JP3981514B2 - Ground injection method - Google Patents
Ground injection method Download PDFInfo
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- JP3981514B2 JP3981514B2 JP2000083193A JP2000083193A JP3981514B2 JP 3981514 B2 JP3981514 B2 JP 3981514B2 JP 2000083193 A JP2000083193 A JP 2000083193A JP 2000083193 A JP2000083193 A JP 2000083193A JP 3981514 B2 JP3981514 B2 JP 3981514B2
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- phosphoric acid
- crude phosphoric
- water glass
- water
- aqueous solution
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- 238000002347 injection Methods 0.000 title claims description 7
- 239000007924 injection Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 124
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019353 potassium silicate Nutrition 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 239000007788 liquid Substances 0.000 description 34
- 238000001879 gelation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229940010048 aluminum sulfate Drugs 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 iron Chemical compound 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229940035125 aluminum sulfate anhydrous Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- JVGVKBYFQRJVOQ-UHFFFAOYSA-H dialuminum phosphoric acid trisulfate Chemical compound S(=O)(=O)([O-])[O-].[Al+3].P(O)(O)(O)=O.S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].[Al+3] JVGVKBYFQRJVOQ-UHFFFAOYSA-H 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000002934 lysing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Consolidation Of Soil By Introduction Of Solidifying Substances Into Soil (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は水ガラスと粗リン酸を主成分として含む地盤注入用薬液に係り、特に、ゲル化時間の瞬結領域が広く、かつ固結体の収縮が極めて少ない瞬結性地盤注入用薬液に関する。
【０００２】
【従来の技術】
水ガラスに対する瞬結性の無機系硬化剤として、従来、硫酸あるいはリン酸が衆知のものである。
【０００３】
【発明が解決しようとする課題】
しかし、硫酸、リン酸ともに水ガラスの瞬結領域が狭くて使用量の調整に難がある。また、生成固結体は収縮が大きく、このため、遊離した離漿水が逸脱し易く、止水性の低下等、耐久性低下の原因にもなりかねない。
【０００４】
さらに、硫酸およびその含有物は硫酸が10％以上の濃度になると、毒物および劇物取締法の法的規制を受ける。また、リン酸は実用に供するにはかなり高価である。
【０００５】
そこで、本発明の目的は水ガラスの硬化剤として、リン酸を主成分とするにもかかわらず、水ガラスの瞬結領域を広めて、生成固結体の収縮を極めて少なくし、離漿水の逸脱による耐久性の低下を極力小さくでき、上述の公知技術に存する欠点を改良した水ガラス−リン酸系の地盤注入用薬液を提供するものである。
【０００６】
【課題を解決するための手段】
前記の目的を達成するため、本発明の水ガラス−リン酸系地盤注入用薬液によれば、水ガラスと、不純物として鉄分およびアルミニウムを少なくとも含む粗リン酸と、硫酸または水溶性アルミニウム塩とを含み、前記粗リン酸がリン鉱石を過剰の硫酸で分解の後、石膏を濾別して得られる精製前の粗リン酸であることを特徴とする。
