavoidable, and since these problems are unresolved, product troubles cease. .
[0013]
There are many improvement studies to solve these problems, especially studies on curing agents and curing conditions, and various improvements and development techniques have been proposed. Some of these research achievements are “inorganic adhesives” [Journal of Japan Adhesion Association12 394 (1976)]. A typical technical disclosure regarding self-hardening type alkali silicate is disclosed in US Pat. No. 2,662,202 (1953). Furthermore, the technical disclosure of a cured composition comprising a combination of a modified water glass solution and an inorganic phosphate is disclosed in JP-B 53-24212, JP-B 53-109558, JP-B 56-6387, JP-B 57-42581, etc. In Japanese Patent Publication No. 53-24206, various silicon phosphates effective for alkali silicates are described in detail. In addition, an example of acid-resistant mortar made by reacting water glass with sodium silicofluoride as a curing agent was reported (kiln cooperation).69 284 (1961).
[0014]
In addition, the disclosure of one-pack inorganic binder compositions based on powdered alkali silicate is disclosed in JP-B 58-58306, JP-B 1-53230, JP-B 2-1791, and JP-B 2-56299. It is shown in the issue. In particular, Japanese Patent Publication No. 1-353230, Japanese Patent Publication No. 2-1791 and Japanese Patent Publication No. 2-56299 are special under the conditions specified for powdery one-pack inorganic binder compositions (high-temperature heat treatment at 700 ° C or higher). It is disclosed that the fluidity of the paste slurry is improved by using the produced crystalline or amorphous barium silicate powder together. Furthermore, Japanese Patent Publication No. 53-24206 in the above-mentioned patent gazette has a technical disclosure of a water glass composition containing a curing agent that specifies the sustained release of phosphoric acid.
[0015]
As shown in the above technical disclosure, in a silica-based binder, a method in which an acidic curing agent is used in combination with an alkali silicate is common. In particular, when curing an alkali silicate at room temperature, the specified aluminate composition is blended in a specified range without blending an acidic curing agent or the like, and free from the siloxane bond produced at this time. The technology to fix the coming alkali component as an aluminosilicate zeolite or zeolite precursor composed of silica, alumina, alkali, and other problems in the prior art (working time, early physical properties, water resistance, whitening problems, etc.) In addition, there is no specific technical disclosure or example of the idea to efficiently solve the problem in the prior art.
[0016]
In addition, in the silica-based binder mainly composed of alkali silicate, accompanying the immobilization of the alkali component liberated from the generated siloxane bond as a zeolite or zeolite precursor of aluminosilicate composed of silica, alumina and alkali. Thus, for example, there is no disclosure of a technique for fixing harmful heavy metals contained in waste or the like and making heavy metals non-eluting from the solidified product.
[0017]
Furthermore, in a silica-based binder containing alkali silicate as a main component, a molded product is obtained by using a binder technology in which an alkali component is fixed by non-firing to give heat resistance and water resistance, either alone or in combination. Furthermore, this binder technology should be used as an adhesive product that is a coating material or an adhesive, and this binder technology should be used as an antibacterial product to which a material having an antibacterial function is added. No specific technical disclosure has yet been made for each application and application, such as granulated granule products and composite products of these products.
[0018]
[Problems to be solved by the invention]
At present, “energy problems” and “environmental problems” are seriously addressed as the issues of human existence. In particular, there is a strong demand for exhaustion of resources such as petroleum and carbon dioxide emission regulations related to global warming, and the production of inorganic products by a melting or sintering method using a large amount of thermal energy tends to be avoided. As an alternative, there is a demand for an effective method for obtaining a safe and stable inorganic solidified body without using a large amount of heat energy.
[0019]
On the other hand, easy landfill and dumping of waste containing toxic heavy metals is not allowed for environmental protection and environmental destruction, but rather, reuse of waste as a resource is required.
However, the treatment and disposal technology for effectively reusing waste discharged in large quantities is immature, and its establishment is urgent.
[0020]
As a method that can cope with these problems, a method has been proposed in which wastes are solidified by non-firing and disposed of. However, even if wastes are solidified with a cement-type solidifying agent, a solidified body that is useful for treatment disposal cannot be expected and has not been put to practical use. On the other hand, there is a proposal of a solidification technique by adopting a silica-based binder as a solidifying agent. However, there are various problems in the prior art of the silica-based binder, and a product trouble has actually occurred. The main cause of the trouble is that free alkali components produced as a by-product when the solidified product is generated from the alkali silicate, which is the main raw material of the silica-based binder, remain in the solidified product.
[0021]
The conditions for forming a solidified body imparted with water resistance at room temperature without heating the so-called water glass, which is the main component of the silica-based binder, have not been established. In particular, in order to give water resistance to inorganic solidified bodies composed of silica-based binders, the establishment of technology for immobilizing alkali components that are by-produced and formed in the free state during solidified body formation is incomplete, leaving problems Yes.
[0022]
Moreover, in the silica-alkali composition of the main component constituting the silica-based binder, another aspect is required that can secure a silanol group that effectively exhibits the binder effect at a low cost. In this embodiment, a silica-alkali composition obtained by reacting an alkali component with a clay mineral mainly composed of ferrosilicate forming a silica polymer body is required to have conditions as a silica-based binder. It is done.
[0023]
Furthermore, a pre-prepared powdery one-pack product is effective in order to save labor for complicated processes encountered at the construction site of the silica-based binder and secure a transport container that does not generate secondary pollution. The one-pack product is required to have conditions as a silica-based binder.
[0024]
Furthermore, it is necessary to secure and control the working life of the silica-based binder composed of the silica-alkali composition and the aluminate. It is necessary to select a regulator that can adjust the pot life, and it is necessary to study a pot life regulator using barium salts.
[0025]
As a result of various investigations and investigations on the problems related to the hydraulic silica-based binder, it was determined that the following 9 points were the main problems regarding “silica polymer and its use”.
(1) Take advantage of the heat resistance and acid resistance that are the characteristics of silica-based binders.
(2) Immobilize water-soluble alkali salt as a by-product to ensure water resistance.
(3) An acidic curing agent is not adopted in order not to produce a soluble alkali salt.
(4) The reaction is carried out by non-firing at room temperature without using special heat energy.
(5) Aluminosilicate is formed to fix the alkali component.
(6) Immobilize harmful heavy metals contained in wastes in a water-insoluble state.
(7) A general-purpose inorganic product is obtained in the form of a molded body, an adhering body, a granule, a composite and the like.
(8) Contribute to the resolution of environmental problems by making it possible to reuse waste as resources.
(9) A silica-based binder is used as a material that is inexpensive and ensures the work efficiency.
[0026]
OBJECT OF THE INVENTION
An object of the present invention is to prepare a hydraulic silica-based binder composed of a silica-alkali composition, an aluminate composition, an additive material added as necessary, and water, and this hydraulic silica. Water resistance applied to fixed bodies, molded bodies, adhering bodies, granules, heated granules, or aggregate hardened bodies, with a composite matrix made of silica polymer containing aluminosilicate released at least to room temperature as a binder -To provide a heat-resistant solidified body. Furthermore, through the provision of water- and heat-resistant solidified bodies, the heavy metals contained in the waste are fixed, and the wastes are safely reused as resources to contribute to solving environmental problems.
[0027]
[Means for Solving the Problems]
  According to the present invention, water of a wet fluid in which a three-component mixture in which water is mixed is homogeneously dispersed with respect to a two-component mixed composition comprising a silica-alkali composition and an aluminate composition. In hard silica binders;
  Said silica-alkali composition has the following composition formula (1)
  M₂O ・ aSiO₂・ BH₂O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (1)
(Wherein M is lithium, an alkali metal element of the sodium or potassium group, a is a number of 1.8 to 3.5, and b is a number of 2.5 to 50.0). Or a liquid or powdery silica-alkali composition (A) comprising two or more combined basic standard compositions (A1);
  The aluminate composition (B) is composed of an aluminate composition in which aluminum hydroxide and an alkaline earth metal are mixed in advance, and the aluminum hydroxide is an easily reactive hydroxide. Aluminum hydroxide (BH) composed of aluminum, the alkaline earth metal silicate is represented by the following composition formula (6)
  iDO ・ SiO ₂ ・ JH ₂ O (6)
(Wherein D is an alkaline earth metal element selected from the group of calcium or magnesium, i is a number between 0.2 and 5.0, and j is a number of 6.6 or less including zero) Single or two or more combined alkaline earth metal silicates (BC) selected from the salt group, and alkaline earth metal silicates per 100 parts by weight of the above aluminum hydroxide (BH) An aluminate composition (B) comprising a precursor composition (B2) in which (BC) is homogeneously mixed in an amount of 2 to 30 parts by weight.;
  The above two-component mixed composition is 10 to 310 parts by weight of the above liquid or powdery silica-alkali composition (A) with respect to 100 parts by weight of the above powdered aluminate composition (B). A mixed liquid or powdered two-component composition (CD);
  The above three-component mixture is a three-component mixture (WT) of a wet fluid that is homogeneously dispersed in an amount of 200 parts by weight or less of water with respect to 100 parts by weight of the above-mentioned two-component mixed composition (CD). A hydraulic silica-based binder is provided.
[0028]
  Further, according to the present invention, the silica-alkali composition (A) is a liquid silica-alkali composition that has been previously mixed and modified by adding an alkali salt compound and water to a powdery clay mineral.There;
  The powdery clay mineral is a powdery clay mineral (E) composed of a 2: 1 layered smectite group of hydrous ferrosilicate;
  The alkali salt compound has the following composition formula (3):
  M₂O ・ eY ・ fH₂O (3)
(Wherein M is lithium, an alkali metal element of the sodium or potassium group, Y is an oxyacid of one or more of the elements of carbon, boron or silicon, e is a number of 4.0 or less including zero, f Is a single or a combination of two or more alkali salt compounds (F) selected from the group of alkali salt compounds represented by
  The silica-alkali composition is mixed by adding 30 to 300 parts by weight of the alkali salt compound (F) and 100 to 350 parts by weight of water to 100 parts by weight of the powdered clay mineral (E). A hydraulic silica-based binder which is a liquid silica-alkali composition (A) comprising a slurry-like clay-modified composition (A2) that has been modified is provided.
[0029]
  Further, according to the present invention, a silica-alkali composition in which a buffer zone forming agent is mixed in advance with the basic standard composition (A1) or the clay-modified composition (A2).Because;
  The buffer zone forming agent is a buffer zone forming agent (AT) composed of a boron-containing compound soluble in an alkaline solution alone or a combination of two or more boron-containing compounds (T);
  Liquid or powdery boron composite composition (A3) in which the buffer zone forming agent (AT) is homogeneously mixed and composited in an amount of 40 parts by weight or less with respect to 100 parts by weight of the silica-alkali composition (A). A hydraulic silica-based binder which is a silica-alkali composition (A) is provided.
[0030]
  Further, according to the present invention, a silica-alkali composition in which crystal growth seed is mixed and mixed in advance with the basic standard composition (A1) or the clay-modified composition (A2).Because;
  The crystal growth seed has the chemical composition formula (4)
  M_{x / n}・ [(AlO₂)_x・ (SiO₂)_y] ・ WH₂O (4)
(In the formula: MIsValence n metal cation, x + y is crystal growth seed (KS) made of aluminosilicate zeolite (S) expressed by tetrahedral number per unit cell);
  From the liquid or powdery seed composite composition (A4) in which the crystal growth seed (KS) is homogeneously mixed and compounded at 0.01 to 10 parts by weight with respect to 100 parts by weight of the silica-alkali composition (A). There is provided a hydraulic silica-based binder which is a silica-alkali composition (A).
[0031]
  Further, according to the present invention, a silica-alkali composition in which a curing regulator is mixed and mixed with the basic standard composition (A1) or the clay-modified composition (A2).Because;
  The curing modifier is the following composition formula (5)
  BaO ・ gSiO₂・ HH₂O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (5)
(Wherein, g is a number including zero of 4.0 or less, h is a number including zero of 9.0 or less) selected from the group of powdered barium salts soluble in an alkaline solution, or a combination of two or more kinds of barium A curing modifier (KJ) comprising a salt (J);
  From the liquid or powdered barium composite composition (A5) in which the curing modifier (KJ) is uniformly mixed and combined at 0.1 to 10 parts by weight with respect to 100 parts by weight of the silica-alkali composition (A). There is provided a hydraulic silica-based binder which is a silica-alkali composition (A).
[0032]
  Further, according to the present invention, a silica-alkali composition in which a viscosity modifier is mixed and mixed in advance with the basic standard composition (A1) or the clay-modified composition (A2).Because;
  The viscosity modifier is a viscosity modifier (GS) composed of an easily reactive calcium silicate (G); the viscosity modifier is based on 100 parts by weight of the silica-alkali composition (A). A hydraulic silica-based binder which is a silica-alkali composition (A) comprising a liquid or powdery calcium composite composition (A6) in which (GS) is homogeneously mixed and composited in an amount of 70 parts by weight or less is provided. The
[0033]
  Further, according to the present invention, the basic standard composition (A1) or the clay-modified composition (A2) includes a buffer zone forming agent (AT), a crystal growth seed (AS), a curing regulator (AJ) or a viscosity. A silica-alkali composition in which a plurality of composite agents composed of a modifier (AG) are mixed and mixed in advanceBecause;
  A combination of two or more selected from the group consisting of the buffer zone forming agent (AT), crystal growth seed (AS), curing modifier (AJ), and clay modifier (AG). Complex agent (AM);
  Liquid or powdery multiple composite composition (A7) that is homogeneously mixed and composited in an amount of 70 parts by weight or less of the multiple composite agent (AM) with respect to 100 parts by weight of the silica-alkali composition (A). A hydraulic silica-based binder which is a silica-alkali composition (A) is provided.
[0042]
  Further, according to the present invention, a liquid or powdery two-component mixed composition (CD) comprising the silica-alkali composition and the aluminate composition.100 parts by weight, 1 to 200 parts by weight of antimicrobial agent, functional material, fine aggregate or recycled material selected from a group of single or two or more kinds of combined powder (K) In addition, 300 parts by weight or less of water is homogeneously dispersed in 100 parts by weight of the above three-component mixed composition to form a wet fluid.A hydraulic silica-based binder is provided. .
[0046]
  Further, according to the present invention, the powder and granule-added material (K) isTreated from single or two or more combined wastes selected from the group of fly ash, slug, sludge and incinerated ash containing at least 25 wt% silicates with particle sizes in the range of 0.1 μm or 5 mm WasA hydraulic silica-based binder that is a recycle material (KR) is provided.
[0049]
  The hydraulic silica-based binder is released in an atmosphere of 5 to 180 ° CBeen hereComposite matrix composed of aluminosilicate to be formed and silica polymer with siloxane bond as main chainBecause, A hardened body as a stationary body that prevents the elution of contained heavy metals from waterWater resistance characterized by being-A heat-resistant solidified body is provided.
[0054]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have determined that the adoption of a hydraulic silica-based binder is effective for forming a non-fired, water-resistant and heat-resistant inorganic solidified body. However, in the prior art, the hydraulic silica-based binder adopted in the room temperature curing system forms a solidified body using an acidic curing agent. As a result, since a water-soluble alkali salt compound is by-produced in the produced solidified product, the produced solidified product is dissolved in water, and a solidified product with water resistance cannot be expected.
[0055]
Therefore, in order to achieve the object of the present invention, it is necessary to solve these problems of the conventional hydraulic silica binder. In order to effectively complete the provision of a water-resistant and heat-resistant inorganic solidified body, which is the object of the present invention, the present inventors conducted extensive studies and conducted experiments.
[0056]
As a result, the present inventors can use a two-component mixed composition (CD) composed of a silica-alkali composition (A) and an aluminate composition (B) without using an acidic curing agent, or as necessary. A water-dispersed three-component mixture prepared by adding water to a three-component mixed composition (CT) composed of an additive material (K) added to a two-component mixed composition (CD). It has been found that a hydraulic silica-based binder which is a wet fluid of (WT) or a three-component blend (WQ) can be provided.
[0057]
Further, when the present inventors release this hydraulic silica-based binder to a non-firing atmosphere of 180 ° C. or less, a nonflammable silica polymer having a polysiloxane bond as the main chain is formed, and at the same time, the alkali component contained therein is water. It has been found that an aluminosilicate immobilized as an insoluble salt is produced, and that water resistance and heat resistance are imparted to an inorganic solidified body composed of a composite matrix of a silica polymer and an aluminosilicate.
[0058]
Furthermore, when the present inventors process this water-resistant and heat-resistant inorganic solidified body into various products according to various purposes of use, a fixed body (water-insoluble heavy metals), a molded body (secondary molding), respectively. It has been found that the present invention can be effectively applied as products, etc.), adherents (binders, paint coatings, etc.), granules (granulated products, granule products, etc.) and aggregated cured products (foaming products, filter agents, etc.).
[0059]
The water resistance and heat resistance exhibited by the solidified inorganic body formed of the composite matrix formed according to the present invention are considered to be due to the following chemical phenomenon generated by the conditions and processes found by the present inventors.
(1) Under the conditions of the present invention, a silanol group component rich in raw materials reacts at least at room temperature to form a silica polymer having a polysiloxane bond (Si—O—Si) as the main chain, The resulting solidified product is given "heat resistance" and "acid resistance".
(2) Under the conditions of the present invention, alkali reacts with coexisting alumina and silica at room temperature to form an aluminosilicate such as a water-insoluble zeolite / zeolite precursor, and the resulting solidified product has “water resistance” and “ "Water insolubility of heavy metals".
[0060]
That is, the silica polymer that forms the composite matrix of the solidified body of the present invention has a dealkalization reaction that occurs in an alkali silanol group (—Si—OM) [M: is Li, Na, K] having a silica-alkali composition (A), Next, water molecules (H from the dehydration reaction occurring at the hydroxyl group of silanol group (-Si-OH))₂O) A polymer whose main chain is a heat-resistant polysiloxane bond (-Si-O-Si-) formed by detachment. Therefore, the solidified body of the present invention is fundamentally different from a solidified body having no heat resistance formed of a hydrated mineral produced by a hydration reaction of cement or gypsum, and forms a solidified matrix having heat resistance. It is understood.
[0061]
On the other hand, the aluminosilicate that forms the composite matrix of the solidified body of the present invention coexists without dealkalizing from the alkali silanol group (-Si-OM) to liberate alkali components that are by-produced or become water-soluble salts. It reacts with alumina and silica to form a water-insoluble zeolite or zeolite precursor. Therefore, it is understood that the solidified body of the present invention fixes the alkali component in water insoluble and forms a solidified matrix having water resistance.
[0062]
The silica-alkali composition (A) adopted as the basic raw material of the present invention can include seven types. These 7 types are standard liquid or powdery basic standard composition (A1); slurry-like clay-modified composition (A2) modified from clay mineral (E) and alkali salt (F); boron A boron-modified composition (A2) mixed and mixed with a buffer zone forming agent (AT) comprising a compound (T); a crystal growth seed (KS) comprising a zeolite (S) which is an aluminosilicate Seed composite composition (A4); Barium composite composition (A5) mixed and mixed with a curing preparation agent (KJ) comprising a barium salt compound (J) soluble in an alkaline solution; adjusting the viscosity of the liquid composition A calcium composite composition (A6) mixed and mixed with a viscosity modifier (GS) comprising calcium silicate (G), and a plurality of composite agents (AM) of the above silica-alkali composition (A) [(A3 ), (A4), (A5), and (A6)] can be classified into a plurality of composite compositions (A7).
[0063]
The aluminate composition (B) adopted as the basic raw material of the present invention can include nine types. These nine types are alumino powder (B1), which is an alkaline earth metal aluminate; a precursor composition in which alkaline earth metal silicate (BC) is mixed with aluminum hydroxide (BH) ( B2); waste powder such as fly ash, slug, incinerated ash, etc. (B3); cement powder such as Portland cement and alumina cement (B4); surface area of lightweight powder (BA) is improved by impregnation solution (AP) A modified composition (B5); a pretreatment composition (B6) in which a phosphorus oxyacid-containing compound (BP) is neutralized with a calcium salt (GC); and an organic compound (BC) Organic-containing composition (B7); Carbon-containing composition of carbon-alumina composite (B8) prepared by dry distillation treatment of organic substance-containing aluminate; Aluminate composition [(B1), ( B2), (B3), (B4), (B5), (B6), (B7), (B8)] can be classified into multifunctional compositions (B9) consisting of two or more combinations
[0064]
In the water-resistant / heat-resistant solidified body of the present invention, in order to allow the solidified body to be increased, reinforced, modified, improved workability, improved various functions, etc. It is effective to prepare in advance a hydraulic silica binder in which the additive material (K) is mixed as a base material.
[0065]
The additive material (K) adopted as the basic raw material of the present invention can be broadly classified into four types. These four types are antimicrobial agents (KZ) having antibacterial properties, antifungal properties, and algal control properties; functional materials (KF) that are pigments, colorants, activators, fillers, and functionalizing agents; Natural aggregates, processed aggregates, modified aggregates and fine aggregates (KM) that are processed aggregates with a particle size of 0.1 mm to 5 mm; wastes with a particle size of 0.1 mm to 5 mm It can be classified as recycled material (KR) of reused granular material.
[0066]
The basic raw material of the hydraulic silica-based binder of the present invention is achieved by the above-described three-combination mixed composition of the silica-alkali composition (A), the aluminate composition (B), and the additive material (K). This combination mixed composition is composed of a two-component mixed composition (CD) of a silica-alkali composition (A) and an aluminate composition (B), and a silica-alkali composition (A) and an alumate composition. It is roughly divided into the case of the three-component mixed composition (CT) of the product (B) and the additive material (K). In addition, when each mixed composition is configured by one-pack mixing of only powder, it becomes possible to commercialize as a powder mixture composition (CH), the hydraulic properties of the wet fluid of the present invention Silica-based binder can be prepared at the construction site.
[0067]
The wet fluid hydraulic silica-based binder of the present invention is a water dispersion in which water is added to the above two-component mixed composition (CD) or three-component mixed composition (CT) and dispersed uniformly. There are two types of blends. These two types include a binder of a three-component mixture (WT) in which a two-component mixed composition (CD) composed of a silica-alkali composition (A) and an aluminate composition (B) is homogeneously dispersed in water. A three-component mixed composition (CT) obtained by further adding an additive material (K) to a two-component mixed composition (CD) is classified into a four-component mixture (WQ) binder dispersed in water.
[0068]
The wet fluid hydraulic silica-based binder of the present invention prepared as an admixture is present in water when released in an atmosphere of 5 to 180 ° C, and optionally when heated at 180 to 900 ° C. The raw material mixture composition reacts to form a water resistant and heat resistant composite matrix composed of silica polymer and aluminosilicate.
[0069]
The water- and heat-resistant solidified body of the present invention based on this composite matrix can be processed and manufactured into applied products according to each purpose. There are six types of application products made of this water / heat resistant solidified material. These applied products are fixed bodies to which heavy metals contained in wastes are fixed; shaped molded products such as bricks, furnace materials, sanitary ware, and building materials as molded secondary products; various base materials Adhesives adhering to the surface as a coating, coating material, coating film, adhesion, binder, etc .; granules applied to aggregates, roadbed materials, fillers, purification treatment materials, etc .; using the above granules as raw materials Collective hardened materials applied to secondary processing of soundproofing materials, heat insulating materials, greening floors, on-site construction type body, etc .; it can be classified into 6 types of applied products.
[0070]
Hereinafter, a silica-alkali composition (A), an aluminate composition (B), and an additive material (K) that are adopted as basic raw materials of the present invention, and a wet preparation prepared by adding water to the basic raw material composition. Regarding the hydraulic silica binder of the fluid, and further, the silica polymer formed from the hydraulic silica binder, the water-resistant and heat-resistant solidified body of the composite matrix composed of aluminosilicate, and its application products, along with each component Each embodiment and its features will be described with specific examples.
[0071]
In the present specification, “wet fluid” is a generic term for water-dispersed homogeneous compositions that are fluid or plastic, or slurry or paste.
In addition, the term “powder” in the present specification is a generic term for solid materials in the form of powder, sand, lump, granule, sphere, hollow or various shapes having a particle size in the range of 0.1 mm to 5 mm. Typically, a powdery body, a sand grain body, a crushed stone body, etc. can be mentioned.
In addition, in this specification, “quantity” such as “parts” and “%” indicates “weight” unless otherwise specified.
[0072]
The seven types of silica-alkali compositions (A) adopted in the present invention are all composed mainly of alkali silicate, and the basic composition thereof is collectively represented by the following composition formula (1)
M₂O ・ aSiO₂・ BH₂O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (1)
(Wherein M is lithium, an alkali metal element of sodium or potassium group, a is a number of 1.8 to 3.5, b is a number of 2.5 to 50.0) (A1).
[0073]
The alkali metal silicate alkali metal species (M) generically named in the basic standard composition (A1) is generally sodium (Na) because it is generally available and inexpensive. Among them, JIS water glass is industrially produced in large quantities and is suitable as a basic raw material for the product of the present invention. However, depending on the application field and purpose of use of the solidified body, as well as the workability and physical properties of the solidified body, and the shape of the solidified body, potassium (K) and lithium (Li) may be included alone or in the alkali metal species. It can be appropriately selected and used as a composite alkali silicate of a combination of alkali metals.
[0074]
The number of a and b in the composition formula (1) of the basic standard composition (A1) adopted in the present invention is slightly different depending on the type of the silica-alkali composition (A) selected. Is preferably in the range of 1.8 to 3.5, especially when a is in the range of 2.0 to 3.2 and b is in the range of the number of 2.5 to 50.0, the preparation of the hydraulic silica-based binder of the present invention is powdery. Or it can implement suitably with a liquid state.
[0075]
At this time, when a in the composition formula (1) is smaller than 1.8, the water resistance is inferior due to too much alkali component and slowing down the curing rate of the solidified product, or causing whitening phenomenon in the formed solidified product. There is a tendency. On the other hand, when a is larger than 3.5, the amount of reactive silanol groups decreases, and effective polymer formation consisting of a siloxane bond is not expected, and a solid body having a high hardness tends not to be obtained.
[0076]
When b in the composition formula (1) of the basic standard composition (A1) of the present invention is a number of 2.5 to 50.0, the alkali silicate of the basic standard composition (A1) is obtained as a powder. This powdery alkali silicate is suitable as a raw material for the powder / mixture composition (CH) [one-pack product].
[0077]
In the present invention, when b in the compositional formula (1) of the powdery alkali silicate is larger than 5.0, deliquescence is caused in the powdered calcium silicate, and the preservability of the powdery one-pack product is reduced. The shelf life of the granular material mixture composition (CH) of the present invention is impaired and is not appropriate. In addition, when b in the composition formula (1) is less than 2.5, the solubility of the powdered silica-alkali composition in water is impaired, and the silica-alkali composition cannot be effectively used to achieve the object of the present invention. Can not. Accordingly, it is important that b in the composition formula (1) representing the powdery alkali silicate is a powdery alkali silicate having a number in the range of 2.5 to 5.0. From this range, the solidified product of the present invention can be used. A powdery alkali silicate can be selected at any time according to the purpose, application, construction conditions, and the like.
[0078]
On the other hand, when b in the composition formula (1) of the basic standard composition (A1) is in the range of 5.0 to 50.0, it is generally a liquid alkali silicate, and the liquid composition of the basic standard composition (A1) It is suitable as a raw material for the simple liquid silica-alkali composition (A). In particular, when the liquid composition is so-called liquid water glass of sodium silicate, it is a JIS-designated industrial chemical and is suitable as a raw material of the present invention because it is inexpensive. When b in the composition formula (1) is larger than 50.0, the substantial concentration of the liquid silica-alkali composition (A) is lowered and the binder effect tends to be lowered.
[0079]
As another form of the silica-alkali composition (A) adopted for the hydraulic silica-based binder of the present invention, clay prepared in advance by reaction / curing with three components of powdered clay mineral, alkali salt compound and water A modified composition (A2) can be mentioned.
[0080]
The powdery clay mineral used as a raw material for the clay-modified composition (A2) is a hydrous ferrosilicate compound that is easily reactive to the alkali of the alkali salt compound (F) solution described below, particularly a 2: 1 layer type. A powdery clay mineral (E) made of a smectite-containing hydrous ferrosilicate compound is preferred. The powdery clay mineral (E) composed of these hydrous ferrosilicate compounds has abundant silanol groups in the polymer due to the siloxane bond, and is effective for the formation of the silica polymer that is the composite matrix of the solidified product of the present invention. is there.
[0081]
In general, a hydrous phyllosilicate compound is a generic term for a hydrous layered silicate compound based on a layered silicate structure bonded to each other centered on a Si-O tetrahedron. It hits. This phyllosilicate compound is roughly classified into a hexagonal network layered body and a quadrangular network layered body, and most silicate compounds are formed from a hexagonal network layered body. The unit constituting this phyllosilicate compound is classified into three, a face, a sheet, and a layer, and there are a tetrahedral sheet and an octahedral sheet. The unit layer composed of this tetrahedron sheet and octahedron sheet is layered to form a phyllosilicate compound, and between the layers contains cations with water molecules, Forming a state.
[0082]
According to the classification of the layered clay mineral which is a hydrous ferrosilicate compound, the 1: 1 layer type kaolinite is classified into a two-octahedron type and a three-octahedron type. On the other hand, the 2: 1 layer type includes pyrophyllite, talc, smectite, vermiculite, mica, chlorite, and the like, which are classified into a two-octahedron type and a three-octahedron type, respectively.
[0083]
However, layered clay minerals such as 2: 1 layer type smectite group 2 octahedral type montmorillonite have unstable bond of aluminum and silicon contained compared to layered clay minerals such as 1: 1 layer kaolinite. It is rich in reactivity, has a large specific surface area, high adsorption performance, and is excellent in exhibiting the binder effect in the present invention.
[0084]
As a typical hydrous ferrosilicate compound of the powdery clay mineral (E), a 2: 1 layer type smectite group ferrosilicate compound can be mentioned. The smectite dioctahedral type includes montmorillonite and beidellite, and the trioctahedral type includes saponite, hectorite, and soconite.
[0085]
Among these, montmorillonite is preferable because it has excellent reactivity and is easily available. Montmorillonite (Na, Ca_1/2)_0.33(Al_1.67Mg_0.33) Si_FourO_Ten(OH)₂ It is shown by the composition structural formula (however, interlayer water is omitted). In this montmorillonite, the distance between positive and negative charges is large, the interaction force is weak, and cation exchange occurs easily.
In addition, the amount of interlayer water varies depending on the environment, and water and organic substances tend to enter the interlayer to widen the bottom surface spacing, and have swelling properties. This montmorillonite is classified into bentonite and sub-bentonite (acid clay) that is not so swellable.
[0086]
However, since the hydrous layered clay mineral is a naturally occurring mineral, various impurities generally coexist. Therefore, in the present invention, in the case of a water-containing layered clay mineral coexisting with impurities, if the clay mineral contains at least 50% by weight or more of an active ingredient as a clay mineral, for example, montmorillonite, the object of the present invention is impaired. It can be adopted as a powdered clay mineral (E).
[0087]
Generally, the phyllosilicate compound contains moisture in an amount range of 20% by weight or less even in a dry product. However, it is important that the hydrous phyllosilicate adopted as the powdery clay mineral (E) is a dry powder. The moisture content is 20% by weight or less, preferably 18% by weight or less of dry powder, and its fineness is pulverized and classified into a powder that substantially passes at least 80% through a 65 mesh sieve. Is preferable in handling.
