TWI375742B - - Google Patents

Description

1375742 六、發明說明： * 【發明所屬之技術領域】 * . 本發明係關於地盤注入工法（以下亦僅稱爲「注 法j)，詳細而言，係關於用以防護既存或地盤改良 建造的混凝土結構物或土中埋設物，免受地下水中所 之導致混凝土結構物或土中埋設物的劣化之離子，尤 海水或硫酸離子等的影響之地盤注入工法。尤其關於 φ 含有磷酸化合物等的螯合劑之螯合系非鹼性二氧化矽 下稱爲「罩護二氧化矽溶液」）來擷取混凝土表面的 或Mg2+，而在混凝土表面形成二氧化矽的防護被覆層 下稱爲「罩護二氧化矽」），以防止存在於地下水面 混凝土結構物的劣化或是劣化混凝土結構物的修補， 將反應生成物降低至最低程度之環境保全性高之地盤 工法。再者，係關於對於地盤中應施予耐震補強之基 施，例如設置有電信及電話之共通溝，或是隧道、地 φ 路、瓦斯管路、人孔、上下水道等之具有中空部之混 結構物，或是混凝土枕、鋼管樁等之由存在於地下水 ' 之混凝土或金屬所構成的中空結構物（是指構成土中 物之壁面之中，一面面向地盤且另一面面向大氣者） 防止劣化之地盤改善工法。 【先前技術】 應用在軟弱地盤的基礎強化或是挖掘時的地盤安 液狀化對策工程之技術，爲人所知者有依據非鹼性二 入工 後所 含有 其是 藉由 (以 Ca2 + (以 下之 並且 注入 礎設 中管 凝土 面下 結構 ，可 定及 氧化 -5- 1375742 矽漿料所進行之地盤改良技術。當將非鹼性二氧化矽漿料 注入於地盤中並使其固結時，在到達地盤中之前’該固結 體會先接觸於所存在之混凝土結構物或土中埋設物（各種 管路、地中管線、人孔等）。此外，即使在預先挖掘固結 後的地盤來建造混凝土結構物或土中埋設物時，固結體亦 接觸於混凝土結構物或土中埋設物。此時，酸性二氧化矽 漿料中的反應生成物溶出，而接觸於此等混凝土結構物或 土中埋設物，或是溶出於地下水中並接觸於混凝土結構物 或土中埋設物，可能對水質產生影響。本發明中，所謂混 凝土結構物，是指由混凝土所建造之結構物，除了隧道等 之地下結構物、擋土牆、護岸結構物、住宅、道路、槽等 之結構物之外，亦包含劣化而產生龜裂之混凝土結構物等 0 一般而言，存在於地盤中之混凝土結構物，乃具有溶 出鹼而呈中性化之傾向。此外，當鹼性水玻璃系漿料的固 結體接觸於混凝土結構物時，會由於從混凝土結構物所溶 出之鹼，而存在使水玻璃凝膠的二氧化矽成分溶解之傾向 。亦即，水玻璃系漿料的水玻璃材料在臨時設置用途中並 無問題，但從長期耐久性之觀點來看時，容易受到存在於 地盤中或是挖掘後所建構之混凝土結構物的鹼之影響。 因此，係有人提出藉由對水玻璃進行離子交換處理來 去除鹼之活性二氧化矽漿料、混合水玻璃與酸而成之酸性 二氧化矽漿料、以及進一步將pH緩衝劑或鹼劑添加於酸性 二氧化矽而成爲中性並調整其凝膠化時間之非鹼性二氧化 -6- 1375742 矽漿料。該二氧化矽漿料，由於凝膠化時間長，廣範圍滲 透性佳，並且以酸來去除成爲水玻璃漿料的劣化因素之鹼 ，因此，就可得到在長凝膠化時間下該長期耐久性佳，且 廣範圍耐久性佳的固結區域之觀點來看，乃具有其他鹼性 區域的水玻璃漿料中所無法得到之特異的特性。1375742 VI. Description of the invention: * [Technical field to which the invention pertains] * The present invention relates to a site injection method (hereinafter also referred to simply as "injection j"), and in detail, to protect existing or site improved construction. Concrete structures or buried in soil, protected from groundwater in the concrete structure or buried in the soil, especially seawater or sulfate ions, etc. Especially for φ containing phosphoric acid compounds, etc. The chelating agent is called "covering cerium oxide solution" under non-alkaline cerium oxide to extract the surface of the concrete or Mg2+, and the protective coating layer forming cerium oxide on the concrete surface is called "hood". "Cerium dioxide" is used to prevent the deterioration of the concrete structure in the groundwater surface or to repair the deterioration of the concrete structure, and to reduce the reaction product to a minimum environmental safety. Furthermore, it is related to the application of the earthquake-resistant reinforcement to the ground, for example, a common ditch for telecommunications and telephone, or a hollow portion such as a tunnel, a ground φ road, a gas pipeline, a manhole, an upper and lower water passage, and the like. A mixed structure, or a hollow structure composed of concrete or metal existing in groundwater as a concrete pillow or a steel pipe pile (refers to the wall surface constituting the soil, one side facing the ground and the other facing the atmosphere) Improve the construction method of the site to prevent deterioration. [Prior Art] The technique used in the reinforcement of the foundation of a weak site or the technical solution of the liquidification of the site during excavation is known to have a basis for non-alkaline two-in-one work (by Ca2+). (Following and injecting the underlying structure of the pipe in the foundation, the site improvement technique of oxidizing -5 - 1375742 矽 slurry can be determined. When the non-alkaline cerium oxide slurry is injected into the site and made During consolidation, the consolidated body will first come into contact with the existing concrete structure or buried material (various pipes, ground pipes, manholes, etc.) before reaching the site. In addition, even before pre-excavation consolidation When the rear site is used to construct a concrete structure or a buried material in the soil, the consolidated body is also in contact with the concrete structure or the buried material in the soil. At this time, the reaction product in the acidic ceria slurry is dissolved and contacted. When the concrete structure or the buried material in the soil, or dissolved in the groundwater and in contact with the concrete structure or the buried material in the soil, may have an impact on the water quality. In the present invention, the so-called concrete structure is Structures constructed of concrete, in addition to structures such as underground structures such as tunnels, retaining walls, revetment structures, houses, roads, troughs, etc., also contain concrete structures that are degraded and cracked. In general, the concrete structure existing in the ground has a tendency to be neutralized by the dissolution of the alkali. In addition, when the consolidated body of the alkaline water glass-based slurry contacts the concrete structure, it is due to the concrete structure. The alkali which is eluted by the substance has a tendency to dissolve the ceria component of the water glass gel. That is, the water glass material of the water glass type slurry has no problem in temporary use, but from the viewpoint of long-term durability When viewed, it is susceptible to the alkali present in the construction site or the concrete structure constructed after excavation. Therefore, it has been proposed to remove the alkali active cerium oxide slurry by ion exchange treatment of water glass. An acidic ceria slurry obtained by mixing water glass with an acid, and further adding a pH buffer or an alkali agent to the acidic ceria to become neutral and adjusting the gelation thereof Non-alkaline dioxide-6- 1375742 bismuth slurry. The cerium oxide slurry has a long gelation time and a wide range of permeability, and the acid is used to remove the alkali which becomes a deterioration factor of the water glass slurry. Therefore, it is possible to obtain a consolidation region which is excellent in long-term durability and has a wide range of durability under a long gelation time, and is not obtained in a water glass slurry having other alkaline regions. Specific characteristics.