【０００７】
上述の構成からなる本発明地盤注入用薬液はゲル化時間の瞬結域が広く、かつ得られた固結体の収縮が極めて少ない。
【０００８】
【発明の実施の形態】
以下、本発明を具体的に詳述する。
【０００９】
本発明に用いられる水ガラスはＪＩＳ１号、２号、３号、その他各種モル比の珪酸ソーダである。
【００１０】
本発明に用いられるリン酸は粗リン酸である。通常の精製リン酸は不純物として塩化物、硫酸塩、重金属、鉄等を含有するが、その量は何れも数ppm 以下である。これに対して、本発明の粗リン酸はリン鉱石を過剰の硫酸で分解の後、石膏を濾別して得られる精製処理前の粗リン酸であって、これは一般にＳＯ3 、Ｆｅ2 Ｏ3 、Ａｌ2 Ｏ3 、ＳｉＯ2 、Ｆ等の不純物を１〜２％以下含有している。
【００１１】
本発明にかかる地盤注入用薬液は上述の水ガラスと、粗リン酸とを主成分として含有するが、この二成分系にさらに、硫酸を含有してもよく、また、水溶性アルミニウム塩を含有することもできる。
【００１２】
上述の硫酸としては、通常の工業用硫酸はもちろんのこと、その他、不純物の含有量が多い各種粗硫酸、廃硫酸等が用いられる。
【００１３】
水溶性アルミニウム塩としては、ポリ塩化アルミニウム、塩化アルミニウム、硫酸アルミニウム、硝酸アルミニウム、アルミニウム明ばん等が用いられ、この中で特にポリ塩化アルミニウムが優れている。
【００１４】
上述の構成からなる本発明薬液は従来の水ガラス−無機酸系薬液と比較すると、ゲル化時間の瞬結領域が広くなり、かつ得られた固結体の離漿水も少なく、これにより、固結体の収縮が極めて少なくなり、したがって、離漿水の逸脱による固結体の収縮が防止されて止水性が向上され、これにともなって耐久性の低下も防止される。このような現象は本発明薬液が特にアルカリ領域において顕著である。
【００１５】
さらに、上述の本発明薬液はゲル化時間を長く調整し得るのみならず、瞬結に至るまでのゲル化の調整が容易である。この現象は本発明薬液が特に酸性〜中性領域において顕著である。これらの本発明にかかる現象は水ガラス−粗リン酸系において顕著に現れ、粗リン酸の代わりに精製リン酸を用いたのではこのような現象は達成され得ない。
【００１６】
一般に、離漿水はゲル（コロイド）中に存在する液体が遊離して生じるものである。本発明はゲル中の液体を凝結剤で凝固することにより、離漿水としての遊離を抑制する。
【００１７】
すなわち、本発明の水ガラス−粗リン酸系では、粗リン酸中の不純物、特に鉄分がリン酸鉄の形で存在し、このリン酸鉄がゲル（コロイド）の凝結剤として作用してゲル中の液体を凝結し、離漿水としての遊離を抑制する。
【００１８】
また、本発明の水ガラス−粗リン酸−硫酸の系では、粗リン酸中の不純物、特に鉄分が硫酸と反応して硫酸鉄を生成し、この硫酸鉄がコロイドの凝結剤として作用してゲル中の液体を凝結し、離漿水としての遊離を抑制する。
【００１９】
さらに、本発明の水ガラス−粗リン酸−可溶性アルミニウム塩の系では、可溶性アルミニウム塩自体がコロイドの凝結剤として作用するとともに、粗リン酸中の不純物、特に鉄分が可溶性アルミニウム塩の凝結作用を助長する働きを呈してあたかも触媒として作用し、これによりゲル中の液体を凝結し、離漿水としての遊離を抑制する。
【００２０】
上述本発明における各成分の配合はいかなる方法を用いてもよいが、通常、水ガラス水溶液をＡ液とし、粗リン酸水溶液、または粗リン酸水溶液と硫酸の混合水溶液、または粗リン酸水溶液と水溶性アルミニウム塩の混合水溶液をＢ液とし、これらＡ液およびＢ液を２ショット方式により混合して地盤中に直接注入する方法が採用されている。
【００２１】
さらに、他の配合方法として、上述のＡ液およびＢ液を酸性水ガラス液を得るような配合で混合して緩結性配合液を調製し、これをそのまま地盤中に注入するか、あるいはこの配合液にさらに水ガラスやその他のゲル化促進剤を添加混合して後に地盤中に注入する。
【００２２】
さらにまた、別の配合方法として、Ａ−Ｂ合流液によるアルカリ側の瞬結性配合液と、Ａ液に対するＢ液の配合比率を増加して得られる弱酸性から酸性側の緩結性配合液とを併用して注入してもよく、また、セメント、ベントナイト等を一次注入した後に上述の緩結性配合液を二次注入してもよい。
【００２３】
【発明の実施例】
以下、本発明を実施例によって具体的に詳述するが、本発明はこれら実施例によって限定されるものではない。
【００２４】
１．使用材料
（１）水ガラス
比重（20℃) 1.３２、モル比 3.７５の珪酸ソーダを使用。
【００２５】
（２）リン酸
（ａ）工業用リン酸（精製リン酸）
75％の工業用精製リン酸を使用。不純物としては塩化物、硫酸塩、重金属、鉄等を含有するが、いずれも数ppm 以下である。
【００２６】
（ｂ）粗リン酸
75％の粗リン酸を使用。不純物として、Ｆｅ2 Ｏ3 1.１％、Ａｌ2 Ｏ3 0.８％、ＣａＯ 0.１％、ＳｉＯ2 0.５％、Ｆ 1.２％、その他微量の有機物、Ｃｒ、Ｍｏ、Ｎａ、Ｋ等を含有する。
【００２７】
（３）硫酸
７1.２％の工業用硫酸を使用。
【００２８】
（４）水溶性アルミニウム塩
（ａ）硫酸アルミニウム
無水の硫酸アルミニウム〔Ａｌ2(ＳＯ4)3 〕を使用。
（ｂ）ポリ塩化アルミニウム
Ａｌ2 Ｏ3 10％の液体ポリ塩化アルミニウムを使用。
【００２９】
２．Ａ液
20容量／容量％の水ガラス水溶液を作成してＡ液とした。