[0088]
On the other hand, an alkali salt compound that is reacted and prepared in advance with the powdery clay mineral (E) to produce a silica-alkali composition (A) having a silanol group is represented by the following composition formula (3):
M₂O ・ eY ・ fH₂O (3)
(Wherein, M is an alkali metal element selected from the group consisting of lithium, sodium and potassium, Y is an oxyacid of an element consisting of carbon, boron or silicon, or a combination of two or more, and e is 4.0 or less including zero. The aqueous solution having a concentration of 25% by weight or more, preferably 35% by weight or more of the alkali salt compound (F) alone or in combination of two or more of the alkali salt compounds represented by the following formula: Is desirable from the viewpoint of securing a silanol group.
[0089]
Specific examples of the alkali salt compound (F) represented by the above compositional formula (3) include an alkali hydroxide lithium hydroxide in which e in the compositional formula (3) is zero, does not contain an oxyacid, and f is 1. Sodium hydroxide and potassium hydroxide can be mentioned. Among them, sodium hydroxide is preferable because it is generally inexpensive and easily available.
[0090]
When Y in the above composition formula (3) is a carbon oxyacid, each alkali carbonate in which e is 1 and f is zero, specifically, lithium carbonate, sodium carbonate, and potassium carbonate can be mentioned. In addition, since these alkali carbonates are powders, it is preferable to select them by dissolving them in water in the present invention.
[0091]
Further, various alkali borates in which Y in the compositional formula (3) is an oxyacid of boron, e is 1 to 2, and f is 0 to 10 can be exemplified. For example, boron-containing compounds such as potassium borate and sodium borate can be selected.
[0092]
When Y in the compositional formula (3) is an oxyacid of silicon, mention may be made of alkali silicates having e of 2.0 to 3.5 and f of 2.5 to 5.0. These alkali silicates may be the same as the powdery alkali silicate of the composition formula (1) described above. Specific examples include lithium silicate, sodium silicate, and potassium silicate. Since these alkali silicates are powders, it is preferable to use them by dissolving them in water in the present invention.
[0093]
When e in the above composition formula (3) is larger than 4.0 and f is larger than 28.0, it is generated by reaction with powdered clay mineral (E) because the alkali component in the alkali salt (F) is insufficient. A satisfactory amount of silanol groups can not be expected.
[0094]
The clay-modified composition (A2) employed in the silica-alkali composition (A) of the present invention is 30 to 300 parts by weight of the alkali salt compound (F) with respect to 100 parts by weight of the powdery clay mineral (E). Further, it is preferable that water is mixed, reacted and cured in an amount of 100 to 350 parts by weight and prepared in advance into a three-component mixture (WT). In the preparation at this time, it is important to mix a predetermined amount of raw materials and then react and cure under normal temperature or 90 ° C. with stirring to generate silanol groups.
[0095]
The silica polymer comprising siloxane bonds in the present invention basically comprises a polymer matrix in which tetravalent silicon (Si) and divalent oxygen (O) are regularly arranged. However, the silica polymer produced from the alkali silicate tends to shrink in the polymer matrix due to dehydration, and strain energy is generated and accumulated in the solidified body due to the shrinkage.
[0096]
Moreover, since the polymer matrix is regularly formed, there is no room, and the generated strain energy accumulates with no escape. As a result, as a method for eliminating strain energy, there is a tendency to generate cracks and cracks in the polymer to eliminate strain energy. The occurrence of cracks and cracks causes troubles in commercialized products.
[0097]
Therefore, a field capable of absorbing the strain energy generated in the polymer, that is, a so-called “play field” is required, and this field needs to be formed as a buffer zone in the polymer. The application of this phenomenon is similar to the behavior of borosilicate glass in glass. Even in the silica polymer composed of siloxane bonds produced in the present invention, it is possible to provide a buffer zone in the polymer by appropriately containing trivalent boron elements having different valences in the polysiloxane bond, and shrinkage strain. Trouble caused by can be solved.
[0098]
In the present invention, the basic standard composition (A1) is used as another form of the silica-alkali composition (A) in the hydraulic silica-based binder in order to eliminate the shrinkage strain generated in the resulting solidified product from the above phenomenon. Alternatively, mention may be made of a liquid or powdery boron composite composition (A3) in which a boron-containing compound is mixed and compounded in advance as a buffer zone forming agent to a silica-alkali composition (A) which is a clay-modified composition (A2). Can do.
[0099]
The buffer band forming agent selected in the present invention is easily soluble in an alkaline solution and easily reactive with a siloxane bond which is a skeleton of a silica polymer, and has a trivalent valence different from a tetravalent silicon valence. A buffer zone forming agent (AT) comprising a boron-containing compound (T) containing boron is preferred.
[0100]
As the boron-containing compound (T) soluble in the alkaline solution selected in the present invention, an alkali salt which is an alkali borate is suitable, and the alkali element is preferably potassium or sodium, for example, potassium borate or boron. An acid soda can be mentioned. Further, since alkali borate is a powder, it is preferable to select from anhydrous salt, trihydrate, pentahydrate, heptahydrate and decahydrate.
[0101]
Further, as other boron-containing compound (T), various borate compounds can be appropriately selected instead of alkali salts. Examples of the borate compound include industrial chemicals such as boron oxide, boric acid, boron phosphate, zinc borate, and calcium borate.
[0102]
The boron composite composition (A3) of the present invention comprises the above-mentioned buffer band with respect to 100 parts by weight of the silica-alkali composition (A) comprising the basic standard composition (A1) or the clay-modified composition (A2). Occurs in the silica polymer produced by preparing in advance a silica-alkali composition (A) in which the forming agent (AT) is homogeneously mixed and compounded in an amount of 40 parts by weight or less, preferably 30 parts by weight or less. This is effective in eliminating the shrinkage distortion.
[0103]
As another form of the silica-alkali composition (A) adopted for the hydraulic silica-based binder of the present invention, a silica-alkali composition comprising the basic standard composition (A1) or the clay-modified composition (A2), As a crystal growth seed of the solidified product of the present invention, there can be mentioned a powdery or liquid seed composite composition (A4) in which the aluminosilicate zeolite is mixed and composited in advance.
[0104]
In the present invention, when the three-component mixture (WT) of the silica-alkali composition (A), the aluminosilicate (B) and water is released to at least room temperature, the water-insoluble in which the alkali component is immobilized. A composite matrix composed of zeolite or zeolite precursor, which is an aluminosilicate, and silica polymer is produced.
[0105]
In order to quickly produce the zeolite or zeolite precursor produced here, it is important to keep zeolite (S), which is an aluminosilicate, as a seed for crystal growth (KS) in a three-component mixture (WT). The invention is effective for solidified body formation.
[0106]
The aluminosilicate effective as seed for crystal growth (KS) is the chemical composition formula (4)
M_{x / n}・ [(AlO₂)_x・ (SiO₂)_y] ・ WH₂O (4)
(Wherein: metal cation with M valence n, x + y is the number of tetrahedra per unit cell) and is an aluminosilicate with zeolite structure (S), effective as crystal growth seed (KS) It is. These zeolites (S) are effective for both natural minerals and artificially synthesized minerals.
[0107]
The seed composite composition (A4) of the present invention is a crystal growth seed (100% by weight) based on 100 parts by weight of the silica-alkali composition (A) comprising the basic standard composition (A1) or the clay-modified composition (A2). A silica-alkali composition (A) in which KS) is homogeneously mixed and compounded in an amount of 0.01 to 10 parts by weight is effective in effectively and rapidly producing zeolite in the solidified product of the present invention.
[0108]
When the hydraulic silica-based binder of the present invention is subjected to work at the construction site, the hydraulic silica-based binder ensures the workability necessary for construction and keeps the fluid working time throughout the work. It is important to have.
[0109]
In order to ensure this working life, as another form of the silica-alkali composition (A) adopted for the hydraulic silica-based binder of the present invention, a basic standard composition (A1) or a clay-modified composition ( Examples thereof include a liquid or powdered barium composite composition (A5) in which a barium salt compound is preliminarily mixed and compounded with a silica-alkali composition (A) comprising A2) as a curing regulator.
[0110]
As the curing regulator selected in the present invention, a curing regulator (AJ) comprising a powdered barium salt compound (J) having a soluble content in an alkaline solution capable of adjusting the gelation reaction of alkali silicate is suitable. is there.
[0111]
The barium salt compound effective as the curing regulator is the following composition formula (5)
BaO ・ gSiO₂・ HH₂O (5)
(Wherein g is a number including zero of 4.0 or less, and h is a number including zero of 9.0 or less) A powdered barium salt having a soluble content in an alkaline solution represented by A curing regulator (AJ) comprising the combined barium salt compound (J) is preferred.
[0112]
In the present invention, the “soluble matter in an alkaline solution” for specifying a powdered barium salt compound adopted as a curing modifier (AJ) means that 10 g of barium salt compound is added to 100 ml of a 1N caustic soda solution at 25 ° C. After stirring and dispersing for 10 minutes, the sample solution was filtered to remove barium ions (Ba⁺⁺) And the amount (%) of barium (Ba) eluted in the 1N sodium hydroxide solution with the total amount of barium element (Ba) in the collected sample as the standard (100).
[0113]
The soluble content of the powdered barium salt compound (J) of the present invention in an alkaline solution is preferably 10% or more in order to secure a wet fluid of a hydraulic silica-based binder. When a barium salt compound (J) having a soluble content in an alkaline solution of 10% or less is adopted, a pot life that can secure a fluid necessary for the construction work of the hydraulic silica binder cannot be expected. On the other hand, the barium salt compound (J) having a soluble content in an alkaline solution of 90% or more secures the pot life of the hydraulic silica-based binder, but prolongs the time to cure, resulting in the formation of the silica polymer Proper formation is impaired, and formation of a homogeneous solidified body is hindered.
[0114]
In general, as a barium salt compound (J) that satisfies the above-mentioned soluble content in an alkaline solution and is easily available and inexpensive, the chemical formula Ba (OH) commercially available as an industrial product is used.₂・ 8H₂Barium hydroxide represented by O is preferred. It is also effective to adopt barium oxide having the chemical formula BaO 3. However, the amount of soluble matter in an alkaline solution can be controlled, and the wet fluid of a hydraulic silica-based binder and the pot life can be adjusted and managed. Therefore, in the present invention, barium silicate that exhibits mild activity of barium ions is used. Is preferred.
[0115]
This barium silicate has a soluble content of 10% or more in an alkaline solution prepared by treating a mixture of barium hydroxide and reactive silicic acid as raw materials at a low temperature (preferably 100 to 200 ° C.). A simple powdered barium silicate is preferred in the present invention because it can manage the wet fluid of the hydraulic silica-based binder, the pot life and the curing time.
[0116]
In this case, the simplified powdered barium silicate preferably has a composition formula (5) g of 4.0 or less, and if it is 4.0 or more, the activity of barium ions cannot be used effectively. Further, the number of composition formula (5) h is preferably 9.0 or less, and when the number is 9.0 or more, the storage stability of the barium salt compound (J) in the one-pack product (G) in the present invention is particularly good. Is not secured and the object of the present invention cannot be achieved.
[0117]
The powdered barium salt compound (J) having a soluble content in an alkaline solution is used for 100 parts by weight of the silica-alkali composition (A) comprising the basic standard composition (A1) or the clay-modified composition (A2). The barium composite composition (A5) is preferably mixed and composited in the range of 0.1 to 10 parts by weight.
[0118]
When the amount of the barium salt compound (J) is less than 0.1 parts by weight, it becomes difficult to ensure a pot life suitable for construction workability and a wet fluid of a hydraulic silica-based binder. When the amount of the barium salt compound (J) is more than 10 parts by weight, the working life is sufficient, but the curing rate of the solidified body becomes slow, and the productivity and practicality of the solidified body tend to be impaired. is there.
[0119]
In the present invention, the silica-alkali composition (A) in the hydraulic silica-based binder is used in order to ensure fluidity or plasticity suitable for workability without reducing the silica concentration of the prepared hydraulic silica-based binder. As another form, a silica-alkali composition (A) composed of the basic standard composition (A1) or the clay-modified composition (A2) was premixed and mixed with a readily reactive calcium silicate as a viscosity modifier. Examples thereof include a powdery or liquid calcium composite composition (A6).
[0120]
As the viscosity modifier selected in the present invention, a viscosity modifier (AG) composed of calcium silicate (G) that can adjust the sol-gel reaction of alkali silicate and is easily reactive to alkali silicate is preferable. It is.
[0121]
Specific examples of the readily reactive calcium silicate (G) adopted in the present invention include wollastonite or natural calcium silicate having an amorphous structure and synthetic calcium silicate. The powdery material is inexpensive and can be suitably selected because it is easily available.
[0122]
These calcium silicates (G) are mixed with the above viscosity modifier (AG) with respect to 100 parts by weight of the silica-alkali composition (A) comprising the basic standard composition (A1) or the clay-modified composition (A2). ) Is prepared in advance in a calcium composite composition (A6) that is homogeneously mixed and compounded in an amount of 70 parts by weight or less, preferably 60 parts by weight or less, thereby ensuring suitable workability and working life. A hydraulic silica-based binder is prepared.
[0123]
This calcium composite composition (A6) mixed with calcium silicate (G) forms a stable water-dispersed silica-alkali composition (A) and is a liquid as a wet fluid of a hydraulic silica-based binder. This is important for forming a solidified product for the purpose of the present invention.
[0124]
In the silica-alkali composition in which calcium hydroxide or calcium oxide is simply adopted instead of the calcium silicate adopted in the present calcium composite composition (A6), gelation occurs immediately, and a suitable working life time. It is not possible to prepare a hydraulic silica-based binder that is a wet fluid and has a fluidity or plasticity suitably secured.
[0125]
In the present invention, when the calcium composite composition (A6) is adopted to prepare a hydraulic silica-based binder that is a wet fluid, the silica-alkali composition (A) must contain a calcium component stably in advance. Therefore, the aluminate composition (B) can be widely selected regardless of the content of the alkaline earth metal component of the aluminate composition (B) described later, and the whitening phenomenon is suppressed. is there.
[0126]
As other forms of the silica-alkali composition (A) adopted for the hydraulic silica-based binder of the present invention, the basic standard composition (A1) which is each silica-alkali composition (A) of the previous period, a clay-modified composition A composite mixture of two or more selected from the group consisting of a product (A2), a boron-containing composition (A3), a seed-containing composition (A4), a barium-containing composition (A5) and a calcium-containing composition (A6) A powdery or liquid multiple composite composition (A7) can be mentioned.
[0127]
These multiple composite compositions (A7) can be used according to the conditions (type, blending amount, etc.) confirmed by preliminary experiments conducted in advance depending on the purpose or workability of the hydraulic silica-based binder of the present invention and the price. It is preferably adopted by mixing a plurality of compositions.
[0128]
According to the present invention, there are nine types of aluminate compositions (B) selected together with the silica-alkali composition (A) selected as the basic raw material, and these nine types of aluminate compositions (B) are , Both of which are composed mainly of an aluminate compound, and the following composition formula (2)
cQO ・ Al₂O_Three・ DH₂O (2)
(Wherein Q is an alkaline earth metal element selected from the group of calcium or magnesium, c is a number of 0.8 to 6.0, and d is a number of 6.5 or less including zero). Mention may be made of a readily reactive alumino powder (B1) comprising a compound.
[0129]
In general, it is said that an aluminate compound is formed by dissolving alumina or aluminum hydroxide in an alkaline solution. Specific examples of the easily reactive alumino powder (B1) comprising a typical alkaline earth metal aluminate compound represented by the composition formula (2) of the present invention include calcium aluminate and a spinel structure. Examples thereof include magnesium aluminate and alumina cement.
[0130]
These alumino powders (B1) are excellent in reactivity and catalytic action with the silica-alkali composition (A), and the above alumino powders (B1) are easily available as industrial chemicals. It is suitable as a raw material for silica-based binders.
[0131]
In the aluminate compound composition (B) of the hydraulic silica-based binder of the present invention, it is preferable that Q represented by the composition formula (2) is an alkaline earth metal element for the production of zeolite. This is important because the metal element exhibits a catalytic action and imparts water resistance to the resulting solidified body. Examples of the compound containing an alkaline earth metal generally include slaked lime and lime, and salts such as magnesium and magnesium hydroxide.
[0132]
When c in the composition formula (2) of the aluminate composition (B) is larger than 5.0, the amount of alumina necessary for forming the zeolite fixing the by-product alkali component is reduced, and a suitable zeolite formation cannot be expected. . On the other hand, when c is less than 0.8, the amount of the alkaline earth metal compound that acts as a catalyst during the formation of the zeolite decreases, and the formation of the zeolite cannot proceed rapidly, and the development of water resistance cannot be expected.
[0133]
Further, when d in the composition formula (2) of the aluminate composition (B) is larger than 3.5, the moisture content of the aluminate composition (B) cannot maintain the ascending powder form, and the alumina of the present invention The acid salt composition (B) is not suitable. However, when the silica-alkali composition to be reacted as a silica binder is a high-concentration liquid, it is possible to adopt an aluminate composition (B) in which d is greater than 3.5.
[0134]
The aluminate composition (B) of the alumino powder (B1) represented by the composition formula (2) of the present invention generally has an alumina content as the main component.₂O_Three 4 to 70% by weight of silica, silica content is SiO₂Contains 10 to 70% by weight, 10 to 65% by weight of alkaline earth metal oxide based on QO, and has a specific surface area of 2,000 to 100,000 cm²It is effective for preparing a hydraulic silica-based binder of an excellent wet fluid having excellent reactivity with the silica-alumina composition (A) and easy workability.
[0135]
In the aluminate composition (B) of the present invention, when the alumina content as the main component is less than 4% by weight, the alkali component produced as a by-product during the formation of the silica polymer cannot be fixed, and the solidified product has water resistance. Cannot be granted. When the alumina content is more than 70% by weight, the alkaline earth metal component, which is another component, is reduced and the rapid production of zeolite tends to be impaired.
[0136]
In addition, in order for the aluminate composition (B) to efficiently achieve the binder effect through the joint work with the silica-alumina composition (A), the specific surface area of the aluminate composition (B) is 2,000 to 100,000 cm.²It is important that the powder be / g. The specific surface area at this time is 2,000 cm²When it is smaller than / g, the reactivity of the aluminate composition (B) decreases, and it becomes difficult to fix the alkali component.
[0137]
Meanwhile, the specific surface area is 100,000 cm²When the light weight powder (BA) is larger than / g, the silica-alumina composition (A) is mixed with the liquid silica-alumina composition (A) and the aluminate composition (B) powder. The liquid part of the mixture is absorbed and the admixture is in a “bubbly” state, and cannot be secured in a continuous layer in which the hydraulic silica-based binder is integrated, and it is not possible to expect the formation of a solid integrated body that is homogeneously integrated. .
[0138]
As another form of the aluminate composition (B) adopted for the hydraulic silica-based binder of the present invention, a precursor of an aluminate compound that has been mixed with aluminum hydroxide and an alkaline earth metal silicate is used. And a precursor composition (B2) forming a body compound.
[0139]
As said aluminum hydroxide, composition formula Al₂O_Three・ 3H₂Water-containing aluminum oxide represented by O is preferable because it is easily reactive and easily available. On the other hand, as the alkaline earth metal silicate, calcium silicate and magnesium silicate are preferable because they are easily reactive and easily available. However, the alkaline earth metal silicate adopted in the present invention is silicate SiO₂The molar ratio of the alkaline earth metal oxide MO is not limited to 1: 1, and the molar ratio can be selected from the range of 0.3 to 3: 0.3 to 3.
[0140]
Further, the alkaline earth metal silicate adopted in the precursor composition (B2) of the present invention is not limited to calcium silicate and magnesium silicate, but includes blast furnace slug containing calcium silicate and the like. Silicates containing a large amount of calcium such as Portland cement are also effective in achieving the object of the present invention. Among them, Portland cement is a material having hydraulic properties and is suitable for the present invention.
Preparation of this precursor composition (B2) can be accomplished by simple intimate mixing of aluminum hydroxide and alkaline earth metal silicate.
[0141]
As another form of the aluminate composition (B) adopted as the hydraulic silica-based binder of the present invention, a waste containing an aluminate compound that has received a thermal history as a by-product from each field And waste powder (B3) such as fly ash, slug and incinerated ash.
[0142]
Waste powder (B3) containing aluminate compounds subjected to the above thermal history is discharged from fly ash by-produced from coal-fired power plants, slug by-produced during steelmaking and various metallurgical metallurgy, and paper industry. Waste powder (incineration ash of paper sludge, incineration ash of various garbage including general waste, incineration ash of sewage sludge and other sludge, incineration ash of various fermentation residues, etc.) B3).
[0143]
Although these waste powders have a thermal history, they may have a large specific surface area.
In such a case, it belongs to the field of lightweight powder (BL), which will be described later, and it is preferably adopted as a waste powder (B3) after being subjected to a treatment step for reducing the specific surface area of the powder.
[0144]
What is important in the present invention is that harmful heavy metals contained in these wastes are fixed as water-insoluble salts by the zeolite produced during the solidification process of the hydraulic silica-based binder of the present invention. . That is, when wastes are adopted for the hydraulic silica-based binder of the present invention, the heavy metals contained in these wastes become insoluble salts, elution into water is prevented, and the wastes can be safely recycled. It is possible to use. Therefore, it is possible to prevent pollution of these harmful heavy metals to the environment, which is important in that the technology of the present invention can contribute to solving environmental problems.
[0145]
Coal ash is a generic term for fly ash and clinker ash, but in this specification, description will be given focusing on fly ash. The general chemical composition (wt%) of fly ash is SiO₂: 48.2 to 61.3, Al₂O_Three : 20.0 to 26.8, Fe₂O_Three : 3.6 to 7.5, MgO: 0.8 to 2.7, CaO: 3.0 to 8.5, and specific surface area (cm²/ g) is 2400 or more, and 45 μm sieve residue is 40% or less powder. Thus, fly ash contains silica and alumina as main components and contains calcium, and is easily reactive with the silica-alkali composition and is suitable as the aluminate composition (B) of the present invention.
[0146]
The coal ash clinker ash is obtained by crushing the coal ash that has fallen into the water tank at the bottom of the boiler in a red hot state and adjusting the particle size, and is chemically stable because it is rapidly cooled from the red hot state. The chemical composition (wt%) of clinker ash is SiO₂: 51.6 to 64.0, Al₂O_Three : 17.3 to 26.9, Fe₂O_Three: 3.7 to 10.9, MgO: 0.9 to 2.6, CaO: 1.9 to 8.8, almost the same as fly ash, mainly composed of silica and alumina.
[0147]
As another form of the aluminate composition (B) adopted as the hydraulic silica-based binder of the present invention, cement powder which is a hydraulic cement powder composed of an aluminate compound containing a calcium salt mineral as a main component (B4).
[0148]
These cement powders (B4) can be appropriately selected from known and publicly available hydraulic cement powders. Specific examples include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistance) and mixed cement (blast furnace cement, silica cement, fly ash cement) specified in JIS R 5200, and Examples include powders of hydraulic cement minerals such as various special cements (white Portland cement, alumina cement, super fast setting cement, colloidal cement, oil well cement, geothermal well cement, swelling cement, and other special cement). .
[0149]
These powders of hydraulic cement minerals themselves form hydrates by mixing with water to form solidified bodies. However, in the present invention, these hydraulic cement mineral powders are effective as an inexpensive aluminate composition raw material for the hydraulic silica-based binder of the present invention and can be suitably selected.
[0150]
As another form of the aluminate composition (B) adopted for the hydraulic silica-based binder of the present invention, a modification in which the surface area of a lightweight powder containing aluminate is modified using an impregnation solution A composition (B5) can be mentioned.
[0151]
The lightweight powder containing aluminate has almost the same composition as the alumino powder (B1), and the alumina content is Al.₂O_Three 10 to 85% by weight, silica content is SiO₂Contains 10 to 75% by weight on the basis, 2 to 40% by weight on the basis of CaO, and has a specific surface area of 100,000 cm²It is a lightweight powder (BL) that is large and bulky at / g or more. When the light-weight powder (BL) is mixed with the liquid silica-alkali composition (A), the mixture becomes “basal”, and the wet-type hydraulic silica binder of the present invention is intended. The performance cannot be exhibited effectively. .
[0152]
Specific examples of lightweight powder (BL) include paper sludge as industrial waste, various incineration ash, fine powder waste from ceramic products, and various constitutions consisting of fine powders such as calcium silicate and aluminum silicate. Examples thereof include pigments, finely divided clay minerals mainly composed of aluminum silicate, hydrous soil / sedimentary soil, sludge, volcanic ash, and the like.
[0153]
The impregnating solution is preferably a liquid impregnating solution (AP) composed of an alkali silicate represented by the above composition formula (1) alone or in combination of two or more. In general, liquid sodium silicate, so-called water glass, which is inexpensive and easily available, is preferable.
[0154]
In the present invention, the light weight powder (BL) having a large specific surface area is impregnated with an impregnation solution (AP) made of alkali silicate and dried, and the pores of the light weight powder (BL) are included. Silica is deposited on the powder surface, and the specific surface area of the lightweight powder (BL) is 2,000 to 100,000 cm.²Preparation in advance in the modified composition (B5) by modifying to the range of / g can be suitably adopted as the aluminate composition (B) of the present invention.
[0155]
The treatment process for reducing the specific surface area is carried out by impregnating 100 parts by weight of the lightweight powder (BL) with the impregnation solution (AP) in an amount of 80 parts by weight or less and then drying at a temperature of 120 ° C. or less. By doing so, it becomes possible to prepare a modified composition (B5) with a reduced specific surface area, which is effective.
[0156]
As another form of the aluminate composition (B) adopted for the hydraulic silica-based binder of the present invention, a pretreatment composition in which the phosphorus oxyacid-containing aluminate compound is neutralized with a calcium salt (B6) can be mentioned.
[0157]
In general, when a compound on the acidic side containing phosphorus oxyacids is to be formed into cement by cements, the solidified product is caused by the fact that the oxyacid of phosphorus reacts with the calcium salt of the cement mineral to eliminate the solidification function. Formation is difficult. Similarly, in the hydraulic silica-based binder of the present invention, when adopting a phosphorus oxyacid-containing aluminate compound powder (BP), the neutralization reaction with the silica-alkali composition (A) has priority. Inhibits solidified body formation. Therefore, it is necessary to neutralize the phosphorus oxyacid-containing compound in advance with a calcium salt or the like.
[0158]
The phosphorus oxyacid-containing aluminate compound adopted in the pretreatment composition (B6) described above contains phosphorus oxyacid content as a main component.₂O_Five2 to 35% by weight, alumina content is Al₂O_Three 4 to 30% by weight, silica content is SiO₂A powdery phosphorus oxyacid-containing aluminate compound (BP) containing 5 to 50% by weight on a standard basis and 3 to 25% by weight on an alkaline earth metal oxide content on a QO basis. Specifically, it can be selected from incineration ash of sewage sludge and sludge treatment soil such as sludge.
[0159]
Calcium salts for neutralizing these phosphorus oxyacid-containing aluminate compound powders (BP) include slaked lime and quick lime, which are inexpensive and easily available, and also lime carbonate, calcium silicate, cements, etc. The calcium salt (GC) is preferred.
[0160]
The pretreatment composition (B6) was prepared by a method of preparing 5 to 50 parts by weight of calcium salt (GC) and 0 parts by weight of water for 100 parts by weight of phosphorus oxyacid-containing aluminate compound powder (BP). The pretreatment composition (B6) was neutralized by mixing and mixing in an amount of 100 parts by weight, followed by reaction and curing at 20 to 80 ° C., and neutralizing the phosphorous oxyacid in advance. ) Is preferably prepared in advance.
[0161]
As another form of the aluminate composition (B) adopted for the hydraulic silica-based binder of the present invention, an organic-containing composition (B7) comprising an aluminate carrying an organic compound in a homogeneous dispersion state is used. Can be mentioned.
[0162]
As the above organic compounds, natural organic compounds such as animals, plants, fermented products and their products, various synthetically produced organic compounds, and various plastics and processed polymers And organic compounds (BC) such as organic compounds.
[0163]
Specific examples of the organic-containing composition (B7) comprising an aluminate in which the organic compound (BC) is supported in a homogeneous dispersion state include paper sludge and fats and oils containing the above-mentioned waste pulps. Examples include waste white clay containing oil as a refining treatment agent, various fermentation residues containing organic matter, sludge containing sludge such as swamps, lakes and dams, and animal manure. it can.
[0164]
The general main chemical composition of organic-containing composition (B7) (% by weight on dry matter basis) is SiO₂: 5.0 to 30.0, Al₂O_Three : 1.0 to 30.0, Fe₂O_Three : 0.1 to 10.0, MgO: 0.1 to 8.0, CaO: 0.1 to 8.0, loss on ignition: 10.0 to 65.0, and specific surface area (cm²/ g) is 2400 or more, and a powder prepared such that the 45 μm sieve residue is 50% or less is suitable.
[0165]
As another form of the aluminate composition (B) adopted for the hydraulic silica-based binder of the present invention, a carbon-containing composition of a carbon-alumina composite prepared by dry distillation treatment of an organic substance-containing aluminate (B8) can be mentioned.
[0166]
The above-mentioned carbon-alumina composite is used as a dry distillation raw material, such as paper sludge containing waste pulps that are organic component-containing aluminate and decolorizing and refining treatment agent for fats and oils, and waste white clay containing oil. A carbon-alumina composite (BA) in which the organic component-containing aluminate is carbonized in the dry distillation step is preferred. The carbonization process at this time is preferably a method in which the contained organic component is carbonized by dry distillation in a temperature range of 300 to 950 ° C. using a publicly known and publicly available carbonization apparatus.
[0167]
The general main chemical composition (% by weight) of carbonized carbon-alumina composite (BA) is C: 3.0 to 50.0, SiO₂: 10.0 to 40.0, Al₂O_Three : 5.0 to 35.0, Fe₂O_Three : 0.5 to 10.0, MgO: 0.1 to 8.0, CaO: 0.1 to 8.0, specific surface area (cm²/ g) is 2400 or more, and the powder carbon-containing composition (B8) having a 45 μm sieve residue of 40% or less is suitable.
[0168]
As another form of the aluminate composition (B) employed in the hydraulic silica-based binder of the present invention, the alumina powder (B1) that is each of the aluminate compositions (B), a precursor composition (B2), waste powder (B3), cement powder (B4), modified composition (B5), pretreatment composition (B6), organic-containing composition (B7) and carbon-containing composition (B8) And a multifunctional composition (B9) comprising a combination of two or more of the above.
[0169]
These multifunctional compositions (B9) are prepared by mixing a plurality of compositions according to the conditions confirmed by preliminary experiments according to the purpose or workability of the hydraulic silica-based binder of the present invention and the price. This is preferable because it can exhibit the above functionality.
[0170]
In the present invention, the two-component mixed composition (CD) composed of the silica-alkali composition (A) and the aluminate composition (B) is the powdery aluminate composition (B). The liquid or powdery silica-alkali composition (A) is preferably mixed at 10 to 310 parts by weight with respect to 100 parts by weight.
[0171]
When the silica-alkali composition (A) is less than 10 parts by weight, the solidifying binder effect of the hydraulic silica-based binder of the present invention is reduced, which is not preferable. In addition, when the amount of the silica-alkali composition (A) is more than 310 parts by weight, no particular binder effectiveness can be found in the hydraulic silica-based binder of the present invention.
[0172]
The method for preparing the two-component mixed composition (CD) of the present invention is achieved by simple mixing of the silica-alkali composition (A) and the aluminate composition (B) at a predetermined ratio.
In this case, the mixing method differs depending on whether the silica-alkali composition (A) is liquid or powdery, but in any case, it can be generally achieved by adopting a publicly known / official mixing method. In addition, in mixing with water, which will be described later, it is effective from the viewpoint of productivity to simultaneously mix these two components.
[0173]
In the hydraulic silica-based binder of the present invention, a liquid or powdery two-component mixed composition (CD) composed of the silica-alkali composition and the aluminate composition is further added to various granular materials ( Providing a wet fluid hydraulic silica-based binder comprising a quaternary mixture (WQ) in which water is homogeneously dispersed and mixed with a ternary mixture composition (CT) in which K) is mixed. it can.