亦即，在以水玻璃爲原材之漿料中，藉由將成爲劣化 因素之水玻璃中的鹼予以脫鹼化來構成酸性二氧化矽漿料 ，可得到長期耐久性=此爲二氧化矽溶膠漿料。相對於此 ，藉由將水玻璃中的鹼進行離子交換處理予以增粒而呈膠 體化’來進一步提升該耐久性。此爲二氧化矽膠體。以該 二氧化矽膠體爲主材料並加入酸或鹼以達活性化之漿料， 爲活性二氧化矽膠體，係用作爲永久漿料。第13圖係顯示 二氧化矽溶液的pH與凝膠時間之關係之圖表。 一般的溶液型鹼系注入材料，其耐久性差且凝膠化時 間短。相對於此，酸性二氧化矽溶膠的長期耐久性佳，活 性二氧化矽膠體的永久性佳。如液狀化對策工程般，於廣 範圍的滲透注入時’必須依據脫鹼來進行長時間凝膠化， 於鹼的中和與長時間凝膠化時，係使用酸。然而，當使用 硫酸做爲該酸時’爲人所知者使硫酸離子對混凝土會造成 不良影響。含有硫酸鹽之土壤及水對混凝土所造成之作用 ，如下列表中所示。 1375742 [第1表] 硫酸鹽作用的程度 土壤試料中的可溶 性硫酸鹽(S〇4)(%) 水溶劑中的硫酸鹽 似 S04 計）（ppm) 可忽視 0.01-0.10 0-150 僅有些許 0.10-0.20 150-1000 有某種程度 0.20-0.50 1000-2000 非常嚴重 0.50以上 2000以上 (從混凝土工學手冊摘錄) 此外，二氧化矽溶液在酸性區中，會因酸的多寡而使 凝膠化時間受到較大影響，故難以控制凝膠化時間，僅因 酸量的些微不同’就會使pH大幅變動而導致凝膠化時間大 幅變化。因此，係多量使用酸性反應劑（以下亦稱爲「硬 化劑」），並使用在pH 1 ~3附近具有安定的長凝膠化時間 之二氧化矽用溶液》此時，由於產生較多的反應生成物， 所以不僅對混凝土會造成不良影響，並且就水質保全之觀 點來看亦不佳。 酸性二氧化矽溶液的酸性反應劑，爲了有效率地進行 水玻璃的鹼中和，係使用硫酸、磷酸或此等的混合物，或 是此等的酸性鹽。此時，酸性二氧化矽溶液的反應生成物 ，爲不溶性的二氧化矽，與硫酸鈉或磷酸鈉等等之水溶性 無機鹽或過剩的酸。此等水溶性的反應生成物，會有對地 下水的水質或地中結構物造成某種影響之疑慮。此外，酸 雨的影響、溫泉地帶或火山堆積物中的隧道、煤灰上之埋 塡物的建築物基礎等所造成之硫酸離子的影響、或是海水 等的影響，會導致混凝土結構物的中性化或劣化者，亦爲 人所熟知。 -8- 1375742 另一方面，近年來伴隨著地震的頻繁產生，混凝土結 ' 構物或土中埋設物等之液狀化對策工程等的耐震補強，乃 ' - 逐漸成爲社會問題。爲了解決此問題，係要求可經濟性地 使大容量的土滲透於土粒子之間，以形成具有耐久性之地 盤者。因此，必須將注射孔間隔設爲寬廣範圍（1.5m〜4m )，將具有數小時至十幾個小時的長凝膠化時間之耐久性 •漿料，一邊以低吐出滲透於土粒子之間一邊固結。因此， ,φ 必須使用以酸將成爲水玻璃的劣化因素之鹼予以去除，並 具有數小時~十幾個小時的凝膠化時間且耐久性佳之酸性 區的二氧化矽溶液之二氧化矽溶膠，或是將水玻璃進行離 子交換處理予以脫鹼化並進一步增粒之二氧化矽膠體。此 時，爲了得到長凝膠化時間，必須設定在較低的pH酸性値 ，故需探討酸性區的二氧化矽溶液對混凝土結構物所造成 之影響，因而存在下列課題，亦即過剩的硫酸或硫酸鈉等 之水溶性反應生成物溶出於地下水所導致之環境負荷，或 # 是對混凝土結構物或土中埋設物所造成的影響。 • 在該背景下，本發明者們係經過長時間對下列情形進 ' 行探討，亦即當地下水中含有硫酸離子或海水時或是將含 有硫酸離子之注入材料注入於地下水面下的地盤中時，凝 膠化後的凝膠中之反應生成物的動作、以及對混凝土結構 物等所造成之影響進行探討，結果發現下列內容。 (1 )在無限開放的地盤條件下之地下水面下，在注 入於地盤中之溶液型酸性二氧化矽漿料的凝膠中所形成之 反應生成物，會隨著時間經過從凝膠中溶出並擴散於地下 -9 - 1375742 水中而被稀釋，結果使該反應生成物的濃度降低。若反應 生成物的濃度相較於對周邊結構物造成不良影響之期間更 快速地降低時，則實際上不會有問題。 (2) 雖然在開放的地盤條件下，反應生成物的濃度 降低速度快，但在封閉的區域中，反應生成物不易擴散且 不易被稀釋。此外，在濃度較濃的條件下，反應生成物容 易對周邊結構物造成不良影響。 (3) 在藉由混凝土結構物等使一方被封閉之地盤條 件下，反應生成物容易受限制，而往地下水中呈開放之區 域的方向擴散。 根據上述發現，本發明者們爲了防止硫酸離子對混凝 土所造成的不良影響，而對含有磷酸化合物或金屬離子封 閉劑之二氧化矽漿料對混凝土所造成的影響進行硏究，結 果發現到由此般二氧化矽漿料所起因而在混凝土表面所產 生之白色被覆層（罩護二氧化矽），可保護混凝土。根據 該發現，本發明者們在專利文獻1中，提出一種將含有螯 合劑而成之二氧化矽溶液（罩護二氧化矽溶液）注入於地 盤中使地盤固結，並且在地盤中的混凝土建造物或水泥硬 化物的表面形成防護被膜（罩護二氧化矽）之地盤注入工 法。 [先前技術文獻] [專利文獻] [專利文獻1]日本特許第3072346號公報 -10- 1375742 * 【發明內容】 •. (發明所欲解決之問題） 地盤之設置在地下水面下的共通溝或是隧道、雨水溝 、瓦斯、自來水、電信、電話的管路般之具有中空部之混 凝土結構物中，當產生混凝土的劣化，或龜裂的產生或接 縫的劣化等情形時，會使二氧化矽漿料中含有硫酸離子或 ,φ 是地下水含有硫酸離子或鹽，使得含有此等之地下水通過 混凝土的裂縫或劣化部分而流入混凝土結構物的中空部， 然後經由風乾狀態使硫酸鹽或NaCl濃縮，而更進一步使混 凝土劣化。 亦即，當具有中空部之土中結構物存在於地下水面下 時，若硫酸離子流入於此般土中結構物，則水分會於中空 部蒸發而使硫酸離子濃縮，將造成極大問題。因此，爲了 謀求該土中結構物的耐震補強，重要的是抑制此般過程所 φ 導致之土中結構物的劣化。根據上述奪利文獻1所記載之 技術，雖然可得到防止來自混凝土等之鹼的溶出，並防止 所接觸之漿料中之二氧化矽膠體的劣化及弱化之效果，但 上述專利文獻1中，並未考量到此般具有中空部之土中結 構物，就該點而言仍不充分。 因此，本發明之目的在於提供一種當藉由耐久性佳之 二氧化矽漿料對具有中空部之土中結構物進行耐震補強時 ，可抑制因反應生成物所造成之土中結構物的劣化，並且 藉由將注入區域整體的反應生成物量降低至最低程度，以 -11 - 1375742 將注入區域整體之二氧化矽漿料的反應生成物所 響抑制在最低程度，而謀求混凝土的防劣化與水 共存之地盤注入工法。 (用以解決問題之技術手段） 本發明者們係爲了解決上述課題而進行精心 果發現下列內容。 亦即，在地下水面下之具有中空部之土中結 如第14圖所示般設置固結層時，由於混凝土本身 許的透水性，所以在地下水面下因水壓的作用而 成物流入於中空部，或是混凝土塊體被夾持於中 大氣與含有硫酸之固結層間，可能使硫酸固結層 離子與地下水一同通過混凝土層而流入於中空部 混凝土劣化、產生龜裂或使接縫劣化時，該傾向 。此時，流入於中空部之硫酸鹽或NaCl，會風乾 土急速劣化" 相對於此，如第1圖所示，當混凝土與硫酸 間存在含有螯合劑之二氧化矽層時，首先螯合劑 二氧化矽成分及地下水一同侵入於混凝土中，或 劣化部分，與混凝土表面的Ca、Mg離子反應而 氧化矽（磷酸鈣矽酸鹽或氫氧磷灰石）充塡於表 部分而呈不透水化，以防止硫酸離子對混凝土之子 本發明者們，係從上述觀點中進一步探討： 少固結地盤中的反應生成物，有效地進行具有中 造成之影 質保全之 探討，結 構物中， 仍具有少 使反應生 空部等之 中的硫酸 。尤其當 愈趨顯著 而使混凝 固結層之 成分會與 是裂縫或 將罩護二 面或龜裂 聲蝕。 儘可能減 空部之土 -12- 1375742 中結構物的修補或補強，並且應用地下水的動作，以較少 * 的注入量在混凝土表面上形成對混凝土具有保護功能之被 •. 膜層。結果發現到：使用含有螯合劑之非鹼性二氧化矽溶 液，於混凝土結構物或埋設管等之土中結構物的附近部， 以既定範圍設置改良地盤，並將非鹼性二氧化矽溶液的注 入條件設定在既定條件內，應用地下水會因水壓而浸潤於 位於地下水面下之中空部內的特性，將具有混凝土的保護 ,φ 功能之注入液的反應生成物，與混凝土表面的Ca、Mg進 行反應，而可藉此解決上述課題，因而完成本發明。 亦即，本發明之地盤注入工法，是將以螯合劑作爲有 效成分之非鹼性二氧化矽溶液，注入於：將既存或預定建 造的土中結構物周圍予以包圍之地盤中之地盤注入工法， 並且前述土中結構物的至少一部分是存在於地下水面下， 構成該土中結構物之壁面之中，一面面向地盤且另一面面 向大氣之地盤注入工法，其特徵爲：注入前述非鹼性二氧 # 化矽溶液，以使前述地盤中之前述螯合劑的含量於前述土 中結構物的表面每1 m2爲3 6 g以上。 此外，本發明之其他地盤注入工法，是將以螯合劑作 爲有效成分之非鹼性二氧化矽溶液，注入於：將既存或預 定建造的土中結構物周圍予以包圍之地盤中之地盤注入工 法，並且前述土中結構物的至少一部分是存在於地下水面 下，構成該土中結構物之壁.面之中，一面面向地盤且另一 面面向大氣之地盤注入工法，其特徵爲：將前述非鹼性二 氧化矽溶液中之前述螯合劑的離子含量設爲3 000 ppm以上 -13- 1375742 ，並且將固結層距離前述土中結構物表面的厚度，以均質 凝膠（Homo-Gel)換算設爲1 cm以上。 再者，本發明之其他地盤注入工法，是將以螯合劑作 爲有效成分之非鹼性二氧化矽溶液，注入於：將既存或預 定建造的土中結構物周圍予以包圍之地盤中之地盤注入工 法，並且前述土中結構物的至少一部分是存在於地下水面 下，構成該土中結構物之壁面之中，一面面向地盤且另一 面面向大氣之地盤注入工法，其特徵爲：至少使含有前述 螯合劑之二氧化矽溶液成分，較該螯合劑以外的二氧化矽 溶液成分更先接觸於前述土中結構物。’ 再者，本發明之其他地盤注入工法，是將以螯合劑作 爲有效成分之非鹼性二氧化矽溶液，注入於：將既存或預 定建造的土中結構物周圍予以包圍之地盤中之地盤注入工 法，並且前述土中結構物的至少一部分是存在於地下水面 下，構成該土中結構物之壁面之中，一面面向地盤且另一 面面向大氣之地盤注入工法，其特徵爲：前述非鹼性二氧 化矽溶液的二氧化矽濃度[Si〇2](質量％ )係滿足下列式 (A) 2 質量 ％S[SiO2]S50 質量 ％: 其中該非鹼性二氧化矽溶液包含磷酸化合物作爲螯合 劑，且該非鹼性二氧化矽溶液的磷離子濃度[p] ( ppm )滿 足下列式， (B ) 3000 ppmS [P]S 120000 ppm。 本發明之地盤注入工法中，較佳係將固結層距離前述 -14- 1375742 土中結構物表面的厚度設爲〇.5m以上。此外，在將 鹼性二氧化矽溶液中含有前述磷酸化合物之組成分 於包圍前述土中建造物周圍之地盤中後，在把以前 性二氧化矽溶液之中的硫酸化合物作爲有效成分之 ，注入於該含有磷酸化合物組成分的注入區域周圍 佳係將該含有硫酸化合物組成分的磷離子濃度[P]( 設爲由下列式表示之範圍內， 前述非 ，注入 述非鹼 組成分 時，較 ppm )In other words, in the slurry using water glass as a raw material, an alkali cerium slurry is formed by de-alkalinizing the alkali in the water glass which is a deterioration factor, and long-term durability can be obtained.矽 Sol slurry. On the other hand, this durability is further enhanced by increasing the particle size by ion-exchange treatment of the alkali in the water glass. This is a cerium oxide colloid. The slurry of the cerium oxide colloid as a main material and added with an acid or a base to activate the active cerium oxide colloid is used as a permanent slurry. Figure 13 is a graph showing the relationship between the pH of the cerium oxide solution and the gel time. A general solution type alkali-based injection material has poor durability and a short gelation time. On the other hand, the acid cerium oxide sol has a long-term durability, and the active cerium oxide colloid has a good permanent property. For example, in the case of liquefaction countermeasures, it is necessary to carry out gelation for a long period of time in accordance with the alkali removal, and to use acid when neutralizing the alkali and gelling for a long period of time. However, when sulfuric acid is used as the acid, it is known that sulfate ions have an adverse effect on concrete. The effect of soil containing sulphate and water on concrete is shown in the following table. 