【００３０】
３．Ｂ液
次の（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）の５種類をそれぞれＢ液とした。
（ａ）工業用リン酸（精製リン酸）の希釈水溶液
（ｂ）粗リン酸の希釈水溶液
（ｃ）粗リン酸90重量％と、硫酸10重量％からなる混合液の希釈水溶液
（ｄ）粗リン酸90重量％と、硫酸アルミニウム10重量％からなる混合液の希釈水溶液
（ｅ）粗リン酸90重量％と、ポリ塩化アルミニウム10重量％からなる混合液の希釈水溶液
【００３１】
４．配合と物性
上記Ａ液２00mlに対して、上記各種Ｂ液（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）をそれぞれ表１に示す配合比率で配合してＡ−Ｂ合流液を調製し、これらＡ−Ｂ合流液について、それぞれ、20℃におけるゲル化時間（秒) と固結体の収縮率（％）を測定し、結果を表１に示した。ゲル化時間はカップ倒立法で測定し、また、固結体の収縮率は密閉容器中に固結体を20℃で10日間放置し、生じた離漿水の量から算出した。
【００３２】
【表１】
表１中、比較例No.1〜７は水ガラス−工業用リン酸系、実施例No.1〜７は水ガラス−粗リン酸系、実施例No.8〜15は、水ガラス−粗リン酸・硫酸混合液系、実施例 No.16〜24は水ガラス−粗リン酸・硫酸アルミニウム混合液系、実施例 No.25〜33は水ガラス−粗リン酸・ポリ塩化アルミニウム混合液系である。
【００３４】
Ｂ液量（硬化剤量）に対応するゲル化時間を図１のグラフ、Ｂ液量に対する固結体の収縮率（％）を図２のグラフにそれぞれ示した。
【００３５】
図１、２中、曲線１は水ガラス−工業用リン酸（精製リン酸）系、曲線２は水ガラス−粗リン酸系、３は水ガラス−粗リン酸−硫酸系、曲線４は水ガラス−粗リン酸−硫酸アルミニウム系、曲線５は水ガラス−粗リン酸−ポリ塩化アルミニウム系の試料についての、それぞれ、Ｂ液（硬化剤）添加量（ml) とゲル化時間（秒）の関係、Ｂ液（硬化剤）添加量（ml) と固結体の収縮率との関係を表したグラフである。
【００３６】
図１において、Ｕ字形曲線の瞬結域（例えば、ゲル化時間20秒以内) の幅を比較すると、硬化剤として工業用リン酸（ａ）を用いた比較例の系（曲線１）では、他の本発明にかかる系よりも明らかに幅が狭い。
【００３７】
本発明における系の中では、単なる水ガラス−粗リン酸（ｂ）系（曲線２）よりも、水ガラス−粗リン酸−硫酸（ｃ）系（曲線３）、水ガラス−粗リン酸・水溶性アルミニウム塩（ｄ）（ｅ）系（曲線４、５）の方が明らかに瞬結域の幅が広い。水溶性アルミニウム塩としては硫酸アルミニウム（実施例 No.16〜24）（曲線４）よりポリ塩化アルミニウム（実施例 No.25〜33）（曲線５）の方がＵ字形曲線の幅が広く効果的である。
【００３８】
すなわち、本発明の系では、従来の水ガラス−リン酸系の瞬結域に使用する硬化剤添加量の領域を広め得ることが伺える。したがって、本発明は瞬結域の調整が容易であるということができる。
【００３９】
図２を観察すると、硬化剤の添加量、すなわち、ゲル化時間の長短によって固結体の収縮率はもちろん変動するが、相対的にみて硬化剤として工業用リン酸（精製リン酸）（曲線１）を用いた系では、他の本発明にかかる系に比べて収縮率が大きい。
【００４０】
本発明の系の中では単なる水ガラス−粗リン酸の系（曲線２）よりも水ガラス−粗リン酸・硫酸系（曲線３）、水ガラス−粗リン酸・水溶性アルミニウム塩系（曲線４、５）の方が相対的に収縮率は小さい。水溶性アルミニウム塩としては、ポリ塩化アルミニウム（曲線５）が効果的である。
【００４１】
このように本発明の系では、固結体の収縮を小さくすることができ、したがって離漿水の逸脱による耐久性の低下も少なくなることが期待できる。
【００４２】
さらに、本実施例はもちろん本発明にかかる系において、硬化剤中の硫酸の使用量は純硫酸として10％以下で充分であり、したがって、毒物および劇物取締法の適用を受けることはなく、また、粗リン酸はもちろん精製リン酸より安価であるという利点がある。
【００４３】
【発明の効果】
以上の結果から、水ガラスの硬化剤として、粗リン酸さらに粗リン酸と硫酸の系、または粗リン酸と水溶性アルミニウム塩（特に、ポリ塩化アルミニウム）の系を使用することにより、従来からの水ガラス−リン酸系、さらに広く水ガラス−無機酸系に比べて明らかに次の効果を奏し得るものである。
【００４４】
１．瞬結域に使用する硬化剤の添加量の幅が広くできるので、瞬結型グラウトとしての瞬結領域の調整が容易となる。
【００４５】
２．固結体の収縮率が少ない。すなわち、固結率に優れている。したがって、離漿水の逸脱による収縮や止水性等の耐久性の低下を少なくすることに期待がもてる。
【図面の簡単な説明】
【図１】Ｂ液（硬化剤）添加量とゲル化時間との関係を表したグラフである。
【図２】Ｂ液（硬化剤）添加量と固結体の収縮率との関係を表したグラフである。[0001]
[Industrial application fields]
The present invention relates to a chemical solution for ground injection containing water glass and crude phosphoric acid as main components, and more particularly, to a chemical solution for ground-setting ground injection having a wide gelation time and a very small shrinkage of a solidified body. .