[0174]
As an additive material of the granular material adopted for the hydraulic silica-based binder of the present invention, one or two or more selected from the group of granular materials of antimicrobial agent, functional material, fine aggregate or recycle material The combination granular material addition material (K) is preferred.
[0175]
The granular material suitable as the additive material (K) of the present invention can include not only a fine powder having a particle size of less than 50 μm but also a granular material having a particle size in the range of 50 μm to 5 mm.
Specific shapes include powder, sand, lump, needle, column, sphere, hollow, fiber, plate, flake, deformed or various shapes of fine powder or granule Can be named generically.
[0176]
In addition, as the material added to the water / heat resistant solidified body of the present invention, “aggregate” blended in the solidified body such as concrete product can be selected. The “aggregates” at this time are classified into “fine aggregates” made of sand and crushed sand having a particle size of 5 mmφ or less and “coarse aggregates” made of gravel and crushed stone having a particle size of 5 mmφ or more. In this specification, “coarse aggregate” is regarded as a purely expanded aggregate, and the effect of adopting coarse aggregate is a common sense in the industry, and does not impair the essential characteristics of the water / heat resistant solidified body. Unless otherwise specified, “coarse aggregate” is not incorporated into the powder-added material (K) of the present invention.
[0177]
In the present invention, in order to exert the antibacterial effect such as antibacterial, antifungal and antialgae to the water / heat resistant solidified body of the present invention, a hydraulic silica system composed of a three-component mixed composition (CT) An antimicrobial agent (KZ) can be given as an example of the powder material (K) that is adopted as the binder.
[0178]
As the above-mentioned antimicrobial agent (KZ), it can be appropriately selected and adopted from antimicrobial agents prepared from known and publicly used organic compounds and inorganic compounds, but in the water / heat resistant solidified product of the present invention, Antimicrobial agents capable of forming ionic zinc or copper by contact with water such as oxyacid salts with zinc-containing compounds or copper-containing compounds are effective, and these effectively exhibit antimicrobial properties.
[0179]
In particular, as the antimicrobial agent, the following composition formula (7)
EO_y・ ADO_x・ BH₂O (7)
(Wherein E is silver, monovalent or divalent copper or zinc element, D is calcium, magnesium, boron, aluminum, carbon, silicon, nitrogen, phosphorus or sulfur element, a is a number from 0.1 to 3.5, b is A number of 24.0 or less including zero, y is a number between 0.5 and 1.0, and x is a number between 0.5 and 3.0). A microbial agent (KZ) can be preferably used as the powder and granule-added material (K).
[0180]
The zinc oxyacid salt compound selected as the antimicrobial agent (KZ) can be selected from commercially available reagents and industrial chemicals. Specific examples include zinc oxide [ZnO], zinc hydroxide [Zn (OH)₂], Zinc chloride [ZnCl₂], Zinc sulfite [ZnSO_Three・ 2H₂O], zinc sulfate [ZnSO_Four・ 2H₂O], zinc phosphate [Zn_Three(PO_Four)₂・ 4H₂O], zinc nitrite [Zn (NO₂)₂・ H₂O], zinc nitrate [Zn (NO_Three)₂ ・ 6H₂O], zinc borate [ZnB_FourO₇・ 4H₂O], zinc acetate [Zn (CH_ThreeCOO)₂・ 2H₂O], zinc oxalate [Zn (C₂O_Four) ・ 2H₂O], various zinc-containing solid melts (Mg_0.9Zn_0.1O 、 3MgO ・ Al₂O_Three-ZnO etc.] alone or in combination.
[0181]
Various compounds including chelate compounds containing monovalent or divalent copper in are also effective antimicrobial agents (KZ) that exhibit antimicrobial effects such as antibacterial, antifungal and antialgal, specifically copper oxide. [CuO], cuprous oxide [Cu₂O], copper carbonate [Cu₂CO_Three], Copper borate [Cu₂B_FourO₇・ 4H₂O], copper silicate [CuSiO_Three], Various chelate compounds of copper, etc. can be mentioned preferably.
[0182]
Other antibacterial fillers (KZ) also include complex oxides in which calcium ions or hydroxides or oxides of zinc or zinc ions and copper ions or silver ions are combined and dissolved in calcium or magnesium hydroxide. be able to. Furthermore, a clay mineral composed of zeolite or ferrosilicate having a supporting property, zirconium phosphate having an adsorptive power, etc., or an antimicrobial of a single material or a combination of materials in which these zinc-containing compounds are supported on activated carbon or silica gel. Agent (KZ) is also effective.
[0183]
When the zinc compounds of these antibacterial fillers (KZ), particularly water-soluble zinc salts, are incorporated in the hydraulic silica binder of the present invention, the zinc salts are silica-alkali compositions in the hydraulic silica binder. It is effective because it reacts with (A) to form zinc silicate and is fixed in the solidified body, slowly releases zinc ions, and exhibits an antibacterial effect in a water-resistant solidified body for a long time. Is preferred.
[0184]
The three-component mixed composition (CT) mixed with the antimicrobial agent (KZ) in the present invention is the two-component mixed composition of the silica-alkali composition (A) and the aluminate composition (B). Preferably, the antimicrobial agent (KZ) is mixed in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the product (CD), and the antimicrobial agent is 1 part by weight. When the amount is less than 10 parts by weight, no antimicrobial effect appears, and when the amount is more than 70 parts by weight, no significant improvement is observed.
[0185]
4-component mixture (WQ) that exhibits antimicrobial properties by mixing water in an amount of 1 to 200 parts by weight with 100 parts by weight of the above-mentioned 3-component mixture composition (CT) and dispersing homogeneously. A wet fluid hydraulic silica-based binder is prepared.
[0186]
In the present invention, in order to impart various diversity and functionality to the water-resistant and heat-resistant solidified body of the present invention, the addition of a granular material adopted as a hydraulic silica-based binder composed of a three-component mixed composition (CT) Examples of the material (K) include functional materials (KF) such as pigments, colorants, activators, fillers, and function-imparting agents.
[0187]
As the functional material (KF), pigments, colorants, activators, fillers that are generally adopted in various fields such as praxis processing, paints, adhesives, cement processing, etc. Any functional material (KF) composed of a functionality-imparting agent can be suitably employed.
[0188]
These functional materials (KF) are powdered, fibrous, massive, granular, spherical, flakes, depending on the physical properties, functionality, workability, purpose of use, etc. required for the water / heat resistant solidified product of the present invention. Selected from the group of powders, activators, colorants, fillers, and functional agents, which have various shapes such as shapes, cullet shapes, and specific shapes, and those particles that have been previously pasted with a solvent such as water be able to. Preferred examples of the functional material (KF) employed in the present invention are shown below. However, the granular additive material (K) adopted in the present invention is not limited to the examples shown here.
[0189]
As the pigment, various colored or extender pigments generally known and used in the art can be employed. Examples of inorganic pigments include carbon black, titanium dioxide, iron oxide, iron hydroxide, dial, magnetic material, chromium oxide, chrome lead, ultramarine, various colored metal oxides, etc., fired pigments, inorganic colored pigments, and metals, Alloys, non-oxides, oxides, etc., silica fine powders, white carbon, alumina, calcium, calcium carbonate, magnesia, fused alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide, various silicic acids It can be selected from inorganic functional pigments such as salt and clay powder, extender pigments and the like according to the purpose.
[0190]
Examples of organic pigments include insoluble azo pigments, soluble azo pigments, condensed polycyclic pigments, quinacridone pigments, isoindolinone pigments commonly used in red and yellow, and blue and green pigments. And cyanine blue and cyanine green. Of these, pigments that are highly alkaline are suitable.
As the colorant, the above inorganic pigments and organic pigments can also be used, but it is desired to select a known organic coloring compound, inks and dyes of each color, which are widely used in the industry, alone or in combination of two or more. It is possible to impart a hue to the solidified product.
[0191]
As the activator, powder products such as boric acid-containing compounds, lead-containing compounds, chromic acid-containing compounds, and phosphoric acid-containing compounds can be selected. By pre-mixing these activators in the hydraulic silica binder of the present invention, for example, when a metal such as iron is selected as a coated substrate, a coating material or a binder by the polymer composition and the substrate It is possible to improve the adhesion of the material and to expect anticorrosion. Further, when an acid salt is selected, it can also be expected as a neutralizing agent for neutralizing the alkali component of the silica-alkali composition.
[0192]
The fillers include flakes, pastes, powders of metals and alloys such as stainless steel, silicon, zinc, aluminum and iron, glass powders, glass cullet, ceramic powder, ceramic cullet, diamond powder, silicon oxide (silica sand powder, Meteorite powder, silica powder, silica fume, fused silica powder, etc.), magnesia powder, calcium carbonate, zircon sand, rock powder (serpentine, andesite, meteorite, etc.), various clays (bentonite, smectite, gillome, kibushi clay, etc.) Products), calcined clay (baked products such as bauxite, montmorillonite, kaolin), gypsum, calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, water Barium oxide, aluminum silicate Can be appropriately selected glaze having various compositions contents, talc, mica, from the particle size 200 micron powder such as fly ash.
[0193]
As the function-imparting agent, all the function-providing agents known in the art and publicly used and their materials can be adopted. Specific examples of these functionalizing agents include various rust preventives made of inorganic or organic materials, antioxidants, anti-slip agents, blocking materials, incombustible / flame retardants, ultraviolet / infrared absorbers, anti-fogging agents. Agent, repellent, insecticide, luminous pigment, luminous body, photocatalyst, heat conductor, conductor, dielectric, electromagnetic wave absorption / shielding agent, insulating pigment, heating element, expansion body, water absorbing agent, elastic body, Examples thereof include powders such as antistatic agents, activators, adsorbents, deodorants, deodorants, fragrances, anti-condensation agents, various fertilizers, various plant species, and various drugs. When the functionality-imparting agent is a liquid, it can be prepared in advance as a composite powder in which these liquids are supported on a specific powder and can be adopted as the functional material (KF) of the present invention.
[0194]
The three-component mixed composition (CT) mixed with the functional material (KF) in the present invention is the two-component mixed composition of the silica-alkali composition (A) and the aluminate composition (B). A 4-component mixed composition (CT) in which the functional material (KF) is mixed in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the product (CD) is preferred, and the functional material (KF) is 1 When the amount is less than parts by weight, the effect of the functional material (KF) does not appear, and when the amount is more than 200 parts by weight, no significant improvement is observed.
[0195]
In the present invention, in order to impart reinforcement and filling properties to the water-resistant and heat-resistant solidified body of the present invention, a granular material added to a hydraulic silica-based binder composed of a three-component mixed composition (CT) ( Examples of K) include natural aggregates, processed aggregates, modified aggregates, and fine aggregates (KM) that are processed aggregates having a particle size in the range of 0.1 mm to 5 mm.
[0196]
In addition, these fine aggregates (KM) are respected for their shape and particle size composition, but their purpose of use and functionality of the fine aggregate (KM) are respected and further processed, improved, After being treated and modified, it is appropriately selected as processed aggregate, improved aggregate, or treated aggregate according to each purpose.
[0197]
The fine aggregate (KM) of the present invention is a natural aggregate generally represented by “sand” and has a water absorption of less than 0.4 ml / g and a particle size of 5 mm or less. Typical fine aggregates (KM) include glass with a particle size of 0.2 mm to 10 mm, ceramics, ceramics, silicon oxide (eg, cinnabar, meteorite, sea sand, quartz, silica fume, fused silica), calcium carbonate, zircon sand, Various clays (refined products such as bentonite, smectite, gillome, kibushi clay), calcined clay (bauxite, kaolin), gypsum, aluminum silicate, calcium silicate, magnesium silicate, barium carbonate, mica, asbestos, mica, Rustite, feldspar, chamotte, mullite, alumina, dolomite, magnesia, calcia, zirconia, volcanic ash and volcanic lava grains in various regions, glazes of various compositions, heat-resistant refractories such as carbon, graphite, carbide, nitride, etc. Powder and granular products; Flakes and powders of metals and alloys such as stainless steel, lead and iron; Glass fiber, rock It can be selected as needed singly or two or more kinds selected from the group such as; Le, natural mineral fibers, inorganic fibers such as carbon fibers.
[0198]
These various fine aggregates (KM) are composed of the above-mentioned various aluminate compositions (B) [powder composition (B1), precursor composition (B2), industrial waste composition (B3), cement composition] (B4), modified composition (B5), pretreatment composition (B6), carbon-containing composition (B7), organic-containing composition (B8), multifunctional composition (B9)] for 100 parts by weight Addition and mixing treatment in an amount of 400 parts by weight or less is important for effectively exhibiting the performance of the hydraulic silica-based binder of the present invention according to the purpose.
[0199]
In the present invention, in order to impart reinforcement and filling properties to the water-resistant and heat-resistant solidified body of the present invention, a granular material added to a hydraulic silica-based binder composed of a three-component mixed composition (CT) ( Examples of K) include a waste recycling material having a particle size in the range of 0.1 mm to 5 mm and a recycling material (KR) which is a recycling material.
[0200]
As the recycled material (KR) in the present invention, various general and industrial wastes containing at least 10% by weight of silicates are processed in the form of powder, sand, column, lump, Recycled or recycled waste that has been processed into granules, spheres, hollow bodies, flakes, fibers, unspecified shapes, solidified bodies of various shapes, melts, glass bodies, etc. It can be selected from materials according to the purpose.
[0201]
Recycled material (KR) with a particle size of 0.2 mm to 10 mm made of wastes selected here is blast furnace slug, etc. discharged from metal smelters that are silicate-containing waste, copper, aluminum red Sludges such as mud; fly ash discharged from coal-fired power plants; paper sludge discharged from the paper industry; various incineration ash by-produced from incineration ash and wastewater treatment of garbage; stone, clay and ceramics Dust powder discharged from the ceramic industry handled; various shellfish and shellfish waste such as scallops and oysters; sludge discharged from ships, etc .; sludge and sediments discharged from dams and rivers, and various water treatments; water Examples thereof include silicate-containing wastes such as construction-related industrial wastes, processed aggregates, improved aggregates and treated aggregates thereof.
[0202]
However, these wastes, especially silicate-containing wastes, such as paper sludge, various incineration ash, and volcanic ash, have undergone a thermal history, and many pores and pores are formed on the particle surface. It has a large surface area and a large water absorption of 0.4ml / g or more. In this way, it is physically difficult to form a solid solidified body by covering the waste recycling material (KR) having a large specific surface area and a large amount of water absorption with a hydraulic silica-based binder. In this case, as described above, it is preferable to reduce the specific surface area by applying the treatment process using the impregnation solution (AP) and adopt it as the reusable material (KR) of the present invention.
[0203]
These various recycled materials (KR) include the above-mentioned various aluminate compositions (B) [powder composition (B1), precursor composition (B2), industrial waste composition (B3), cement composition] (B4), modified composition (B5), pretreatment composition (B6), carbon-containing composition (B7), organic-containing composition (B8), multifunctional composition (B9)] for 100 parts by weight The addition and mixing treatment in an amount of 400 parts by weight or less is important for effectively exhibiting the performance of the hydraulic silica binder of the wet fluid of the present invention depending on the purpose.
[0204]
A mixing treatment in which the additive material (K) adopted in the present invention is blended and mixed in the hydraulic silica-based binder or in the silica-alkali composition (A) or the aluminate composition (B) as each raw material is Effectively blending and mixing according to the purpose of the present invention by selecting from various mixers, blenders, kneaders, dispersers, etc. known and publicly used in this industry and the cement and concrete industries. I can do it.
[0205]
Each of the above additive materials (K) takes into account the purpose of use of the solidified product of the present invention and the like in advance with sufficient consideration for properties such as particle size constitution, shape, pore volume, specific surface area, water absorption, oil absorption and the like. It is preferable to use the additive material (K) subjected to drying, pulverization, classification, mixing, sintering, purification, etc. alone or in combination of two or more. Further, depending on workability, purpose of use, etc., these additive materials (K) can be surface-treated with various coupling materials, surfactants, etc. in advance and adopted in the hydraulic silica-based binder of the present invention.
[0206]
In the present invention, the three-component mixed composition (CT) mixed with the powder and granule-added material (K) is the two components of the silica-alkali composition (A) and the aluminate composition (B). It is generally preferable to mix 1 to 200 parts by weight of the above-mentioned granular material (K) with respect to 100 parts by weight of the admixture, and 1 part by weight of the granular material (K). When the amount is less, the effect of the powder and granule-added material (K) does not sufficiently appear, and when the amount is more than 200 parts by weight, no significant improvement is observed.
[0207]
In the present invention, when the silica-alkali composition (A) is in powder form, the above-mentioned two-component mixed composition (CD) and three-component mixed composition (CT) are pre-packed in one powder form. It becomes possible to prepare it as a powder / particle mixture composition (CH). This powdery one-pack powder / mixture composition (CH) has the merit that it can be blended with water at the construction site when used to prepare a wet fluid hydraulic silica-based binder.
[0208]
Therefore, when adopting the two-component mixed composition (CD) or the three-component mixed composition (CT) powder mixture composition (CH), these products do not contain water. There is no need to pay the transportation cost for water when transporting. Moreover, since the binder product is transported in powder form, it is possible to adopt, for example, a paper bag that can be easily post-processed as compared to liquid transport, and post-treatment of the container used when the liquid binder is transported. There is no need to consider it, and problems associated with container processing can be solved, and labor saving and simplification can be realized.
[0209]
In the powder and particle mixture composition (CH), the aluminate composition (B) is 50 to 1000 per 100 parts by weight of the silica-alkali composition (A) of the powder composition (A2). It is important that they are mixed in the amount of parts by weight and packed in one pack to ensure the shelf life of the one-pack product.
[0210]
The wet fluid hydraulic silica-based binder in the present invention is a two-component mixed composition (CD) composed of the silica-alkali composition (A) as a raw material and the aluminate composition (B). In addition, the three-component mixed composition (CT) constituted by adding the above-mentioned additive material (K), if necessary, or the powder mixture composition (CH) prepared into a powdery one-pack product On the other hand, by mixing a predetermined amount of water and mixing them uniformly, it can be prepared as a binder which is a fluid or plastic wet fluid that is optimal for workability and effective in achieving the object.
[0211]
The water adopted at this time is not limited to pure water or tap water, and does not impair the performance of solidified bodies according to the purpose, such as well water, rainwater, river / lake water, factory wastewater recycled water, etc. You can choose by range. The mixing ratio of water with respect to the raw material at this time is the selected two-component mixed composition (CD) or three-component mixed composition (CT) or the powder mixture composition (CH) that is a powdery one-pack product. Although it depends on the contents, further required workability, and intended use of each solidified product, it is generally preferable to select water in an amount of 300 parts by weight or less with respect to 100 parts by weight of these raw materials.
[0212]
When the raw material selected at this time already has water, the water to be blended may be substantially zero. However, in the construction site where the flowability of the binder is required, it is preferably in the range of 50 to 100 parts by weight. On the other hand, in the field where plasticity is required for the binder, the range is preferably 30 to 50 parts by weight. Further, when a material having high water absorption is selected as the additive material (K), it is preferably in the range of 100 to 300 parts by weight. In any case, these water blending amounts can be easily determined by conducting a simple preliminary experiment.
[0213]
The important thing when preparing a binder for wet fluids is that a solidified body with the desired performance and function is formed, but at the same time, the construction work to form the target solidified body is achieved with high productivity. It is in. For this purpose, it is necessary to mix water with sufficient consideration for the working life of the binder.
[0214]
A method for preparing a hydraulic silica-based binder composed of a three-component blend (WT) or a four-component blend (WQ), which is a wet fluid of the present invention, into a homogeneous blend is commonly used in the public and public industry. This can be easily achieved by selecting from a method in which the raw materials are homogeneously mixed using a mixer, a stirrer, a disperser or the like.
[0215]
What is important in the present invention is that the hydraulic silica-based binder of the wet fluid prepared in advance under each of the above conditions is released at least at room temperature and, if necessary, at 5 to 180 ° C. The silica-alkali composition (A) and the aluminate composition (B) coexisting in the binder are reacted in the presence of water, and a curing step is added as necessary to form siloxane bonds in the main chain. A non-flammable silica polymer is produced, and at the same time, an aluminosilicate consisting of a zeolite or zeolite precursor of a water-insoluble salt in which an alkali component as a by-product is immobilized is produced, and a composite matrix of silica polymer and aluminosilicate A water-resistant and heat-resistant solidified body is formed.
[0216]
When forming the hydraulic silica-based binder of the wet fluid of the present invention into a water / heat-resistant solidified body composed of a composite matrix of silica polymer and aluminosilicate, the release temperature of the hydraulic silica-based binder is not particularly limited. Even when the release temperature is 5 ° C. or lower, the reaction is delayed and it takes time to form a composite matrix, which tends to be unfavorable in terms of construction workability and productivity.
[0217]
Moreover, even if the release temperature is 180 ° C. or higher, there is no particular merit and only wasteful consumption of heat energy is caused. However, when the granule product is modified as described later, if the granule raw material contains an organic component, or if it is desired to improve the performance of the produced granule product in terms of strength, etc., the temperature will be lowered to 900 ° C or lower. The release is suitable for achieving the purpose.
[0218]
The water-resistant / heat-resistant solidified body composed of the composite matrix of the silica polymer of the present invention and an aluminosilicate is selected from a hydraulic silica-based binder prepared according to each purpose of use, and by a processing means, a fixed body, It can be classified into five types of applied products that are applied as molded bodies, adherent bodies, granules, and aggregate hardened bodies.
[0219]
What is important in the present invention is that the water- and heat-resistant solidified product of the present invention fixes the alkali component by-produced during the production of the solidified product and the heavy metal component contained therein as a water-insoluble zeolite or zeolite precursor, The object is to provide a stable and safe fixed body product that is water resistant and prevents the elution of harmful heavy metals contained therein.
[0220]
Therefore, according to the present invention, harmful heavy metals contained in waste can be fixed to water-insoluble salts at least at room temperature, and environmental pollution caused by heavy metals from waste can be prevented, and waste can be handled safely. This makes it possible to reuse waste as a resource and contribute to the resolution of environmental problems that burden the global environment.
[0221]
In the present invention, the water-resistant and heat-resistant solidified body formed from the hydraulic silica-based binder of the present invention is a molded product that is molded into a specific shape as found in various concrete secondary products and ceramic products. Can be provided.
[0222]
As the means for forming the wet fluid hydraulic silica-based binder, all of the slurry forming means and methods generally employed in this industry and the concrete secondary product manufacturing industry can be adopted. Of course, various means such as normal pressure, pressurization, decompression, vibration, pouring, pushing and casting can be applied for molding. Also in curing, various conditions such as heating curing, steam curing, pressure curing, decompression curing, specific gas replacement curing, etc. can be employed as well as room temperature curing.
[0223]
As the usage of the molded body, it is possible to select all the applications of various molded bodies that are adopted as concrete secondary products or ceramic products manufactured under heating conditions. Examples include various blocks, bricks, tiles, foundation stones, interlocking, tetrapots, partition plates, partition plates, outer wall materials, poles, pillars, stepping stones, various building materials, U-shaped grooves, earthen pipes, fume pipes, pots , Flower beds, ornaments, figurines, sleepers, benches, desks, tiles, porcelain and earthenware, sanitary ware, fire bricks, fishing reefs, various structures, and the like. In particular, since the water / heat resistant solidified body of the present invention basically has acid resistance, it is suitable to be used as a molded product (building material, roofing material, etc.) for acid rain countermeasures.
[0224]
Furthermore, just as general concrete slurry-like milk products are adopted for construction of structures at various construction sites, the hydraulic silica binder of the present invention is adopted for construction of structures at various construction sites. It can be applied effectively.
[0225]
In this invention, the water-proof and heat-resistant solidification body formed from the hydraulic silica type | system | group binder of this invention can be provided as an adhesion body product formed by making it adhere to the surface and inside of various base materials.
[0226]
Various base materials to be covered at this time include concrete products, cement products, various metal products, wood / bamboo products, cloth / nonwoven fabric / fiber products, glass / ceramics / porcelain products, various ceramic products, various coatings And rubber / plastics products as well as various composite products.
[0227]
Specific applications of adherents include various adhesives, binders, binders, joint materials, caulking materials, padding materials, packing materials, hardening materials, backing materials, anchor materials, coating materials, un-toker coats, floors Materials, waterproofing materials, coating materials, throwing away containers, paints / coating films, antimicrobial coatings, anti-condensation materials / coating films, various functional materials / coating films, repair materials for various structures and products, etc. be able to.
[0228]
Adhesive products are prepared in the industry such as dotting, flow coating, brush coating, spraying, spraying, roller coating, trowel coating, penetration method, pulling method, nozzle method, winding method, piling method, patching method, etc. Conventional methods can be adopted.
[0229]
In the present invention, the water- and heat-resistant solidified product formed from the hydraulic silica-based binder of the present invention is provided as a granule such as a sand granule or a granulated product having a particle diameter of 0.1 to 70 mm or a heated granule product. Can do.
[0230]
The granulation method of the granule is a rolling granulation, extrusion granulation, agitation type, which is a known granule / granulation method known and publicly used in the industry, based on the hydraulic silica-based binder of the present invention or a material containing the binder. Adopt granulation, various pelletizers, spray granulation, cast-flow granulation, packing method granulation, etc. to form granules with shapes such as sand, gravel, crushed stone, spherical shape, columnar shape, crushed granular shape, etc. Can do. After granulation, it can be released under a temperature condition of 5 to 180 ° C. to form a granular solid.
[0231]
Further, in the present invention, when the carbon-containing composition (B7) or the organic-containing composition (B8) is selected as the aluminate composition (B) to be adopted as a raw material for the hydraulic silica-based binder, it is processed here. By releasing the granulated material to a high temperature of 180 to 900 ° C., the moisture, carbon and organic components retained in the granule are removed by burning to remove the granule components. A heated granule having a high hardness in which the hardness of the granule is improved by sintering or the like can be secured.
[0232]
These granules or heated granules are aggregates, fillers, roadbed materials and landfills as substitutes for sand, gravel, crushed stone, etc., and various purification treatment agents as granules having various functions, Gas treatment materials, liquid treatment materials, water treatment materials, river and lake water treatment agents, nitrogen and phosphorus adsorbents, deodorants, soundproofing materials, heat insulating materials, heat insulating materials, shielding materials, antimicrobial agents, greening base materials It is effectively applied as a catalyst, a building material, a carrier for the above various functional materials, and the like.
[0233]
In the present invention, as another application mode of the water / heat-resistant solidified body formed from the hydraulic silica-based binder of the present invention, the above-mentioned granules having a particle diameter of 0.1 to 25 mm or heated granules are used as an aggregate. Thus, it is possible to provide an aggregate cured product that is aggregate-molded into a specific aggregate shape using a hydraulic silica-based binder as a binder.
[0234]
In the processing of the aggregated cured product in the present invention, the hydraulic silica-based binder or the specified binder is used with respect to 100 parts by weight of the granule, and the binder is used in an amount of 5 to 65 parts by weight. In addition, after the surface of the granule is coated with the binder, the granule is gathered into a specific shape aggregate, molded into a shape having a through-hole, and then at least at a normal temperature or a temperature range of 180 ° C. A cured product can be completed by forming a binder portion on the cured product and integrating it in a raised shape.
[0235]
As a specific use of the aggregate hardened body, the above granule is combined with itself or various base materials, and various purification treatment agents, building materials, sound insulation materials, heat insulating materials, greening floors, fish reefs, blocks, It can be used for various structures. In particular, cocoon-like aggregate hardened bodies are soundproofing materials, heat insulating materials, heat insulating materials, shielding materials, filter materials, water treatment materials, gas treatment materials, antimicrobial materials, blocks, fish reefs, sea beds such as kelp and seaweed, grass It is useful for floors, river repair materials, mud or water-containing soil repair materials, greening bases, etc., and is effective as an aggregate hardened product that takes advantage of the characteristics of solidified bodies that are water and heat resistant and acid resistant. is there.
[0236]
Furthermore, in connection with the fact that the collective cured product of the present invention can be processed at room temperature, the granule is brought to the construction or use site according to the purpose of use, and the granule is used on site. In addition, the binder (such as the hydraulic silica-based binder of the present invention) is added at the construction site in accordance with the situation of the construction, and the construction process is carried out by the construction method such as spraying, pouring, pressing, etc. in a form suitable for the situation on the site. It is possible to construct and complete a cocoon-like collective hardened body with the same feeling as when a concrete mill is constructed.
[0237]
Therefore, it is not necessary to manufacture the lumped-like collective cured product in advance on the factory line as a collective cured product, and the collective cured product can be produced without consuming wasteful labor and energy associated with transportation of molded products to the site. It can be constructed on site and has the advantage of being adopted as a labor-saving product.
[0238]
It is particularly suitable as a labor-saving product for large-scale construction related to civil engineering and construction, such as soundproofing and heat insulation processing, completion of greening floor processing in rivers and dams, and processing processing of specific shapes in the purification process. can do.
[0239]
Furthermore, as an example of the field construction type of the boom-like collective hardened body of the present invention, civil engineering dam construction, bay construction, riverbed construction, river protection construction, road construction, railway construction, factory construction, ground construction, housing Construction, tank installation, pole installation, park business, tree planting business, local construction structures and building materials can be mentioned, and it can be widely applied in various applications and is effective.
[0240]
【Example】
In this embodiment, the two-component mixed composition (CD) of the silica-alkali composition (A) and the aluminate composition (B) of the present invention, or the two-component mixed composition (CD), as necessary. About the three-component mixed composition (CT) to which the additive material (K) is added, and a hydraulic silica-based binder in which water is dispersed in the mixed composition [three-component blend (WD) and four-component blend (WQ) ], In addition to water- and heat-resistant solidified bodies formed from hydraulic silica-based binders, and also applied products [fixed bodies, molded bodies, adherents, granules, collective curing, which are uses of water- and heat-resistant solidified bodies. Specific examples will be described below with reference examples and examples.
The present invention is not limited to the examples described in this embodiment.
[0241]
[Reference Example 1]
In this reference example, the liquid or powdery basic standard composition (A1) which is the silica-alkali composition (A) employed in the present invention will be described.
The basic standard composition (A1) is a powdered or liquid form of commercially available industrial chemicals (JIS products) and commercially available reagents in which M represented by the compositional formula (1) is lithium, sodium, potassium, and has a molar ratio. I selected the alkali silicate shown in.
The composition components of these basic standard compositions (A1) are also shown in Table 1.
[0242]