1375742 [Table 1] Degree of sulfate action Soluble sulfate in soil samples (S〇4) (%) Sulfate in water solvent like S04) (ppm) Neglectable 0.01-0.10 0-150 Only slightly 0.10-0.20 150-1000 There is a certain degree of 0.20-0.50 1000-2000 very serious 0.50 or more 2000 or more (extracted from the concrete engineering manual) In addition, the cerium oxide solution in the acidic zone will cause gelation due to the amount of acid The gelation time is greatly affected, so it is difficult to control the gelation time, and only due to the slight difference in the amount of acid 'will greatly change the pH, resulting in a large change in the gelation time. Therefore, an acidic reactant (hereinafter also referred to as "hardener") is used in a large amount, and a solution of cerium oxide having a stable long gelation time near pH 1 to 3 is used. The reaction product is not only adversely affected by concrete, but also poor in terms of water quality preservation. In order to efficiently carry out alkali neutralization of water glass, an acidic reactant of an acidic cerium oxide solution is a mixture of sulfuric acid, phosphoric acid or the like, or an acidic salt thereof. At this time, the reaction product of the acidic cerium oxide solution is an insoluble cerium oxide, a water-soluble inorganic salt such as sodium sulfate or sodium phosphate, or an excess acid. These water-soluble reaction products may have some concern about the quality of the groundwater or the structure of the ground. In addition, the influence of acid rain, the influence of sulfate ions caused by tunnels in hot springs or volcanic deposits, the building foundation of burial materials on coal ash, or the influence of seawater, etc., may result in the middle of concrete structures. Sexualized or degraded, also known. -8- 1375742 On the other hand, in recent years, with the frequent occurrence of earthquakes, the earthquake-resistant reinforcement of concrete measures such as concrete structures or soil-embedded materials has become a social problem. In order to solve this problem, it is required to economically infiltrate a large-capacity soil between soil particles to form a durable land. Therefore, it is necessary to set the injection hole interval to a wide range (1.5 m to 4 m), and to have a long gelation time with a durability of from several hours to several ten hours, and to permeate the soil particles with low discharge. Consolidate on one side. Therefore, φ must be removed by using a base which is acid-degraded as a deterioration factor of water glass, and has a gelation time of several hours to several ten hours and is excellent in durability in an acidic region of a cerium oxide solution of cerium oxide sol. Or the cerium oxide colloid which is subjected to ion exchange treatment to de-alkaliize and further increase the particle size. At this time, in order to obtain a long gelation time, it is necessary to set the acidity at a lower pH, so it is necessary to investigate the effect of the cerium oxide solution in the acidic region on the concrete structure, and thus the following problems, that is, excess sulfuric acid Or the environmental load caused by the water-soluble reaction product such as sodium sulfate dissolved in groundwater, or # is the effect on the concrete structure or the buried matter in the soil. • In this context, the inventors have been discussing the following situations for a long time, that is, when the groundwater contains sulfate ions or seawater, or the injection material containing sulfate ions is injected into the ground below the groundwater surface. In the case of the action of the reaction product in the gel after gelation and the influence on the concrete structure, etc., the following contents were found. (1) Under the groundwater surface under infinite open site conditions, the reaction product formed in the gel of the solution-type acidic ceria slurry injected into the site will dissolve out of the gel over time. It is diluted and diffused in the underground -9 - 1375742 water, and as a result, the concentration of the reaction product is lowered. If the concentration of the reaction product is lowered more rapidly than during the period in which the peripheral structure is adversely affected, there is practically no problem. (2) Although the concentration of the reaction product decreases rapidly under open site conditions, in the closed region, the reaction product is not easily diffused and is not easily diluted. In addition, under the conditions of rich concentration, the reaction product easily has an adverse effect on the surrounding structure. (3) Under the condition that one of the concrete structures is closed by a concrete structure or the like, the reaction product is easily restricted and diffuses in the direction of the open area of the groundwater. According to the above findings, the inventors of the present invention have studied the effect of the cerium oxide slurry containing a phosphoric acid compound or a metal ion blocking agent on concrete in order to prevent the adverse effects of sulfate ions on concrete, and found that The white coating layer (covering cerium oxide) produced by the cerium oxide slurry and thus on the concrete surface protects the concrete. According to the findings, the inventors of the present invention proposed a method of injecting a cerium oxide solution containing a chelating agent (covering a cerium oxide solution) into a ground plate to consolidate the ground, and the concrete in the ground. The surface of the building or cement hardened material forms a site for the protective film (covering cerium oxide). [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent No. 3072346 - 10 1375742 * [Disclosed] (The problem to be solved by the invention) The common trench of the ground surface disposed under the groundwater surface or It is a concrete structure with a hollow portion like a pipeline, a rainwater ditch, a gas, a tap water, a telecommunications, and a telephone. When the concrete is deteriorated, or the crack is generated or the joint is deteriorated, etc. The cerium oxide slurry contains sulfuric acid ions or φ is that the groundwater contains sulfate ions or salts, so that the groundwater containing such ground flows into the hollow portion of the concrete structure through the crack or deteriorated portion of the concrete, and then the sulfate or NaCl is air-dried. Concentrate and further deteriorate the concrete. That is, when the structure of the soil having the hollow portion exists under the surface of the groundwater, if the sulfate ions flow into the structure in the soil, the water will evaporate in the hollow portion to concentrate the sulfate ions, which causes a great problem. Therefore, in order to seek the seismic reinforcement of the structure in the soil, it is important to suppress the deterioration of the structure in the soil caused by the process φ. According to the technique described in the above-mentioned Patent Document 1, it is possible to obtain an effect of preventing elution of alkali from concrete or the like and preventing deterioration and weakening of the cerium oxide colloid in the slurry to be contacted. The structure of the soil having a hollow