[0002]
[Prior art]
Conventionally, sulfuric acid or phosphoric acid is a well-known inorganic curing agent having a quick setting effect on water glass.
[0003]
[Problems to be solved by the invention]
However, in both sulfuric acid and phosphoric acid, the instantaneous setting region of water glass is narrow and it is difficult to adjust the amount of use. In addition, the produced solidified body has a large shrinkage, and therefore, the separated separated water is likely to deviate, which may cause a decrease in durability such as a decrease in water stoppage.
[0004]
In addition, sulfuric acid and its contents are subject to legal regulations under the Poisonous and Deleterious Substances Control Law when sulfuric acid is at a concentration of 10% or higher. Moreover, phosphoric acid is quite expensive for practical use.
[0005]
Therefore, the object of the present invention is to spread the flashing region of the water glass as the water glass curing agent, although the main component is phosphoric acid. It is an object of the present invention to provide a water glass-phosphate based chemical solution for ground injection which can minimize the decrease in durability due to deviation from the above and which has improved the above-described drawbacks of the known technology.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, according to the chemical solution for injecting water glass-phosphate system of the present invention, water glass, crude phosphoric acid containing at least iron and aluminum as impurities, and sulfuric acid or a water-soluble aluminum salt. In addition, the crude phosphoric acid is crude phosphoric acid before purification obtained by decomposing phosphorus ore with excess sulfuric acid and then filtering out gypsum .
[0007]
The chemical solution for injecting ground according to the present invention having the above-described structure has a wide instantaneous setting region of gelation time, and the resulting solidified body has very little shrinkage.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0009]
The water glass used in the present invention is silicate No. 1, No. 2, No. 3, and other sodium silicates having various molar ratios.