[0243]
[Reference Example 2]
In this reference example, as another embodiment of the silica-alkali composition (A) adopted in the present invention, a slurry prepared with three components of powdered clay mineral (E), alkali salt compound (F) and water The shaped clay-modified composition (A2) will be described.
The powdery clay mineral (E) used as the raw material for the clay-modified composition (A2) is a natural clay mineral and a two-layer structure (2: 1 layer) that is a layered phyllosilicate. Two types were selected: acidic montmorillonite-type acid clay (E-1) and three-layered (2: 1 layer) 3-octahedral talc talc (E-2).
Each clay mineral (E) was dried at 110 ° C., crushed and classified in advance, and a dry powder product through which 100 mesh sieve was passed was used as a sample.
Table 2 shows the main compositional component [dry matter standard (%)] and various physical properties of the powdered clay mineral (E).
[0244]

[0245]
The alkali salt compound (F) used as a raw material for the clay-modified composition (A2) and reacted with the clay mineral (E) includes sodium hydroxide, lithium carbonate, sodium carbonate, sodium borate, potassium borate from commercially available industrial chemicals. It selected from the alkali salt compound of each powder of No. 2 sodium silicate and potassium silicate.
Table 3 shows the blending ratio of these clay-modified composition (A2) raw material and water.
The slurry-like clay-modified composition (A2) is prepared by mixing the above three components of natural clay mineral (E), alkali salt (F) and water at the blending ratio shown in Table 3 and at room temperature. The mixture was stirred for 8 hours to complete the reaction / curing of the alkali component and ferrosilicate to prepare each sample.
[0246]