portion is not considered, and it is still insufficient in this point. Accordingly, an object of the present invention is to provide a structure for suppressing deterioration of a structure in a soil caused by a reaction product when the structure of the soil having a hollow portion is subjected to seismic strengthening by a cerium oxide slurry having excellent durability. Further, by reducing the amount of the reaction product in the entire injection region to a minimum, the reaction product of the cerium oxide slurry in the entire injection region is suppressed to a minimum with -11 - 1375742, and the concrete is prevented from deteriorating and water. Coexisting sites are injected into the construction method. (Technical means for solving the problem) The inventors of the present invention have carefully discovered the following contents in order to solve the above problems. That is, when the solid layer is formed in the soil having the hollow portion under the groundwater surface as shown in Fig. 14, the concrete is allowed to have water permeability, so that it is flowed under the surface of the groundwater due to the water pressure. In the hollow part, or the concrete block is sandwiched between the middle atmosphere and the solidified layer containing sulfuric acid, the sulfuric acid consolidation layer ions may pass through the concrete layer together with the groundwater and flow into the hollow concrete to deteriorate, crack or make contact. This tendency is the case when the seam is deteriorated. At this time, the sulfate or NaCl flowing into the hollow portion will rapidly deteriorate the air-dried soil. In contrast, as shown in Fig. 1, when a cerium oxide layer containing a chelating agent is present between the concrete and the sulfuric acid, the chelating agent is first. The cerium oxide component and the groundwater invade together with the concrete, or the deteriorated part, reacts with the Ca and Mg ions on the concrete surface, and the cerium oxide (calcium phosphate strontium phosphate or hydroxyapatite) is impervious to the surface part and is impervious to water. The inventors of the present invention have further explored the above-mentioned viewpoints from the above viewpoints: the reaction product in the less-consolidated site is effectively discussed in the form of the image quality preservation, and in the structure, It has a small amount of sulfuric acid in the reaction hollow portion or the like. Especially when it becomes more and more obvious, the components of the coagulated solidified layer may be cracked or eroded by the surface or crack. As much as possible, the repair or reinforcement of the structure in the soil of the -12- 1375742, and the application of groundwater, to form a protective layer on the concrete surface with a small amount of injection. As a result, it was found that a non-alkaline cerium oxide solution containing a chelating agent was used to set a modified site in a predetermined range in the vicinity of the structure in the soil of a concrete structure or a buried pipe, and a non-alkaline cerium oxide solution was prepared. The injection conditions are set within the established conditions, and the applied groundwater will be infiltrated into the hollow portion under the groundwater surface due to the water pressure, and will have the protection of the concrete, the reaction product of the φ function injection liquid, and the Ca on the concrete surface. The present invention can be accomplished by reacting Mg to solve the above problems. That is, the site injecting method of the present invention is to inject a non-alkaline ceria solution containing a chelating agent as an active ingredient into a site in which a site surrounded by a structure in an existing or predetermined structure is surrounded. And at least a part of the structure in the soil is a ground plate injection method which exists under the groundwater surface and constitutes a surface of the structure in the soil, and faces the ground surface on the other side and faces the atmosphere on the other side, and is characterized in that the non-alkaline is injected. The dioxin solution is irrigated so that the content of the aforementioned chelating agent in the above-mentioned land is more than 3 6 g per 1 m 2 of the surface of the above-mentioned soil structure. Further, in another method of injecting a site of the present invention, a non-alkaline ceria solution having a chelating agent as an active ingredient is injected into a site in which a site surrounded by a structure in an existing or predetermined structure is surrounded. And at least a part of the structure in the soil is a method of injecting the ground surface under the surface of the groundwater, forming a surface of the structure in the soil, and facing the ground surface on one side and facing the atmosphere on the other side, characterized in that: The ion content of the aforementioned chelating agent in the alkaline cerium oxide solution is set to 3 000 ppm or more -13 to 1375742, and the thickness of the consolidated layer is from the surface of the structure in the above soil, in terms of homogenous gel (Homo-Gel) Set to 1 cm or more. Further, in another method of injecting a site of the present invention, a non-alkaline ceria solution having a chelating agent as an active ingredient is injected into a site in a site surrounded by a structure in an existing or predetermined structure. And a method for injecting at least a part of the structure of the soil in the soil below the surface of the groundwater to form a ground surface of the structure in the soil, the surface facing the ground surface and the other surface facing the atmosphere, characterized in that at least the foregoing The cerium oxide solution component of the chelating agent contacts the structure in the soil earlier than the cerium oxide solution component other than the chelating agent. Further, in another method of injecting a site of the present invention, a non-alkaline ceria solution having a chelating agent as an active ingredient is injected into a site in a site surrounded by an existing or predetermined structure of the soil. a method of injecting, and at least a part of the structure in the soil is a ground plate surface which is formed under the surface of the groundwater and constitutes a surface of the structure in the soil, the surface facing the ground surface and the other surface facing the atmosphere, wherein the non-alkali is characterized by The cerium oxide concentration [Si〇2] (% by mass) of the cerium oxide solution satisfies the following formula (A) 2% by mass S[SiO2]S50% by mass: wherein the non-basic cerium oxide solution contains a phosphoric acid compound as a chelating A mixture, and the phosphorus ion concentration [p] (ppm) of the non-basic ceria solution satisfies the following formula: (B) 3000 ppmS [P]S 120000 ppm. In the method of injecting the ground of the present invention, it is preferable to set the thickness of the consolidated layer to the surface of the structure in the above -14 to 1375742 to be 〇.5 m or more. In addition, after the composition containing the phosphoric acid compound in the alkaline cerium oxide solution is divided into the ground surrounding the building in the soil, the sulfuric acid compound in the prior cerium oxide solution is injected as an active ingredient. The phosphorus ion concentration [P] of the composition containing the sulfuric acid compound is preferably in the range of the injection region containing the phosphate compound component (in the range represented by the following formula, the above-mentioned non-injection of the non-alkali component, Ppm )

(C ) 0 ^ [P] S 30000 ppm。 再者，本發明中，較佳者是前述非鹼性二氧化 含有水玻璃的二氧化矽，該非鹼性二氧化矽溶液的 矽濃度[Si02](質量％)滿足下列式， (D) 2質量 ％S[SiO2]S10質量 ％。 再者，尤佳者是前述非鹼性二氧化矽溶液中含 磷酸化合物之組成分的磷離子濃度[P] ( ppm )與二 濃度[Si02](質量％)，係滿足下列式， [P]/[Si02] = 60~5000。 本發明之地盤注入工法，可適當地使用在前述 構物之液狀化對策工程、防劣化或修補工程。此外 明之地盤注入工法中，較佳係在注入前述非鹼性二 溶液之前，先將水泥系漿料（Grout )，注入於前 結構物之接觸於地盤之該側的面之周圍的地盤中。 較佳亦從前述土中結構物之面向大氣之該側的面， 置在該土中結構物內之注入孔，注入前述非鹼性二 溶液來進行前述土中結構物之液狀化對策工程、防 矽溶液 二氧化 有前述 氧化砂 土中結 ，本發 氧化矽 述土中 再者， 並由設 氧化矽 劣化或 -15- 1375742 修補工程。 再者，本發明之地盤注入工法，在使用多點地盤同時 注入方式，亦即從前述土中結構物之面向大氣之該側的面 ，經由設置在該土中結構物內且具有吐出口之複數個注入 孔同時注入於複數個注入地點之注入方式，注入前述非鹼 性二氧化矽溶液時， 所使用的注入設備，係具備：從集中注入機具經由複 數條注入管路所連接之複數條注入管、將前述非鹼性二氧 化矽溶液以液體輸送送至前述複數個注入地點並且將該非 鹼性二氧化矽溶液注入於該複數個注入地點之複數個單柱 塞泵、測量前述複數個注入地點中之前述非鹼性二氧化矽 溶液的流量及/或壓力之流量及壓力測量裝置、以及總括 地管理前述複數個單柱塞泵之集中管理裝置， 使前述複數個單柱塞泵動作，一邊根據來自前述流量 及壓力測量裝置的資訊，由前述集中管理裝置來控制該複 數個單柱塞泵的動作，一邊對前述複數個注入地點同時注 入或選擇性地注入前述非鹼性二氧化矽溶液。 發明之效果： 根據本發明，藉由形成爲上述構成，可提供下列地盤 注入工法，亦即一邊將注入區域整體之二氧化矽漿料的反 應生成物的生成量抑制在最低程度以保全水質，一邊在具 有中空部之土中結構物的表面或是該劣化部或龜裂部內， 形成具有保護土中結構物之效果的堅固保護膜或塡充物， -16- 1375742 而得到土中結構物的補強效果，並可藉由二氧化矽的凝膠 耐久性而得到優異固結之地盤注入工法。 【實施方式】 以下係詳細說明本發明之實施形態。 如前述般，當使用非鹼性二氧化矽溶液之固結地盤， 尤其與在無遮蔽物之地下水面下的砂地盤或砂礫地盤內流 .# 動之地下水等接觸時，水溶性反應生成物容易在短時間內 溶出（開放系地盤）。然而，在由混凝土結構物、土中埋 設物或混凝土樁所阻擋，或是結構物正下方之地盤（封閉 系地盤），或是黏性土並存之地盤（複合系地盤）中，來 自固結物的游離成分不易溶出並擴散，水溶性反應生成物 容易長時間停留在地盤中（封閉系地盤）。 因此，在纣閉系地盤或複合系地盤中，當地下水中的 稀釋較少或較慢時，會有所溶出之水溶性反應生成物對混 • 凝土結構物等造成影響之疑慮。此外，不論在開放系地盤 或複合系地盤中，當水溶性反應生成物爲多量時，就環境 負荷而言較不隹。再者，當固結區域爲寬廣範圍時或是地 盤的透水性較少時，反應生成物亦容易存在，容易對混凝 土造成影響。 因此，如上述般，本發明者們首先在專利文獻1中， 提出一種使用螯合劑之二氧化矽漿料作爲用以保護混凝土 結構物等，或是抑制因來自混凝土的鹼溶出所導致之二氧 化矽凝膠的劣化之技術。僅使用螯合劑水溶液，並未在混 -17- 1375742 凝土形成被覆膜。然而，在水玻璃、活性矽酸、膠體二氧 化矽等之二氧化矽溶液中使用螯合劑作爲硬化劑時，當螯 合劑存在於非鹼性二氧化矽溶液中時，會生成混凝土表面 的Mg或Ca離子與二氧化矽一同堅固地納入於混凝土表面 之狀態的被覆膜，而使地盤固結。此時，該二氧化矽溶液 中的二氧化矽分子或二氧化矽膠體，由於螯合劑的螯合作 用，會將先行存在於地盤中之混凝土結構物、或在注入漿 料後所建構之混凝土結構物等的表面上所存在之主要爲鈣 或鎂納入，而在混凝土表面上形成由二氧化矽與P與Mg、 Ca所構成之防護被膜。此般被覆膜，即使在挖掘注入後的 地盤來灌入設置混凝土時，之後亦會形成於混凝土表面。 含有螯合劑之非鹼性二氧化矽溶液，係與混凝土表面 的Ca2 +或Mg2 +反應而在混凝土表面形成防護被膜（罩護二 氧化矽）。 螯合劑較多是使用磷酸系化合物，例子之一的六偏磷 酸鈉，當在混凝土表面般存在有Ca、Mg離子時，由於螯 合作用而封鎖Ca、Mg並釋出Na離子，Ca + +或Mg + +與二氧 化矽一同在混凝土表面上形成以下所示之不溶性的錯合物 ’並阻止離子從內外部的溶出與侵入。(C) 0 ^ [P] S 30000 ppm. Further, in the present invention, the non-basic dioxide-containing cerium oxide containing water glass is preferable, and the cerium concentration [SiO 2 ] (% by mass) of the non-basic cerium oxide solution satisfies the following formula, (D) 2 Mass % S [SiO 2 ] S 10% by mass. Further, it is preferable that the phosphorus ion concentration [P] (ppm) and the two concentration [Si02] (% by mass) of the component containing the phosphoric acid compound in the non-basic ceria solution satisfy the following formula, [P ]/[Si02] = 60~5000. In the method of injecting the ground of the present invention, it is possible to suitably use the liquidification countermeasure project, the deterioration prevention or the repairing work of the above-mentioned structure. Further, in the method of injecting the ground, it is preferred to inject the cement slurry (Grout) into the ground surrounding the surface of the front structure contacting the side of the ground before injecting the non-alkaline two solution. Preferably, the surface of the soil-formed structure facing the atmosphere is placed in the injection hole in the structure of the soil, and the non-alkaline two solution is injected to perform the liquidation countermeasure of the structure in the soil. The anti-caries solution is oxidized by the above-mentioned oxidized sand, and the oxidized cerium is further described in the soil, and is deteriorated by yttrium oxide or repaired by -15-1375742. Furthermore, the method for injecting a site according to the present invention is to use a multi-point grounding simultaneous injection method, that is, a surface facing the atmosphere from the surface of the soil structure, via a structure disposed in the soil and having a discharge port. a plurality of injection holes are simultaneously injected into a plurality of injection sites, and when the non-alkaline ceria solution is injected, the injection device used includes: a plurality of injection lines connected from the centralized injection tool through a plurality of injection lines Injecting a tube, transporting the non-alkaline ceria solution to the plurality of injection sites by liquid and injecting the non-alkaline ceria solution into the plurality of single plunger pumps at the plurality of injection sites, and measuring the plurality of the plurality of plunger pumps a flow rate and pressure measuring device for flow rate and/or pressure of the aforementioned non-alkaline cerium oxide solution at the injection site, and a collective management device for collectively managing the plurality of single plunger pumps to operate the plurality of single plunger pumps Controlling the plurality of single plunger pumps by the aforementioned centralized management device based on information from the flow rate and pressure measuring device Operation, while a plurality of injection of the injection sites simultaneously or selectively non-basic silicon dioxide was injected into the solution. Advantageous Effects of Invention According to the present invention, by forming the above-described configuration, it is possible to provide the following method of injecting a ground, that is, to prevent the generation amount of the reaction product of the cerium oxide slurry in the entire injection region from being minimized to maintain the water quality. In the surface of the structure in the soil having the hollow portion or in the deteriorated portion or the cracked portion, a solid protective film or a filler having the effect of protecting the structure in the soil is formed, -16-1375742, and the structure in the soil is obtained. The reinforcing effect and the excellent consolidation of the ground casting method can be obtained by the gel durability of cerium oxide. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. As described above, when a consolidated ground using a non-alkaline cerium oxide solution is used, especially when it comes into contact with a groundwater or a gravel ground under a groundwater surface without a shield, water-soluble reaction products are formed. It is easy to dissolve in a short time (open system). However, in the case of a concrete structure, a buried material in the soil or a concrete pile, or a site directly below the structure (closed land), or a site where the cohesive soil coexists (composite land), from consolidation The free component of the substance is less likely to be dissolved and diffused, and the water-soluble reaction product tends to stay in the ground for a long time (closed land). Therefore, in the closed or ground system, when the dilution in the groundwater is less or slower, there is a concern that the dissolved water-soluble reaction product has an influence on the mixed structure. Further, in the case of an open system or a composite land, when the amount of the water-soluble reaction product is large, the environmental load is less. Further, when the consolidation area is in a wide range or when the water permeability of the floor is small, the reaction product is also likely to exist, which is liable to affect the concrete. Therefore, as described above, the inventors first proposed in Patent Document 1 a cerium oxide slurry using a chelating agent as a material for protecting a concrete structure or the like, or suppressing alkali dissolution due to concrete. A technique for degrading cerium oxide gel. Only a chelating agent aqueous solution was used, and the coating film was not formed by mixing -17-1375742 concrete. However, when a chelating agent is used as a hardener in a cerium oxide solution such as water glass, active citric acid or colloidal cerium oxide, when the chelating agent is present in the non-alkaline cerium oxide solution, Mg on the concrete surface is generated. Or the Ca ion and the cerium oxide are firmly incorporated into the coating film in the state of the concrete surface, and the ground plate is consolidated. At this time, the cerium oxide molecule or the cerium oxide colloid in the cerium oxide solution, due to the chelation of the chelating agent, will pre-exist the concrete structure existing in the ground or the concrete constructed after the slurry is injected. The surface of the structure or the like is mainly composed of calcium or magnesium, and a protective film composed of cerium oxide and P with Mg and Ca is formed on the surface of the concrete. The film is so covered that it is formed on the concrete surface even after the excavated land is poured into the set concrete. A non-alkaline cerium oxide solution containing a chelating agent reacts with Ca2+ or Mg2+ on the surface of the concrete to form a protective coating on the surface of the concrete (covering cerium oxide). Most of the chelating agents are phosphoric acid compounds. One of the examples is sodium hexametaphosphate. When Ca and Mg ions are present on the concrete surface, Ca and Mg are blocked by chelation and Na ions are released. Ca + + Or Mg + + together with cerium oxide forms an insoluble complex as shown below on the concrete surface and prevents dissolution and intrusion of ions from the inside and the outside.

ο - o = pI 8 Μ ) ca:lo— ο I ρμνοο - o = pI 8 Μ ) ca:lo— ο I ρμνο

ο ο ΟΠΜΡ丨Nao = p IN ο S1 ο -18- 1375742 同樣的，使用磷酸時，混凝土表面的Ca、Mg離子與 螯合劑係以下列方式反應，而在混凝土表面形成罩護二氧 化矽。ο ο ΟΠΜΡ丨Nao = p IN ο S1 ο -18- 1375742 Similarly, when phosphoric acid is used, the Ca, Mg ions and the chelating agent on the concrete surface react in the following manner to form a cerium oxide on the surface of the concrete.

OH OH OH 0HOH OH OH 0H

III I H〇-Si-0-Si-0-Si-0-Ca-0-P=0III I H〇-Si-0-Si-0-Si-0-Ca-0-P=0

111 OH111 OH

OH OH OHOH OH OH

該現象，即使在地下水中或二氧化矽溶液中存在有 so42·或cr等亦相同。因此，可將so42_或海水（cr)等從 混凝土結構物等的外部往內部之侵入予以阻隔，並且可將 鹼從混凝土結構物等的內部往外部之溶出，予以阻隔。此 般藉由混凝土表面的被覆層來阻隔來自混凝土內部的鹼溶 出之現象，可經由當混凝土表面形成有被覆膜時養護水長 期呈中性値之情形來獲得實證。其結果爲，即使在二氧化 矽漿料所含有之反應生成物中存在有硫酸離子，或是地下 水中存在有硫酸離子或海水，亦可防止混凝土構造物等的 劣化或因來自混凝土的鹼溶出所導致之中性化，並且對於 二氧化矽溶液的凝膠化物，亦可防止因來自混凝土結構物 等的鹼溶出所導致之二氧化矽凝膠的溶解，而將地下水保 持在中性區域。形成於該混凝土結構物等的表面之被覆層 ，係達到需藉由刀刃才能刮除之程度，使二氧化矽成份與 存在於混凝土表面之Ca離子或Mg離子藉由螯合作用而堅 固地結合於混凝土表面來形成。下列第2表係顯示在硫酸 離子或氯離子所存在之地盤中，混凝土表面上所生成之防 護被膜（白色覆膜層，罩護二氧化矽）的分析結果之一例 -19- 1375742 [第據] 成分 含量(質量％) Na2〇 11.1 Si〇2 39.4 Ca 2.77 Mg 3.91 P 8.90 S〇4 12.0This phenomenon is the same even in the presence of so42. or cr in groundwater or in the cerium oxide solution. Therefore, the intrusion of so42_ or seawater (cr) from the outside to the inside of the concrete structure or the like can be blocked, and the alkali can be dissolved from the inside of the concrete structure or the like to the outside to be blocked. Thus, the phenomenon of alkali elution from the inside of the concrete is blocked by the coating layer on the concrete surface, and the evidence can be obtained by the fact that the curing water is periodically neutral when the coating film is formed on the concrete surface. As a result, even if sulfate ions are present in the reaction product contained in the ceria slurry, or sulfate ions or seawater are present in the groundwater, deterioration of the concrete structure or the like or alkali dissolution from the concrete can be prevented. The neutralization is caused, and for the gelation of the cerium oxide solution, the dissolution of the cerium oxide gel due to alkali elution from the concrete structure or the like can be prevented, and the groundwater can be maintained in the neutral region. The coating layer formed on the surface of the concrete structure or the like is such that it can be scraped off by the blade, so that the cerium oxide component is strongly bonded to the Ca ion or the Mg ion existing on the concrete surface by chelation. Formed on the concrete surface. The following second table shows an example of the analysis results of a protective film (white film layer, capped cerium oxide) formed on the surface of concrete on the surface of the sulfate ion or chloride ion. -19-1375742 Ingredient content (% by mass) Na2〇11.1 Si〇2 39.4 Ca 2.77 Mg 3.91 P 8.90 S〇4 12.0