[0010]
The phosphoric acid used in the present invention is crude phosphoric acid. Ordinary purified phosphoric acid contains chlorides, sulfates, heavy metals, iron, and the like as impurities, all of which are several ppm or less. On the other hand, the crude phosphoric acid of the present invention is a crude phosphoric acid before purification treatment obtained by decomposing phosphorus ore with an excess of sulfuric acid and then filtering gypsum, which is generally SO 3 , Fe 2 O 3. , Al 2 O 3 , SiO 2 , F and other impurities are contained in an amount of 1 to 2% or less.
[0011]
The chemical solution for ground injection according to the present invention contains the above-mentioned water glass and crude phosphoric acid as main components, but this two-component system may further contain sulfuric acid and also contains a water-soluble aluminum salt. You can also
[0012]
As the above-mentioned sulfuric acid, not only ordinary industrial sulfuric acid but also various crude sulfuric acids and waste sulfuric acid having a high impurity content are used.
[0013]
As the water-soluble aluminum salt, polyaluminum chloride, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum alum and the like are used, and among these, polyaluminum chloride is particularly excellent.
[0014]
Compared with the conventional water glass-inorganic acid-based chemical solution, the chemical solution of the present invention having the above-mentioned configuration has a wide range of gelation time, and the resulting solidified body has less separation water, The shrinkage of the solidified body is extremely reduced. Therefore, the shrinkage of the solidified body due to the deviation of the lysing water is prevented and the water-stopping property is improved, and accordingly, the durability is also prevented from being lowered. Such a phenomenon is remarkable in the chemical solution of the present invention particularly in the alkaline region.
[0015]
Furthermore, the above-mentioned drug solution of the present invention can not only adjust the gelation time longer, but also can easily adjust the gelation until the instantaneous setting. This phenomenon is remarkable especially in the acidic to neutral region of the chemical solution of the present invention. These phenomena according to the present invention remarkably appear in the water glass-crude phosphoric acid system, and such a phenomenon cannot be achieved by using purified phosphoric acid instead of the crude phosphoric acid.
[0016]
In general, the isolated water is generated by the release of the liquid present in the gel (colloid). In the present invention, the liquid in the gel is coagulated with a coagulant to suppress the release as a separation water.
[0017]
That is, in the water glass-crude phosphoric acid system of the present invention, impurities in the crude phosphoric acid, particularly iron, are present in the form of iron phosphate, and this iron phosphate acts as a coagulant for the gel (colloid). It condenses the liquid inside and suppresses liberation as a separating water.
[0018]
In the water glass-crude phosphoric acid-sulfuric acid system of the present invention, impurities in the crude phosphoric acid, particularly iron, react with sulfuric acid to produce iron sulfate, which acts as a colloidal coagulant. It condenses the liquid in the gel and suppresses the release as a separating water.
[0019]
Furthermore, in the water glass-crude phosphoric acid-soluble aluminum salt system of the present invention, the soluble aluminum salt itself acts as a colloidal coagulant, and impurities in the crude phosphoric acid, particularly iron, cause the soluble aluminum salt to coagulate. It acts as a catalyst by promoting the action, thereby condensing the liquid in the gel and suppressing liberation as a separating water.
[0020]
Any method may be used for blending the components in the present invention. Usually, a water glass aqueous solution is A solution, a crude phosphoric acid aqueous solution, or a mixed aqueous solution of a crude phosphoric acid aqueous solution and sulfuric acid, or a crude phosphoric acid aqueous solution. A mixed aqueous solution of a water-soluble aluminum salt is used as B liquid, and these A liquid and B liquid are mixed by a two-shot method and directly injected into the ground.
[0021]
Furthermore, as another blending method, the above-mentioned liquid A and liquid B are mixed by blending to obtain an acidic water glass liquid to prepare a slow-binding liquid mixture, which is poured into the ground as it is, or this Water glass and other gelation accelerators are further added and mixed with the blended solution, and then injected into the ground.
[0022]
Furthermore, as another blending method, an alkali-side instant-bonding compounded liquid by AB combined liquid and a weakly acidic to acidic-side slow-bonding compounded liquid obtained by increasing the blending ratio of B liquid to A liquid May be used in combination, or after the primary injection of cement, bentonite or the like, the above-mentioned slow-binding liquid mixture may be injected secondarily.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely in detail, this invention is not limited by these Examples.