[0247]
[Reference Example 3]
In this reference example, as other embodiments of the silica-alkali composition (A), a boron-containing compound (T) as a buffer zone forming agent (AT), an aluminosilicate (S) as a crystal growth seed (AS), Barium salt compound (J) as a curing modifier (AJ), calcium silicate (G) as a viscosity modifier (AG), and each composite composition (boron composite composition, Seed composite composition, barium composite composition, calcium composite composition, and multiple composite compositions).
[0248]
Samples A1-2, A1-4, A1-5, A2 prepared in Reference Example 1 and Reference Example 2 are included in the basic standard composition (A1) and the clay-modified composition (A2) adopted in this Reference Example. -1 and A2-5 silica-alkali compositions (A).
As the boron-containing compound (T) soluble in the alkaline solution of the buffer zone forming agent (AT) adopted in the composite composition of this reference example, a commercially available sodium borate powder [Na₂B_FourO₇・ 10H₂O (TS)] and potassium borate powder [K₂B_FourO₇・ 8H₂O (TP)].
The aluminosilicate (S) of crystal growth seed (AS) adopted in the composite composition of this reference example has an Al / Si atomic ratio of 4.2, a ring member number of 8, and a secondary particle size of 20 μm or less. Synthetic zeolite A (SS), which is a powder, was selected.
[0249]
As the barium salt compound (J) of the curing modifier (AJ) adopted in the composite composition of this reference example, simplified barium silicate (JS) prepared by the following preparation method was selected.
As a raw material for preparing barium silicate (JS), acid-treated product of acid clay [trade name Sildiphonite made by Mizusawa Chemical: Main component (%) SiO₂ 93.0, Al₂O_Three 1.5, Fe₂O_Three 0.3, MgO 0.3, CaO 0.2, Ig.Loss 3.7] and industrial chemical crystalline barium hydroxide [Ba (OH)₂ ] Was selected. The preparation method of barium silicate (JS)₂The mixture was homogeneously mixed so that the molar ratio of / BaO was 1.0, then dried at 200 ° C. for 60 minutes, and the dried product was pulverized using a hammer impact pulverizer to obtain a 200 mesh pass powder as a sample.
The simple barium silicate prepared here was identified to contain barium silicate as a main component by X-ray diffraction. In addition, the soluble part of the simple barium silicate prepared here in an alkaline solution (Ba⁺⁺) Was 800 mg / l as a result of measurement by the method shown below. It should be noted that other barium salt compounds soluble in alkaline solution (Ba⁺⁺) Is a commercially available reagent powdered barium hydroxide [Ba (OH)₂ ] Was 7300 mg / l, and powdered barium oxide [BaO] had a value of 15000 mg / l.
[0250]
Method for measuring “soluble content of barium salt compound in alkaline solution”:
After 10 g of powdered barium salt compound sample was stirred and dispersed in 100 ml of 1N sodium hydroxide solution at 25 ° C for 10 minutes, the barium ions in the collected solution were quantitatively analyzed by separating the sample solution by filtration, and barium contained in the collected sample. Barium ions (Ba) eluted in 1N sodium hydroxide solution based on the total amount of elements (100)⁺⁺) Amount (mg / l) was calculated.
[0251]
Calcium silicate (G) adopted as the viscosity modifier (AG) of this reference example includes naturally-occurring wollastonite mineral with a fine particle size of calcium silicate (GW) and a synthetic particle. Selected from finely powdered calcium silicate (GS) with a diameter of 10μ or less.
The above contents and blending ratio are displayed together in Table 4.
[0252]