磷酸，當與水玻璃混合時，本身會與水玻璃的鹼中和 而形成酸性二氧化矽溶液，並且亦和二氧化矽成份與混凝 土表面的Ca離子、Mg離子一同形成混凝土被覆膜，而保 護混凝土免受地下水中所存在之so42_s cr的影響。此外 ，磷酸及磷酸化合物，在與硫酸離子共存下，如上述般在 混凝土表面形成保護膜。此時，可考量爲二氧化矽溶液中 所含有之硫酸，分擔將水玻璃的鹼予以中和之作用，磷酸 化合物，分擔與扣除鹼後的二氧化矽成份一同藉由螯合作 用而在混凝土表面形成被覆層之功用。尤其是併用磷酸與 六偏磷酸鈉或倂用磷酸與其他螯合劑之二氧化矽溶液，可 藉由優異的螯合效應來形成被覆層。 本發明中所使用之非鹼性二氧化矽溶液，爲水玻璃、 活性二氧化矽、膠體二氧化矽、或此等之混合物，水玻璃 是通常用作爲工業用途之莫耳比Si02/Na20 = 2~6者。 此外，上述非鹼性二氧化矽溶液，爲去除水玻璃的鹼 之酸性二氧化矽溶液，或是將鹼加入於酸性二氧化矽溶液 -20- ⑧ 1375742 者。該非鹼性二氧化矽溶液，是指藉由酸來去除水玻璃中 ' 的鹸之二氧化矽溶液、以離子交換樹脂或離子交換膜將水 '. 玻璃予以脫鹼化之酸性活性二氧化矽、將水玻璃添加於酸 性活性二氧化矽之鹼性二氧化矽、將鹼性二氧化矽進行加 熱並予以增粒之膠體二氧化矽、以陰離子交換樹脂或陰離 子交換膜將混合水玻璃與酸之酸性二氧化矽之酸的一部分 或全部予以去除之活性二氧化矽、將水玻璃與酸混合於此 等之酸性二氧化矽溶液、或是將由水玻璃與酸所構成之酸 性二氧化矽溶膠溶液加入於此等膠體狀二氧化矽溶液之酸 性二氧化矽溶液。或是可爲金屬二氧化矽溶液。具體而言 ，可使用：使二氧化矽溶液通過離子交換樹脂或離子交換 膜，並藉由加熱等將所得之活性矽酸水溶液縮合爲數萬或 以上的分子量，然後加入鹼或水玻璃而安定成爲弱鹼性， 並混合濃縮爲20〜30質量％的Si02濃度之膠體二氧化矽與酸 之酸性二氧化矽溶液、或上述由膠體二氧化矽與水玻璃所 # 構成的酸性二氧化矽溶液、或是由酸性活性二氧化矽與水 玻璃與酸所構成之酸性二氧化矽。 該膠體二氧化矽，通常其pH呈中性或10附近的弱鹼性 ，藉由添加酸或酸性鹽，亦可呈酸性。此外，亦可混合活 性矽酸（活性二氧化矽）與膠體二氧化矽與水玻璃的2種 或3種，並將酸添加於此而構成中性或酸性二氧化矽溶液 ，或是將混合有水玻璃與酸之酸性水玻璃加入於膠體二氧 化矽或活性矽酸之酸性二氧化矽溶液。再者，膠體二氧化 砂的粒徑可使用Inm〜80nm者，或是混合存在有此等粒徑 -21 - 1375742 者，此外亦可使用經A1改質的膠體二氧化矽。 本發明之所謂具有螯合作用之非鹼性二氧化矽溶液， 是指中性至弱酸性者，係調整至pH 10以下，較佳爲PH6以 下者。Phosphoric acid, when mixed with water glass, itself neutralizes with alkali of water glass to form an acidic cerium oxide solution, and also forms a concrete coating film together with cerium oxide component and Ca ion and Mg ion on the concrete surface. Protect the concrete from the so42_s cr present in the groundwater. Further, the phosphoric acid and the phosphoric acid compound form a protective film on the surface of the concrete as described above in the presence of the sulfate ion. In this case, the sulfuric acid contained in the cerium oxide solution can be considered to share the effect of neutralizing the alkali of the water glass, and the phosphate compound is shared with the cerium oxide component after the alkali-removal by chelation in the concrete. The surface forms the function of the coating layer. In particular, a combination of phosphoric acid and sodium hexametaphosphate or a cerium oxide solution of phosphoric acid and other chelating agents can form a coating layer by an excellent chelation effect. The non-alkaline cerium oxide solution used in the present invention is water glass, active cerium oxide, colloidal cerium oxide, or a mixture thereof, and water glass is commonly used as an industrial use for molar ratio SiO 2 /Na20 = 2~6. Further, the above non-alkaline cerium oxide solution is an alkali acidic cerium oxide solution for removing water glass, or a base is added to an acidic cerium oxide solution -20-8 1375742. The non-alkaline cerium oxide solution refers to an acidic active cerium oxide which is de- basified by removing the cerium dioxide solution in the water glass by acid, and de-basifying the water with an ion exchange resin or an ion exchange membrane. Adding water glass to alkaline cerium oxide of acidic active cerium oxide, colloidal cerium oxide heated and granulated by alkaline cerium oxide, mixing water glass with acid by anion exchange resin or anion exchange membrane An active cerium oxide in which a part or all of the acidic cerium oxide acid is removed, an acidic cerium oxide solution in which water glass and an acid are mixed, or an acidic cerium oxide sol composed of water glass and an acid The solution is added to the acidic ceria solution of the colloidal ceria solution. Or it can be a metal cerium oxide solution. Specifically, it can be used that the cerium oxide solution is passed through an ion exchange resin or an ion exchange membrane, and the obtained active citric acid aqueous solution is condensed to a molecular weight of tens of thousands or more by heating or the like, and then stabilized by adding alkali or water glass. It is weakly alkaline, and is mixed with a concentrated cerium dioxide concentration of 20 to 30% by mass of colloidal cerium oxide and an acidic cerium oxide solution, or the above-mentioned acidic cerium oxide solution composed of colloidal cerium oxide and water glass. Or acidic cerium oxide composed of acidic active cerium oxide and water glass and acid. The colloidal cerium oxide is usually neutral in pH or weakly alkaline in the vicinity of 10, and may be acidic by adding an acid or an acid salt. In addition, two or three kinds of active citric acid (active cerium oxide) and colloidal cerium oxide and water glass may be mixed, and an acid may be added thereto to form a neutral or acidic cerium oxide solution, or may be mixed. An acidic water glass having water glass and acid is added to a colloidal cerium oxide or an active ceric acid acidic cerium oxide solution. Further, the particle diameter of the colloidal silica can be either Inm 80 or a mixture of -21 - 1375742, or a colloidal ceria modified by A1. The non-alkaline ceria solution having chelation for use in the present invention means neutral to weakly acidic, and is adjusted to pH 10 or lower, preferably PH 6 or lower.

此外，本發明中，亦可將磷酸以外的螯合劑倂用於藉 由硫酸或磷酸來去除鹼之非鹼性二氧化矽，而形成罩護二 氧化矽。磷酸以外的螯合劑，由於酸性較弱，單獨使用時 爲了去除鹼，需使用多量。相對於此，磷酸不僅可去除鹼 ，當單獨使用磷酸時亦具有罩護作用，故可形成有效的罩 護二氧化矽。磷酸化合物或螯合劑，係與二氧化矽一同在 混凝土上形成罩護二氧化矽，可防止因共存的硫酸或存在 於地下水中之硫酸離子所導致之混凝土的劣化。磷酸化合 物中，六偏磷酸鈉爲螯合劑，並藉由螯合作用而在混凝土 表面形成罩護二氧化矽，但磷酸或其他磷酸化合物亦形成 具有同樣效果之被覆，因此在本發明中，亦將磷酸化合物 視爲螯合劑，並將含有此之二氧化矽溶液稱爲非鹼性二氧 化矽溶液（罩護二氧化矽溶液）。因此，磷酸以外的螯合 劑，係與磷酸或硫酸倂用而形成非鹼性二氧化矽溶液。使 用磷酸或磷酸鹽作爲該非鹼性二氧化矽溶液者，係較使用 其他螯合劑者更具效果。 本發明中所使用之螯合劑，爲具有螯合效應者，例如 可列舉出各種酸性磷酸鹽、中性磷酸鹽、鹼性磷酸鹽，可 列舉出四多磷酸鹽、六偏磷酸鹽、四多磷酸鹽、焦磷酸鹽 、酸性六偏磷酸鹽、酸性焦磷酸鹽等之縮合磷酸鹽類等， -22- ⑧ 1375742 縮合磷酸鹽類較佳爲鈉鹽。形成非鹼性二氧化矽溶液之磷 酸化合物，由於六偏磷酸鈉可形成特別堅固的罩護二氧化 •. 矽，故較佳。此外，螯合劑除了上述磷酸化合物之外，可 列舉出乙二胺四乙酸、氮基三乙酸、葡萄糖酸、酒石酸或 此等酸之鹽類等，本發明中，磷酸化合物可在二氧化矽溶 液的存在下，在混凝土表面形成最具效果的被覆。 此外，本發明中，亦可倂用不具螯合效應之硬化劑。 φ 該硬化劑可列舉出硫酸等之硫化物 '鹽酸等之氯化物、酸 性鹽、碳酸鹽、碳酸氫鹽、碳酸氣體、碳酸水、鋁酸鹽、 乙二醛、碳酸乙烯酯般之碳酸酯、多元乙酸酯等。除此之 外，亦可單獨使用水泥、石灰、爐渣等作爲硬化劑，或是 與其他硬化劑倂用來使用。此時，可將上述磷酸系化合物 等之具有螯合效應之化合物與不具螯合效應之硬化劑混合 ，並因應所注入之地盤的環境來選擇混合比。再者，亦可 將非鹼性二氧化矽溶液注入於混凝土結構物等之土中結構 • 物的周邊部，並將任意之鹼系的水玻璃注入劑或水泥等之 溶液型漿料注入於該外側區域。當然，亦可添加例如胺基 甲酸酯系樹脂或丙烯酸鹽等之具有凝膠化功能的高分子材 料。 本發明之地盤注入工法中，具體而言，在將以上述螯 合劑作爲有效成分之非鹼性二氧化矽溶液，注入於將土中 結構物的周圍予以包圍之地盤中來改良地盤時，係注入非 鹼性二氧化矽溶液，以使地盤中之螯合劑的含量於土中結 構物的表面每lm2爲36g以上，較佳爲50g~1 000g。藉此， -23- 1375742 可將二氧化矽漿料之水溶性反應生成物的影響抑制在最低 程度，並一邊抑制水質的環境負荷並保持混凝土結構物， 並且可進行耐久性佳之固結。當上述地盤中之螯合劑的含 量未達36g時，可能無法充分地形成不會使硫酸離子或海 水侵入之罩護二氧化矽，而無法得到本發明之期望效果。 此外，本發明之地盤注入工法中，係將非鹼性二氧化 矽溶液中之螯合劑的離子含量設爲3000 ppm以上，較佳爲 3000 ppm~120000 ppm，並且將固結層距離土中結構物表 面的厚度，以均質凝膠（Homo-Gel )換算設爲lcm以上， 較佳爲lcm~30cm，藉此亦可得到與上述相同之效果。上 述地盤中之螯合劑的離子含量未達3000 ppm或上述固結層 的厚度未達1cm時，會部分形成氣泡或未注入區域，使地 下水從該部分滲入，使硫酸離子或海水接觸於混凝土結構 物，而無法得到本發明之期望效果。 再者，本發明之地盤注入工法中，非鹼性二氧化矽溶 液中，係至少使含有上述螯合劑之二氧化矽溶液成分，較 該螯合劑以外的二氧化矽溶液成分更先接觸於土中結構物 ，藉此亦可在硫酸離子的侵入之前，先於土中結構物的表 面形成罩護二氧化矽，而得到與上述相同之效果。 再者，本發明之地盤注入工法中，上述非鹼性二氧化 矽溶液的二氧化矽濃度[Si02](質量％ )係滿足2質量％客 [Si02] S 50質量％，並且包含磷酸化合物作爲螯合劑之非 鹼性二氧化矽溶液的磷離子濃度[P](ppm)滿足3000 ppm S [P] S 1 20000 ppm，藉此亦可得到本發明之期望效果。 -24- 1375742 本發明中，爲了製作出堅固的被覆膜，二氧化矽濃度亦爲 重要。藉此，可將二氧化矽漿料之水溶性反應生成物的影 * . 響抑制在最低程度，並抑制水質的環境負荷，保持混凝土 結構物，並且可進行耐久性佳之固結。 此時，在將非鹼性二氧化矽溶液中含有磷酸化合物之 組成分，注入於包圍土中建造物周圍之地盤中後，較佳係 -把以非鹼性二氧化矽溶液之中的硫酸化合物作爲有效成分 ,φ 之組成分，注入於該含有磷酸化合物組成分的注入區域周 圍。