[0024]
1. Materials used (1) Sodium silicate with water glass specific gravity (20 ℃) 1.32, molar ratio 3.75.
[0025]
(2) Phosphoric acid (a) Industrial phosphoric acid (purified phosphoric acid)
Uses 75% industrial purified phosphoric acid. Impurities include chlorides, sulfates, heavy metals, iron, etc., all of which are several ppm or less.
[0026]
(B) Crude phosphoric acid
75% crude phosphoric acid is used. As impurities, Fe 2 O 3 1.1%, Al 2 O 3 0.8%, CaO 0.1%, SiO 2 0.5%, F 1.2%, other trace organic substances, Cr, Mo, Na , K and the like.
[0027]
(3) Use sulfuric acid for industrial use of 71.2% sulfuric acid.
[0028]
(4) Water-soluble aluminum salt (a) Aluminum sulfate Anhydrous aluminum sulfate [Al 2 (SO 4 ) 3 ] is used.
(B) Polyaluminum chloride Al 2 O 3 10% liquid polyaluminum chloride is used.
[0029]
2. A liquid
A 20 volume / volume% water glass aqueous solution was prepared and used as solution A.
[0030]
3. Liquid B The following five types (a), (b), (c), (d) and (e) were designated as liquid B, respectively.
(A) dilute aqueous solution of industrial phosphoric acid (purified phosphoric acid) (b) dilute aqueous solution of crude phosphoric acid (c) dilute aqueous solution of a mixture of 90% by weight of crude phosphoric acid and 10% by weight of sulfuric acid (d) crude A dilute aqueous solution of a mixed solution consisting of 90% by weight of phosphoric acid and 10% by weight of aluminum sulfate (e) A dilute aqueous solution of a mixed solution consisting of 90% by weight of crude phosphoric acid and 10% by weight of polyaluminum chloride.
4). Blending and physical properties The above-mentioned various B liquids (a), (b), (c), (d) and (e) are blended at the blending ratios shown in Table 1 with respect to 200 ml of the above-mentioned A liquid. Liquids were prepared, gelation time (second) at 20 ° C. and shrinkage rate (%) of the consolidated body were measured for these AB combined liquids, and the results are shown in Table 1. The gelation time was measured by the cup inversion method, and the shrinkage rate of the solidified body was calculated from the amount of the isolated water produced by allowing the solidified body to stand in a sealed container at 20 ° C. for 10 days.
[0032]
[Table 1]
In Table 1, Comparative Examples Nos. 1 to 7 are water glass-industrial phosphoric acid systems, Example Nos. 1 to 7 are water glass-crude phosphoric acid systems, and Examples Nos. 8 to 15 are water glass-coarse. Phosphoric acid / sulfuric acid mixed solution system, Example No.16-24 is water glass-crude phosphoric acid / aluminum sulfate mixed liquid system, Example No.25-33 is water glass-crude phosphoric acid / polyaluminum chloride mixed liquid system It is.
[0034]
The gelation time corresponding to the B liquid amount (curing agent amount) is shown in the graph of FIG. 1, and the shrinkage rate (%) of the solidified body relative to the B liquid amount is shown in the graph of FIG.
[0035]
1 and 2, curve 1 is a water glass-industrial phosphoric acid (purified phosphoric acid) system, curve 2 is a water glass-crude phosphoric acid system, 3 is a water glass-crude phosphoric acid-sulfuric acid system, and
[0036]
In FIG. 1, when comparing the width of the instantaneous setting region of the U-shaped curve (for example, the gelation time is within 20 seconds), in the comparative system (curve 1) using industrial phosphoric acid (a) as a curing agent, Clearly narrower than other systems according to the invention.
[0037]
Among the systems in the present invention, rather than a simple water glass-crude phosphoric acid (b) system (curve 2), a water glass-crude phosphoric acid-sulfuric acid (c) system (curve 3), water glass-crude phosphoric acid. The water-soluble aluminum salt (d) (e) system (curves 4 and 5) clearly has a wider instantaneous banding range. As a water-soluble aluminum salt, polyaluminum chloride (Example No. 25 to 33) (Curve 5) has a wider U-shaped curve and is more effective than aluminum sulfate (Example No. 16 to 24) (Curve 4). It is.