In Table 5, each abbreviation is as follows.
(A1): Basic standard composition, (A2): Clay modified composition, (T): Boron-containing compound
(S): Aluminosilicate, (J): Barium salt compound, (G): Calcium silicate
[0253]
[Reference Example 4]
In this reference example, an alumino powder (B1) and a precursor composition (B2) which are aluminate compositions (B) adopted in the present invention will be described.
As the alumino powder (B1), powdery alkaline earth metal aluminate represented by the composition formula (2) was selected from commercially available industrial chemicals.
In addition, the precursor composition (B2) is a powdery powder prepared by homogeneous mixing using aluminum hydroxide (BH) represented by the composition formula (6) and alkaline earth metal silicate (BC) as raw materials. Aluminate precursor compound (B2) was selected. As alkaline earth metal silicate (BC) at this time, 3CaO · SiO₂ Calcium silicate (BC-3CS) and 2CaO ・ SiO₂ Of calcium silicate (BC-2CS) and magnesium silicate (BC-2MS)].
The above contents, main components, specific surface area and blending ratio are also shown in Table 5.
[0254]

[0255]
[Reference Example 5]
In this reference example, the waste powder (B3) and the cement powder (B4), which are other embodiments of the aluminate composition (B), will be described.
Waste powder (B3) was selected from industrial waste such as fly ash, blast furnace slug, and garbage incineration ash. The cement powder (B4) was selected from JIS standard Portland cement and alumina cement.
As the cement powder (B4), commercially available Portland cement and alumina cement were selected.
The above contents and blending ratio are displayed together in Table 6.
[0256]