[0038]
That is, in the system of the present invention, it can be said that the region of the amount of the hardener added to be used in the conventional water glass-phosphate instantaneous setting region can be widened. Therefore, it can be said that the present invention is easy to adjust the instantaneous banding region.
[0039]
Observing FIG. 2, the shrinkage of the solidified body naturally varies depending on the addition amount of the curing agent, that is, the length of the gelation time, but relative to industrial phosphoric acid (purified phosphoric acid) (curve) as a curing agent. The system using 1) has a larger shrinkage rate than the other systems according to the present invention.
[0040]
Among the systems of the present invention, the water glass-crude phosphoric acid / sulfuric acid system (curve 3) and the water glass-crude phosphoric acid / water-soluble aluminum salt system (curve) rather than the simple water glass-crude phosphoric acid system (curve 2). 4 and 5) have a relatively small shrinkage rate. Polyaluminum chloride (curve 5) is effective as the water-soluble aluminum salt.
[0041]
As described above, in the system of the present invention, the shrinkage of the solidified body can be reduced, and therefore, it is expected that the decrease in durability due to the deviation from the separation water is also reduced.
[0042]
Further, in the system according to the present invention as a matter of course, the amount of sulfuric acid used in the curing agent is 10% or less as pure sulfuric acid, and therefore, it is not subject to the application of the Poisonous and Deleterious Substances Control Law, Moreover, there is an advantage that crude phosphoric acid is cheaper than purified phosphoric acid.
[0043]
【The invention's effect】
From the above results, by using crude phosphoric acid, a system of crude phosphoric acid and sulfuric acid, or a system of crude phosphoric acid and a water-soluble aluminum salt (particularly polyaluminum chloride) as a curing agent for water glass, The following effects can be clearly obtained as compared with the water glass-phosphoric acid type, and more widely than the water glass-inorganic acid type.
[0044]
1. Since the range of the addition amount of the curing agent used in the instantaneous setting region can be widened, it is easy to adjust the instantaneous setting region as the instantaneous setting type grout.
[0045]
2. The shrinkage rate of the consolidated body is small. That is, the consolidation rate is excellent. Therefore, it can be expected to reduce the decrease in durability such as shrinkage and water-stopping due to deviation from the lysed water.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the addition amount of B liquid (curing agent) and gelation time.
FIG. 2 is a graph showing the relationship between the addition amount of B liquid (curing agent) and the shrinkage rate of the consolidated body.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25084596A JP3517530B2 (en) | 1996-09-03 | 1996-09-03 | Chemical for ground injection |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25084596A Division JP3517530B2 (en) | 1996-09-03 | 1996-09-03 | Chemical for ground injection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000319655A JP2000319655A (en) | 2000-11-21 |
| JP3981514B2 true JP3981514B2 (en) | 2007-09-26 |
Family
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25084596A Expired - Fee Related JP3517530B2 (en) | 1996-09-03 | 1996-09-03 | Chemical for ground injection |
| JP2000083193A Expired - Fee Related JP3981514B2 (en) | 1996-09-03 | 2000-03-24 | Ground injection method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25084596A Expired - Fee Related JP3517530B2 (en) | 1996-09-03 | 1996-09-03 | Chemical for ground injection |
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| Country | Link |
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| JP (2) | JP3517530B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3776268B2 (en) * | 1999-10-22 | 2006-05-17 | 強化土エンジニヤリング株式会社 | Chemical solution for ground injection |
| JP5717536B2 (en) * | 2011-05-17 | 2015-05-13 | ライト工業株式会社 | Chemical injection method |
| JP6764177B1 (en) * | 2019-02-13 | 2020-09-30 | 強化土エンジニヤリング株式会社 | Ground injection material and ground improvement method using it |
-
1996
- 1996-09-03 JP JP25084596A patent/JP3517530B2/en not_active Expired - Fee Related
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2000
- 2000-03-24 JP JP2000083193A patent/JP3981514B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3517530B2 (en) | 2004-04-12 |
| JP2000319655A (en) | 2000-11-21 |
| JPH1077473A (en) | 1998-03-24 |
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