[0257]
[Reference Example 6]
In this example, the aluminate lightweight powder (BL) having a large specific surface area, which is another aspect of the aluminate composition (B), is modified using the impregnation solution (AP). The composition (B5) or the pretreatment composition (B6) in which the phosphorus oxyacid-containing powder (BP) is pretreated with a calcium salt will be described.
[0258]
Lightweight powder (BL) is selected from industrial waste paper sludge incineration ash (PS incineration ash: BL-P), clay mineral montmorillonite (BL-M), and Fugendake volcanic ash (BL-V). It is. As the impregnation solution (AP) which is an impregnation modifier, No. 3 sodium silicate (A3-2) of the liquid composition (A3) selected in Reference Example 1 was selected.
The modified composition (B5) was prepared according to the following specifications. To 90 parts by weight of each lightweight powder (BL), 10 parts by weight of an impregnating solution (AP) of sodium silicate (A3-2) and 30 parts by weight of water were added, and the whole was kept wet and mixed. Thereafter, it was dried at 60 to 80 ° C. to prepare modified compositions (B5-1), (B5-2) and (B5-3) in a powder state.
[0259]

[0260]
As the oxyacid-containing powder (BP) of phosphorus, incinerated ash (BP-U) of Sakai city sewer sludge, which is industrial waste, was selected. As the pretreatment agent calcium salt (GC), slaked lime marketed as an industrial chemical was selected.
The pretreatment composition (B6) was prepared according to the following specifications. After adding 30 parts by weight of calcium salt of slaked lime (GC) and 40 parts by weight of water to 70 parts by weight of phosphorus oxyacid-containing powder (BP), the whole was kept wet and mixed well, then 60 Furthermore, it was dried at 80 ° C. to prepare a pretreatment composition (B6-1) in a powder state.
The main components of the light-weight powder (BL) and the phosphorus oxyacid-containing powder (BP) as the raw material are the modified composition (B5) that has been impregnated and the pre-treated composition (B6) that have been pretreated, respectively. The composition and specific surface area are also shown in Table 7.
[0261]
[Reference Example 7]
In this example, an organic-containing composition (B7) containing an organic compound (BC) which is another embodiment of the aluminate composition (B) will be described.
Organic-containing composition (B7) containing organic compound (BC) includes dried paper sludge hydrous cake (B7-1) as industrial waste and waste white clay by-produced by decolorization purification of fats and oils. Three types were selected: (B7-2) and fermentation residue (B7-2) by-produced in shochu production.
These main compositions and specific surface areas are also shown in Table 8.
[0262]

[0263]
[Reference Example 8]
In this example, the carbon-containing composition (B8), which is another embodiment of the aluminate composition (B), will be described.
The carbon-containing composition (B8) is a carbon-alumina-silica prepared by using a paper sludge cake containing pulps discharged from the paper industry as a raw material, and subjecting this paper sludge cake to a dry distillation process. Carbon produced by subjecting the composite [paper sludge carbonized product (B8-1)] and waste clay containing waste oil by-produced from the oil refining industry to the carbonization process. -Two types of alumina-silica composite [waste white clay dry distillation product (B8-2)] were selected.
These main compositions and specific surface areas are also shown in Table 9.
[0264]

[0265]
[Reference Example 9]
In this example, a multifunctional composition (B9) in which two or more kinds of aluminate compositions (B) which are other embodiments of the aluminate composition (B) are combined and mixed will be described.
The multifunctional composition (B9) includes eight types of aluminate compositions (B) [alumino powder (B1); precursor composition (B2); waste powder (B3); cement powder (B4 ); Modified composition (B5); pretreatment composition (B6); organic-containing composition (B7); carbon-containing composition (B8)]. A multifunctional composition was chosen.
The main component compositions of these multifunctional compositions (B9) are also shown in Table 10.
[0266]

[0267]
[Reference Example 10]
In this reference example, the antimicrobial agent (KZ), functional material (KF), fine aggregate (KM), and reusable material (KR), which are additive materials (K) of the granular materials adopted in this example explain.
As the antimicrobial agent (KZ), a powdery monovalent or divalent copper or zinc oxyacid salt compound represented by the composition formula (7) was selected from commercially available reagents. In addition, copper chelate compounds and composite antimicrobial agents were selected from commercially available products.
[0268]
The functional material (KF) was selected from commercially available industrial chemicals, reagents, custom-made pigments, activators, colorants, fillers, and functionality-imparting agents.
The fine aggregate (KM) was selected from river sand, which is a natural aggregate.
Recycled materials (KR) include crushed and classified products such as discarded ceramics, crushed and classified products such as discarded glass bottles, and sludge by melting incineration ash such as garbage at a high temperature of 1200 ° C or higher. Three types of slugs were selected.
The typical properties of each additive material (K) are also shown in Table 11.
[0269]

[0270]
Hereinafter, test methods for evaluating physical properties employed in this example are shown below.
In addition, the evaluation of the silica-based binder is evaluated based on the solidified physical properties at the time of forming the cured body, while evaluating the time during which the wet fluid having fluidity or plasticity capable of working at the time of binder construction is secured as the pot life. did.
[0271]
[Physical property evaluation test method]
1. Usable time of wet fluid
Deformation occurs when a wet fluid (3-component or 4-component mixture) specimen prepared from a specimen kept at 30 ° C is left in a thermostat at 30 ± 2 ° C and external pressure is applied to the specimen. The time until it no longer occurred was measured and displayed as the pot life.
[0272]
The viscosity limit for general construction work of the slurry-like wet fluid in the silica-based binder of the present invention is set so that the viscosity after 10 minutes of silica-based binder preparation does not exceed 8,000 cP, while the workable time for the work is set. Assumed 1 hour. Therefore, a viscosity in which the viscosity of the silica-based binder does not exceed 10,000 cP in the range of 1 hour was determined as “pass” as a silica-based binder having usable workability with good workability. However, when the silica-based binder of the present invention is used as a plastic wet fluid for filling, bonding, joints, etc., the workability of the construction is not impaired even if the binder viscosity exceeds 10,000 cP.
[0273]
2. Shelf life
In a powdered one-pack product, the sample is sealed in a four-layer paper bag and stored in a room maintained at a temperature of 25 ± 5 ° C and a relative humidity of 80 ± 10% for 6 months. Evaluate the pot life when preparing a one-pack product as a wet fluid, and if there is no significant abnormal change in the pot life and the uniaxial compressive strength of the solidified body described later, the shelf life is `` Yes '' evaluated.
[0274]
3. Method for preparing cylindrical or granular specimen
In the uniaxial compressive fracture strength test evaluation, the wet fluid prepared from each sample was poured into a φ60 × 90 mm cylindrical mold and cured at room temperature (about 25 ° C) for a predetermined time (28 days). A columnar specimen was used.
In other test evaluations, a wet fluid was molded into a granule of about 2 to 6 mm, and a granular specimen that was cured at room temperature (about 25 ° C.) for a predetermined time (48 hours) was used.
[0275]
4). Uniaxial compressive strength test
The prepared cylindrical specimen for axial compressive strength measurement (n number = 3) is subjected to a uniaxial compressive fracture strength test using a compressive strength tester, the strength is measured, and Kg / cm²Displayed.
In addition, the uniaxial compressive strength of the specimen of the present invention is 200 kg / cm after 28 days curing.²The case of showing the above strength was set as “pass” as one guideline. However, depending on the purpose of use of the solidified body, the strength value is not restricted.
[0276]
5. Evaluation of solidified body strength
For the strength of the solidified body prepared with granules, select approximately 5 mm type granules (n number = 5), sandwich between two steel plates, and gently place a 50 kg weight on top. The case where it was “not crushed” was evaluated as “solidified body strength”.
[0277]
6). Evaluation of heat resistance
The prepared granular specimen is exposed in an electric oven maintained at 650 ° C. for 24 hours to confirm the compressive strength of the specimen after the exposure. The compressive strength after exposure is 60% compared to the compressive strength before exposure. % Was ensured as having heat resistance.
[0278]
7). Evaluation of water resistance
The prepared granular specimen is left immersed in water kept at about 20 ° C. for 7 days, and when the specimen after standing exhibits a granular solid body strength that is not significantly different from the state before immersion, the water resistance is “ Yes. "
[0279]
8). Water elution test for heavy metals
The prepared granular specimen was subjected to a water elution test for heavy metals according to the method defined in Notification No. 13 of the Environment Agency in accordance with JIS K 0102. The harmful heavy metals include hexavalent chromium, cadmium, lead, all cyan, arsenic, and total mercury. In this example, lead element was selected and measured as a representative of these heavy metals. When displaying the results, the value below the limit of heavy metal concentration detection in the water elution test was displayed as “ND”.
[0280]
9. Adhesion test
In accordance with the method described in JIS K 6852, a base steel plate and a 0.5 mm thick asbestos plate are cut into a 30 x 25 cm rectangle and a test plate is used. Polished until a metallic luster appears, then clean the surface with trichloroethylene and dry.
Next, the silica-based binder of the sample prepared was applied to a thickness of about 2 mm on the 25 × 25 cm area of the rectangular asbestos test plate, and the 25 × 25 cm area of the test piece of the rectangular steel plate was placed on it. Adhere, and set so that the 5 × 25cm parts that are not adhered protrude at the opposite ends of each other in a straight line.
The test piece that has been adhesively set is allowed to stand at room temperature of about 20 ° C. for 7 days. Then, using a compression fracture tester, the ear-shaped part of the test piece is raised and the shear fracture strength is set to the load strength (Kg / cm²) To measure the adhesion.
[0281]
Ten. Antibacterial effect test and pH measurement of treated water
▲ 1 Purification test for hot water mixed with E. coli
Preparation of bacterial solution: 1/50 cc of sterilized purified water with 1/50 concentration of NB medium (bouillon) (10 times the test standard concentration) as nutrients for E. coli (Ec-3), and cultured with shaking at 27 ° C for 16 hours To a final 1 / 10,000 and adjust to pH 7.
Preparation of treated water: Dispense 150 cc of the above Escherichia coli solution into Erlenmeyer flask and seal tightly to make a blank solution (BL). A sample of a predetermined concentration (2 levels of 1 g / 150 cc and 0.5 g / 150 cc) is put into the above E. coli solution, sealed and used as test water.
Test condition: The test treated water is cultured in a constant temperature bath at 40 ° C. for a predetermined time (72 hours), and the number of bacteria is measured.
(2) pH measurement of treated water
The pH of the test treated water (1 g / 150 cc concentration) is measured with a pH meter.
[0282]
[Example 1]
In this embodiment, it consists of a two-component mixed composition (CD) composed of various liquid silica-alkali compositions (A) and an aluminate composition (B), and an additive material (K) added as necessary. Hydraulic silica binder (sample number C series) which is a three-component mixture (WT) or four-component mixture (WQ) of a wet fluid prepared by adding water to a three-component mixed composition (CT), Furthermore, the solidified body cured using this hydraulic silica-based binder will be described.
[0283]
The silica-alkali composition (A) and the aluminate composition (B) constituting the hydraulic silica-based binder, and the additive material (K) are selected from each type shown in Table 12, and these and water are shown in Table 12. Each hydraulic silica-based binder was prepared by homogeneous mixing at a blending ratio.
The prepared hydraulic silica-based binder measures the pot life, while making each specimen according to the specimen preparation method, evaluating the heat resistance and water resistance, and the uniaxial compressive strength after curing for 28 days. Measured, and further conducted a water elution test for heavy metals with lead. The results are also shown in Table 13.
[0284]
Four types of comparative examples were prepared in order to clarify the effects in this example.
Portland cement (H-C1) and (H-C2) and acid-curable water glass binders (H-S1) and (H-S2) were selected as solidified bodies formed by non-firing at room temperature. These specimens are subjected to the same evaluation test as described above, and the results are also shown in Table 13.
Portland cement specimens were prepared by the following preparation method. In the case of commercially available Portland cement and river sand shown in Table 12 (H-C1) and incineration ash of raw garbage (H-C2), each is blended and kneaded to form cement mortar, and then the specified cylindrical shape The sample was poured into a frame (φ60 × 90 mm) and cured for 28 days at room temperature.
[0285]
A specimen of a water glass binder was prepared by the following preparation method. In the case of (H-S1) acid-curing type, in the case of blending commercially available JIS No. 3 liquid water glass and acid curing agent aluminum phosphate (H-S1), and No. 3 product in the proportions shown in Table 10. In the case where aluminum hydroxide was blended in place of the aluminate composition (B) of the present invention in the liquid water glass (H-S2), each was mixed and kneaded by adding water to make a mortar shape, The sample was poured into a mold (φ60 × 90 mm) and cured at room temperature for 28 days to obtain a specimen.
[0286]

[0287]

[0288]
[Example 2]
In this example, three components of a wet fluid prepared by adding water to a two-component mixed composition (CD) of various liquid silica-alkali compositions (A) and aluminate compositions (B). The hydraulic silica-based binder that is a mixture (WT), and granules that are cured in the form of granules using these hydraulic silica-based binders will be described.
[0289]
Table 14 shows the types of silica-alkali composition (A) and aluminate composition (B) constituting the hydraulic silica-based binder and the blending ratio including water added thereto. These three components were homogeneously mixed to prepare each hydraulic silica-based binder.
The prepared hydraulic silica-based binder was measured for pot life, and then granule specimens were prepared in accordance with the method for preparing the granular specimens described above, and the heat resistance and water resistance were evaluated, respectively. The strength of the solidified body after curing is evaluated, a water elution test for heavy metals is conducted with lead, and the results are also shown in Table 15.
[0290]

[0291]

[0292]
[Example 3]
In this embodiment, the three components of the wet fluid prepared by adding water to the two component mixture composition (CD) of the liquid silica-alkali composition (A) and various aluminate compositions (B). The hydraulic silica-based binder that is a mixture (WT), and granules that are cured in the form of granules using these hydraulic silica-based binders will be described.
[0293]
Table 16 shows the types of silica-alkali composition (A) and aluminate composition (B) constituting the hydraulic silica-based binder and the blending ratio including water added thereto. These three components were homogeneously mixed to prepare each hydraulic silica-based binder.
The prepared hydraulic silica-based binder was measured for pot life, and then granule specimens were prepared in accordance with the method for preparing the granular specimens described above, and the heat resistance and water resistance were evaluated, respectively. The strength of the solidified body after curing is evaluated, a water elution test for heavy metals is conducted with lead, and the results are also shown in Table 17.
[0294]

[0295]

[0296]
[Example 4]
In this example, water was added to the powder mixture composition (CH) of the powdery one-pack product preliminarily mixed with the powdery silica-alkali composition (A) and the aluminate composition (B). In addition, a wet fluid hydraulic silica-based binder prepared in addition, and a molded body obtained by press-molding these hydraulic silica-based binders using a mold and then curing will be described.
[0297]
Table 18 shows the types and blending ratios of the powdery silica-alkali composition (A) and the aluminate composition (B) constituting the hydraulic silica-based binder, and the additive material (K) added as necessary. Shown in Each of these two or three components was mixed in advance with a mixer to prepare each powder and particle mixture composition (CH). Each of the prepared powder and particle mixture compositions (CH) prepared here is evaluated and displayed in Table 18 after evaluating the shelf life of the shelf.
[0298]
Each hydraulic particle binder (CH) was prepared by adding water in the proportions shown in Table 18 and mixing. Each prepared hydraulic silica-based binder measures the pot life, while creating a cylindrical specimen in accordance with the above-described cylindrical specimen preparation method, and evaluating the heat resistance and water resistance. The solidified body strength is evaluated by a uniaxial compressive fracture strength test after daily curing, and a water elution test of heavy metals is conducted with lead. The results are also shown in Table 19.
[0299]

[0300]

[0301]
[Example 5]
In this example, in the three-component mixed composition (CT) composed of the silica-alkali composition (A), the aluminate composition (B) and the additive material (K), the additive material (K) is antibacterial and the like. A hydraulic silica binder that is a functional antimicrobial agent (KZ) and is a four-component mixture (WQ) of a wet fluid in which water is added to this three-component mixture composition (CT), and further this hydraulic silica The solidified body cured using the system binder will be described.
[0302]
Table 20 shows the types of silica-alkali composition (A), aluminate composition (B), and antimicrobial agent (KZ) constituting the hydraulic silica-based binder, and the blending ratio including water added to these. . These four components were homogeneously mixed to prepare each hydraulic silica-based binder as a four-component mixture (WQ).
The prepared hydraulic silica-based binder was measured for pot life, and then granule specimens were prepared in accordance with the method for preparing granular specimens described above, and the heat resistance and water resistance were evaluated respectively. The strength of the solidified body after curing was evaluated, and the antimicrobial property was evaluated by applying the antibacterial effect test of the treated water described above. These results are also shown in Table 21.
[0303]

[0304]

[0305]
[Example 6]
In this embodiment, a two-component mixed composition (CD) composed of a silica-alkali composition (A) and an aluminate composition (B), and a three-component mixed composed of an additive material (K) added as necessary. A hydraulic silica-based binder which is a three-component mixture (WT) or a four-component mixture (WQ) of a wet fluid prepared by adding water to the composition (CT), and further using this hydraulic silica-based binder The adhering body cured by this will be described.
[0306]
Silica-alkali composition (A) and aluminate composition (B) constituting the hydraulic silica-based binder, and if necessary, the type of additive material (K) and the mixing ratio including water added to these Are shown in Table 22. These three or four components were homogeneously mixed to prepare a hydraulic silica-based binder as a three-component mixture (WT) or a four-component mixture (WQ).
[0307]
The prepared hydraulic silica-based binder was measured for pot life, and the adhesive strength of each binder was evaluated by measuring shear fracture strength based on a steel plate and an asbestos plate in accordance with the above-described evaluation method of the adhesion test. In addition, after immersing the test piece for adhesion test in water for 24 hours and after exposing it to a dryer at 250 ℃ for 24 hours, the shear fracture strength of each test piece was measured, and the water resistance and heat resistance of each adherent were measured. Evaluated. The results are also shown in Table 23.
[0308]

[0309]

[0310]
[Example 8]
In this example, a granule formed from a wet fluid hydraulic silica-based binder prepared with three components of a liquid silica-alkali composition (A), an aluminate composition (B), and water was prepared. A case will be described in which a brackish aggregate hardened body having through voids is prepared as a raw material and applied as a noncombustible soundproof material (plate).
[0311]
The granule adopted in this example is a granule of sample No. C-22 prepared in Example 2 [A7-2: 20 parts + B3-1: 80 parts] granulated particles having a particle size of 1 to 5 mmφ. I chose the body.
As the binder for integrating the granules, a wet fluid hydraulic silica-based binder having the same quality as the granules prepared in Sample No. C-22 in Example 2 was selected.
The sound insulation board is manufactured by adding about 10 kg of water to 100 kg of granulated granules and wetting the surface of the granules, and then adding 15 kg of a wet fluid hydraulic silica-based binder and mixing them on the surface of the granules. The binder is uniformly distributed, then poured into a 300 × 300 mm mold having a thickness of 30 mm, left at room temperature for at least 24 hours to develop initial hardness, and then demolded. Next, it is left at 80 ° C for 1 hour to complete the solidification and make a soundproof board product.
The soundproofing effect of the manufactured soundproof board product is measured according to JIS A 1416 in accordance with the standards (typical items) shown in Table 24 below, and the results are also shown in Table 24.
[0312]

[0313]
【The invention's effect】
According to the present invention, water- and heat-resistant inorganic solidified bodies that can be produced without firing can be supplied as fixed bodies, molded bodies, adhered bodies, granules, and aggregated cured bodies. Therefore, it is possible to produce an inorganic solid body with energy saving without using a large amount of energy, and further, it is possible to dispose of industrial wastes containing hazardous substances and to recycle and reuse them.

Claims (10)

A wet fluid hydraulic silica-based binder in which a three-component mixture in which water is mixed is homogeneously dispersed with respect to a two-component mixed composition composed of a silica-alkali composition and an aluminate composition. And
Said silica-alkali composition has the following composition formula (1)
M ₂ O ・ aSiO ₂・ bH ₂ O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (1)
(Wherein M is lithium, an alkali metal element of the sodium or potassium group, a is a number of 1.8 to 3.5, and b is a number of 2.5 to 50.0). Or a liquid or powdery silica-alkali composition (A) comprising two or more combined basic standard compositions (A1);
Additional aluminate composition (B) is, are composed of aluminate composition hydroxide aluminum and alkaline earth metals are mixed in advance;
The aluminum hydroxide is aluminum hydroxide (BH) comprising readily reactive aluminum hydroxide;
The alkaline earth metal silicate is represented by the following composition formula (6):
iDO ・ SiO ₂・ jH ₂ O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (6)
(Wherein D is an alkaline earth metal element selected from the group of calcium or magnesium, i is a number between 0.2 and 5.0, and j is a number of 6.6 or less including zero) Single or two or more combined alkaline earth metal silicates (BC) selected from the salt group, and alkaline earth metal silicates per 100 parts by weight of the above aluminum hydroxide (BH) An aluminate composition (B) comprising a precursor composition (B2) in which (BC) is homogeneously mixed in an amount of 2 to 30 parts by weight;
The above two-component mixed composition is 10 to 310 parts by weight of the above liquid or powdery silica-alkali composition (A) with respect to 100 parts by weight of the above powdered aluminate composition (B). A mixed liquid or powdered two-component composition (CD);
The above three-component mixture is a three-component mixture (WT) of a wet fluid that is homogeneously dispersed in an amount of 200 parts by weight or less of water with respect to 100 parts by weight of the above-mentioned two-component mixture composition (CD). A hydraulic silica-based binder characterized by being. The above-mentioned silica-alkali composition (A) is a liquid silica-alkali composition in which an alkali salt compound and water are added to a powdery clay mineral and previously mixed and modified;
The powdery clay mineral is a powdery clay mineral (E) composed of a 2: 1 layered smectite group of hydrous ferrosilicate;
The alkali salt compound has the following composition formula (3):
M ₂ O ・ eY ・ fH ₂ O (3)
(Wherein, M is an alkali metal element of lithium, sodium or potassium group, Y is an oxyacid of carbon, boron or silicon element alone or in combination of two or more elements, e is a number of 4.0 or less including zero, f Is a single or a combination of two or more alkali salt compounds (F) selected from the group of alkali salt compounds represented by the following formula:
The silica-alkali composition is mixed by adding 30 to 300 parts by weight of the alkali salt compound (F) and 100 to 350 parts by weight of water with respect to 100 parts by weight of the powdered clay mineral (E). The hydraulic silica-based binder according to claim 1, which is a liquid silica-alkali composition (A) comprising a slurry-like clay-modified composition (A2) which has been modified. A silica-alkali composition in which a buffer zone forming agent is mixed and mixed in advance with the basic standard composition (A1) or the clay-modified composition (A2);
The above-mentioned buffer zone forming agent is a buffer zone forming agent (AT) comprising a boron-containing compound soluble in an alkaline solution alone or a combination of two or more boron-containing compounds (T);
Liquid or powdery boron composite composition (A3) in which the buffer zone forming agent (AT) is homogeneously mixed and composited in an amount of 40 parts by weight or less with respect to 100 parts by weight of the silica-alkali composition (A). A hydraulic silica-based binder according to claim 1 or 2, which is a silica-alkali composition (A). A silica-alkali composition in which crystal growth seed is mixed and mixed in advance with the basic standard composition (A1) or the clay-modified composition (A2);
The crystal growth seed has the chemical composition formula (4)
M _{x / n}・ [(AlO ₂ ) _x・ (SiO ₂ ) _y ] ・ wH ₂ O (4)
(Wherein M is a metal cation having a valence of n, and x + y is the number of tetrahedra per unit cell), which is a crystal growth seed (KS) made of zeolite (S) of aluminosilicate;
From the liquid or powdery seed composite composition (A4) in which the crystal growth seed (KS) is homogeneously mixed and compounded at 0.01 to 10 parts by weight with respect to 100 parts by weight of the silica-alkali composition (A). The hydraulic silica-based binder according to claim 1 or 2, which is a silica-alkali composition (A). A silica-alkali composition in which a curing modifier is mixed and mixed with the basic standard composition (A1) or the clay-modified composition (A2);
The curing modifier is the following composition formula (5)
BaO ・ gSiO ₂・ hH ₂ O ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (5)
(Wherein, g is a number including zero of 4.0 or less, h is a number including zero of 9.0 or less) selected from the group of powdered barium salts soluble in an alkaline solution, or a combination of two or more kinds of barium A curing modifier (KJ) comprising a salt (J);
From the liquid or powdery barium composite composition (A5) in which the curing modifier (KJ) is uniformly mixed and composited at 0.1 to 10 parts by weight with respect to 100 parts by weight of the silica-alkali composition (A). The hydraulic silica-based binder according to claim 1 or 2, which is a silica-alkali composition (A). A silica-alkali composition in which a viscosity modifier is premixed and mixed with the basic standard composition (A1) or the clay-modified composition (A2);
The viscosity modifier is a viscosity modifier (GS) comprising easily reactive calcium silicate (G); the viscosity modifier is 100 parts by weight of the silica-alkali composition (A). The water according to claim 1 or 2, wherein (GS) is a silica-alkali composition (A) comprising a liquid or powdery calcium composite composition (A6) which is homogeneously mixed and compounded in an amount of 70 parts by weight or less. Hard silica-based binder. The basic standard composition (A1) or the clay-modified composition (A2) comprises a buffer zone forming agent (AT), a crystal growth seed (AS), a curing modifier (AJ), or a viscosity modifier (AG). A silica-alkali composition in which a plurality of composite agents are premixed and mixed;
A combination of two or more selected from the group consisting of the buffer zone forming agent (AT), crystal growth seed (AS), curing modifier (AJ), and clay modifier (AG). Complex agent (AM);
Liquid or powdery multiple composite composition (A7) that is homogeneously mixed and composited in an amount of 70 parts by weight or less of the multiple composite agent (AM) with respect to 100 parts by weight of the silica-alkali composition (A). A hydraulic silica-based binder according to claim 1 or 2, which is a silica-alkali composition (A). 1 to 200 parts by weight of an antimicrobial agent, functional material, fine bone in 100 parts by weight of a liquid or powdery two-component mixed composition (CD) comprising the above-mentioned silica-alkali composition and aluminate composition Single or two or more kinds of combination powder material (K) selected from the powder or recycle material powder group, and 300 parts by weight or less of water are homogeneously dispersed in 100 parts by weight of the above three-component mixed composition The hydraulic silica-based binder according to any one of claims 1 to 7, wherein the hydraulic silica-based binder is a wet fluid . Said powder-added material (K) was selected from the group of fly ash, slug, sludge and incinerated ash containing at least 25% by weight of silicates with a particle size in the range of 0.1 μm to 5 mm alone or two or more recycled material treated processed from the combination waste (KR) in a claim 8 wherein the hydraulic silica binder. Hydraulic silica binder of the claim 9, wherein the 5 to be released in the atmosphere of 180 ° C., the aluminosilicate and a siloxane bond to produce a composite matrix composed of silica polymers whose main chain here there are, water and heat resistance solidified body, which is a cured product of a fixed body that prevents water elution of heavy metals containing.