該含有硫酸化合物組成分的磷離子濃度[P] ( ppm)設 爲0S[P]S3 00 00 ppm之範圍內》藉此，可防護土中結構 物免受硫酸離子及/或海水之影響，並且更可減少反應生 成物。 此外，此時非鹼性二氧化矽溶液係含有水玻璃的二氧 化矽，該非鹼性二氧化矽溶液的二氧化矽濃度[Si〇2](質 量％ )較佳係滿足2質量％ S [Si02] S 10質量％。藉此可得 • 下列效果，亦即形成用以與螯合劑結合而在混凝土結構物 表面形成被膜之充足量的罩護二氧化矽。 再者，此時，將非鹼性二氧化矽溶液中含有磷酸化合 物之組成分的磷離子濃度[P] ( ppm )與二氧化矽濃度 [3102](質量％)之比設爲[P]/[SiO2] = 60〜5000之範圍內， 藉此，可藉由金屬離子封鎖劑來形成更堅固的膜。此外， 將含有上述磷酸離子之固結層距離土中結構物表面的厚度 設爲0.5m以上，例如爲lm以上，並且設爲注入區域的一半 長度以下，藉此可得到確實地防護混凝土之效果。 -25- 1375742 此外，本發明中，爲了將注入區域整體之螯合劑的使 用量降低至最低程度，並將與磷酸化合物共存之硫酸化合 物的合計量抑制在最低程度，考量土中結構物與注入區域 的位置關係之含有酸性反應劑之二氧化矽溶液的組合乃爲 重要。再者，罩護二氧化矽溶液，即使在硫酸或海水的存 在下亦與混凝土表面的Ca或Mg離子反應，並藉由螯合反 應來形成進入於混凝土表面之堅固的被覆層。此般具有混 凝土保護效果之罩護二氧化矽的形成，該pH必須爲非鹼性 ，較佳爲酸性。當二氧化矽溶液中殘存有鹼時，混凝土表 面上之被覆層的形成不充分，使混凝土的防護效果降低。 因此，本發明之地盤注入工法，係使用作爲主劑之二 氧化矽溶液，與磷酸化合物、或以磷酸化合物及硫酸化合 物爲有效成分之非鹼性二氧化矽溶液，並應用藉由將pH値 設爲中性〜酸性區域來形成凝膠化之性質之地盤注入工法 ，或者是在注入地盤區域中，倂用以磷酸化合物爲有效成 分之非鹼性二氧化矽溶液與以硫酸化合物爲有效成分之非 鹼性二氧化矽溶液，使地盤固結之地盤注入工法。 本發明之地盤注入工法，可適當地使用在土中結構物 之液狀化對策工程、防劣化或修補工程，可得到防護土中 結構物免受地盤中的地下水中所含有之硫酸離子或氯離子 的影響之效果。尤其是，本發明乃適合於具有中空部且注 入液的組成分與地下水一同浸潤或流入於該中空部之地下 結構物的修補或液狀化的防止。 本發明中，較佳亦在將上述非鹼性二氧化矽溶液注入 -26- 1375742 於地盤之前，先將水泥系漿料注入於混凝土結構物等的土 •.中結構物之接觸於地盤之該側的面之周圍的地盤中。在此 . ，所謂混凝土表面，是指混凝土結構物中之接觸於地盤的 面。 本發明中，由於以當使用非鹼性二氧化矽溶液之固結 地盤接觸地下水等時所溶出之水溶性反應生成物爲問題對 象，所以是以土中結構物的至少一部分存在於地下水面下 φ 之情形爲前提。此外，所謂在構成土中結構物之壁面之中 一面面向地盤且另一面面向大氣者，除了上述具有中空部 之結構物外，亦包含如後述般一部分建構在土中且其他部 分建構造地上之結構物之槪念。再者，本說明書中，基本 上是說明混凝土結構物，但本發明之所謂土中結構物，亦 包含如前述般由金屬等所構成之結構物，此時，與混凝土 結構物的情形相同，藉由應用本發明，可得到期望效果。 本發明所能夠應用之混凝土結構物等的土中結構物， • 可列舉出具有中空部之隧道、地下鐵、山岳隧道、屏蔽、 電線或電話線路的地中管路、瓦斯、上下水管等之基礎設 備的共同溝，以及鋪設地盤的下部等。以下顯示該具體例 〇 第2圖係顯示在建構共同溝時，將非鹼性二氧化矽溶 液注入於地盤並予以固結之狀態之圖。其係顯示：經由注 入管6，將具有螯合效應之非鹼性二氧化矽溶液注入於挖 掘後預定建構之混凝土結構物10的周邊區域8，並於該周 邊部的區域，設置螯合效應弱（或無螯合效應）之非鹼性 -27- 1375742 二氧化矽漿料的注入區域9之情形。 此外，第3圖係顯示將非鹼性二氧化矽溶液注入於地 下結構物的周圍的地盤之方法之圖。此時，如圖示般，可 從地下結構物10之面向大氣之一側的面鑽孔，於地下結構 物1 0內設置注入孔，並經由該注入孔進行注入。亦即，爲 了防止地下水含有S042·或海水之地盤24、或是建構在火山 堆積物中之隧道之混凝土 10的劣化，或者是爲了修復朽化 的共通溝或地下隧道，係從隧道25內部鑽孔，並於地下結 構物10周圍之地盤（限制系區域）的區域8，注入具有螯 合效應之非鹼性二氧化矽溶液（罩護二氧化矽溶液）。此 外，由於地盤中的混凝土 10可能因地下水或注入液中所含 有之硫酸離子或氯離子而產生劣化，所以將非鹼性二氧化 矽溶液注入於混凝土 10之接觸於地盤之該側的面之周圍的 地盤中，來防止或修補混凝土的劣化。再者，在注入非鹼 性二氧化矽溶液之前，亦可先將水泥系漿料注入於混凝土 10之接觸於地盤之該側的面之周圍的地盤中。 注入，由於可從注入系統28通過送液管27對設置在隧 道內之注入管6來進行，所以可在維持隧道的功能下進行 注入。該注入系統28可使用下列多重注入裝置，其係具備 :用以將地盤注入材料注入於各注入地點的地盤中之複數 條注入管、用以將該各注入管彼此相互連接之複數條送液 管、經由該送液管將地盤注入材料以液體輸送送至各注入 地點並經由注入管將注入材料注入於地盤中之複數個單柱 塞泵、用以在各注入地點中切換地盤注入材料的流路之複 -28- 1375742 數個流路切換閥、用以測量液體輸送之地盤注入材料的流 • 量及/或壓力之流量及壓力測量裝置、以及用以控制此等 •. 單柱塞泵、流路切換閥與流量及壓力測量裝置之集中管理 裝置。該裝置中，可使上述單柱塞泵動作，一邊藉由集中 管理裝置來控制該單柱塞泵與流量及壓力測量裝置，一邊 切換該地盤注入材料的流路而同時且連續地將地盤注入材 料注入於複數個注入地點。此外，藉由將送液管27設計爲 ,φ 較長，即使在遠離的場所，亦可控制注入。因此，即使在 地下鐵、下水道、電話線路等之基礎設施中，亦可在維持 此等的功能之狀態下進行地盤改良。圖中的圖號26爲車。 第4圖、第5圖係顯示依據多點地盤同時注入所進行之 地盤強化方法的一例之槪念圖。圖中，圖號3 1爲設置在應 將非鹼性二氧化矽溶液注入於地盤中之對象地盤的各注入 地點（注入點）之注入管。 第4圖、第5圖中，配置有6台單柱塞泵U1〜U 6，各單 Φ 柱塞泵分別具備動力源3 5，且分別經由送液管3 3及送液管 34連接於注入材料貯藏槽32及各注入地點的注入管31。此 外，注入管31經由流路切換閥38，連接36根於分別配置的 各送液管33。圖號37爲流量及壓力測量裝置，39爲監視盤 ’ 40爲單柱塞泵的驅動指示系統，41爲流量指示系統，42 爲注入液閥開閉系統。 因此，該方法中，在依據集中管理裝置36所進行之總 括管理下，可藉由36台單柱塞泵U1〜U6，經由合計6x6 = 36 根的注入管31同時且連續地注入非鹼性二氧化矽溶液，所 -29- 1375742 以可飛躍性地提升裝置的輕量化及作業性。此外，藉由使 各注入地點的流路切換閥38連續地動作，可選擇性且連續 地對各Y卜6軸上的任意注入管31進行送液。 再者，由於複數根各Y軸方向的送液管33與各X軸方 向的送液管34配置爲俯視呈方格狀，並且在送液管33與送 液管34的各交叉點上設置注入管31，而藉此可任意地選擇 注入管31，因此，亦可對應於地盤或考量到地中結構物的 存在來進行注入材料的注入，而能夠進行嚴謹的地盤改良 〇 當注入地點愈多且注入地點的間隔愈窄時，愈可有效 率且確實地固鎖既定範圍的土，注入地點的數目和間隔， 可考量對象地盤的性狀或經濟性來適當地決定。通常，注 入管的間隔，較佳是因應地盤的性狀等，在〇.5m〜4.0m的 範圍內適當地設定。惟限制既定區域的土並予以固鎖時， 如第5圖所示，較佳係至少在3處設置注入地點。 使用該注入系統時，如圖示般，甚至只需在既定的注 入區域設置多數個注入孔，即可將運轉路線或注入溝配置 在中空部且同時使用中空部，並且可從特定的集中管理室 或地上部來進行注入作業。 第6圖係顯示將非鹼性二氧化矽溶液注入於住宅周圍 的基礎地盤之方法之圖。於結構物（住宅）13周圍的基礎 地盤（限制系區域），注入具有螯合效應之非鹼性二氧化 矽溶液（罩護二氧化矽溶液）8以改良地盤》此外，在未 接觸於結構物13之地盤（開放系區域），注入螯合效應弱 *30- 1375742 (或無螯合效應）之非鹼性二氧化矽溶液9。 * 於改良的地盤中，當以周圍具有地下水的流動並引起 •. 離子的擴散之地盤作爲開放系區域，以周圍存在有結構物 、不透水的地盤、及由注入材料進行改良的地盤等而未引 起離子的擴散之地盤，或是擴散較緩慢之地盤，作爲限制 系區域時，限制系區域中，由於長期來看離子有接觸於結 構物之可能性，故藉由注入具有螯合效應之非鹼性二氧化 φ 矽溶液，可抑制對結構物之影響。尤其在地盤內含有較多 硫酸離子或氯離子時，或是以硫酸系的注入材料對結構物 的周圍進行改良而使結構物附近成爲封閉區域時，在結構 物附近設置具有螯合效應之非鹼性二氧化矽溶液的注入區 域者，乃爲有效。 第7圖係顯示將非鹼性二氧化矽溶液注入於道路或機 場跑道附近的地盤之方法之圖。於道路14附近的地盤（限 制系地盤）之下方的未固結區域1 8下，注入具有螯合效應 # 之非鹼性二氧化矽溶液（罩護二氧化矽溶液）8以改良地 盤。此外，當道路1 4相當於堤防的混凝土結構物時亦相同 。再者，於該下方的地盤（開放系區域），注入螯合效應 弱（或無螯合效應）之非鹼性二氧化矽溶液9。 第8圖係顯示將非鹼性二氧化矽溶液注入於槽的基礎 地盤之方法之圖。於槽等的槽狀結構物15正下方之地盤（ 限制系地盤），注入具有螯合效應之非鹼性二氧化矽溶液 (罩護二氧化矽溶液）8以改良地盤（內部正下方改良區 )。此外，在未接觸於槽等的結構物15之外周及下方的層 -31 - 1375742 (開放系區域）之地盤’注入螯合效應弱（或無螯合效應 )之非鹼性二氧化矽溶液9(外部改良區）。圖中，圖號 8 a爲具有螯合效應之非鹼性二氧化矽溶液（罩護二氧化矽 溶液），16爲液狀化層，17爲非液狀化層。 [實施例] 以下藉由實施例來說明本發明，但本發明並不限定於 此等實施例。 (關於反應生成物） (實驗例1 ) 將作爲酸性中和劑的硫酸、與摻入有螯合劑之硫酸及 螯合劑，分別以水稀釋並加入於二氧化矽溶液（水玻璃） 62ml中，並調配爲全量成爲400ml，測定凝膠時間及PH » 此時的二氧化矽濃度係調整爲使調配液成爲6質量％。該結 果如第9圖及第10圖所示。在此，螯合劑爲75%的磷酸，硫 酸爲75%的硫酸。 第9圖係顯示硫酸、摻入有螯合劑的硫酸及螯合劑的 各酸量與凝膠時間之關係之圖表。此外，第10圖係顯示硫 酸、摻入有螯合劑的硫酸及螯合劑的各pH與（2(TC )凝膠 時間之關係之圖，其係依據下列實施例1 (調配1、調配4 、調配5 )者。 從第10圖中，可得知在硫酸單獨、摻入有螯合劑的硫 酸及螯合劑單獨的情形時，pH與凝膠時間之關係均相同， -32- ⑧ 1375742 pH愈低凝膠時間愈長，在pH3附近得到10〇〇分鐘的凝膠時 * 間。此外，當僅使用磷酸作爲硬化劑時，同一 pH時，與使 用硫酸時相比，必須對二氧化矽溶液添加多量（參照第9 圖及第10圖）。凝膠化時間與pH之關係，不論是磷酸或硫 酸，該強度均相同（參照第10圖）。另一方面，調節凝膠 化時間者，磷酸較硫酸更容易進行（參照第9圖）。相對 於此，雖然硫酸對於凝膠化時間的調節較困難，但即使是 ,φ 少量的添加量不同，亦可大幅改變pH，在同一二氧化矽濃 度、同一 pH、同一凝膠時間下每單位注入地盤體積的硫酸 使用量，可較使用磷酸時更少。因此，水溶反應生成物的 量可較少，且成本亦可抑制較低。 (反應生成物的溶出） (實驗例2 ) 在注入於地盤中之藥液成分之中，未構成凝膠之成分 φ 和未反應而殘留之成分，係被封閉在凝膠中或存在於凝膠 與土粒子之間隙，或是附著於此等的表面並殘留於固結物 中，當固結物暴露在地下水中時，此等除了已凝膠化之二 氧化矽以外的反應生成物，會滲透至地下水中並擴散。以 下係顯示出反應生成物從固結物溶出之例子。 (測定條件） 將非鹼性二氧化矽溶液與豐浦砂混合’製作出直徑 5 cm X高1 〇cm的試體’並以1 〇倍的水進行養護。2 8天後， -33- 1375742 測定溶出於水中之成分。下列第3表係顯示使用硫酸時（ 下列第4表中所示之調配1)與使用磷酸作爲螯合劑時（下 列第4表中所示之調配5 )，測定相對於添加量之溶出率的 結果。 [第3表] 調配1 調配5 溶出率(％) 44.2 43.8 滲透28天後之固結標準砂的養護水中所溶出之p〇43·、 S〇42'，約爲40〜50%«此外，幾乎無Si02的溶出，而Na幾 乎溶出全量。在實際注入於地盤時，可得知藥液成分之中 未成爲凝膠的構成要素之化學成分，亦即水玻璃的鈉或水 溶性反應生成物，係相對較早溶出且被地下水稀釋，並且 該擴散在地下水的開放方向上較快進行，但在封閉的地盤 中，此等成分容易殘留。 因此，可得知由於酸性中和劑的添加量以硫酸者較少 ，所以從二氧化矽溶液的固結砂所溶出之反應生成物，亦 以使用硫酸之情形較少。從以上的試驗結果中，可得知在 使混凝土結構體等之周邊的注入區域固結時，爲了減少水 溶反應生成物並防止混凝土的劣化，將含有螯合劑之二氧 化矽溶液注入於混凝土結構體等的附近區域，並在遠離混 凝土結構體等之區域中，藉由含有硫酸的非鹼性二氧化矽 溶液，或是含有磷酸化合物及/或金屬離子封鎖劑較混凝 土附近更少之二氧化矽溶液來進行固結者，乃爲有效。實 際上，由於在地盤中形成較大固結體，所以反應生成物的 溶出，當固結體愈大或地盤的遮水性愈小時，愈成爲長期 -34- 1375742 間，再者，若經由結構物所遮蔽，則愈會以長期間對地下 結構物或水質造成影響。 (實施例1 ) 爲了觀察非鹼性二氧化矽溶液中的磷酸化合物對具有 中空部之混凝土結構物所帶來的罩護效果，係使用第11圖 所示之實驗裝置，來觀察對混凝土水泥砂漿之影響。首先 φ 將內部具有直徑lcm的空洞5之直徑5cm、高10cm的筒狀水 泥砂漿試體1，設置在體積500cm3 (直徑m = 7cm、高13cm )的容器中，將相當於與水泥砂漿試體1同體積且厚度成 爲lcm之螯合系非鹼性二氧化矽2A充塡於水泥砂漿試體1 的外周使其凝膠化後，以非螯合系非鹼性二氧化矽2B充塡 該周圍使其凝膠化。以使對水泥砂漿之影響僅位於側面之 方式，藉由石蠟4將水泥砂漿試體1、螯合系非鹼性二氧化 矽固結體2A、非螯合系非鹼性二氧化矽固結體2B的上部密 φ 閉，並觀察經過一年後對水泥砂漿試體之影響。此外，爲 了觀察在地下水存在下藥液2A、2B對混凝土結構物之影響 ，係將上述固結物裝入於直徑n = 2 0 cm的密閉容器3，並充 塡2000ml的養護水19於凝膠周圍，並評估經過一年後對混 凝土之影響。 充塡於第11圖所示的容器中之藥液2A、2B，係以下列 第5表所示之組合來使用下列第4表所示之調配者，並將硫 酸單獨、磷酸單獨、硫酸與磷酸兩者作爲硬化劑分別調配 於二氧化矽溶液，並將凝膠化時間設爲1天。下列第4表中 -35- 1375742 ，二氧化砂溶液使用3號水玻璃，硫酸使用75%硫酸，螯合 劑使用7 5 %磷酸。此外，下列第5表中，硬化劑中的螯合劑 係使用做爲磷酸系化合物之磷酸。 藉由養護後的外觀及中空水泥砂漿的單軸壓縮強度， 來評估因螯合濃度（磷離子濃度）的不同而對密閉狀態下 的水泥砂漿試體1所造成之影響。下列第5表係顯示經過一 年後的結果。對水泥砂漿試體之影響，係與同養護期間中 進行水養護後的水泥砂漿比較，並以下列方式進行評估。 此外，測定出固結體2A於一年後的pH之結果，亦一同顯 示於下列第5表。 〇：顯現出同等或以上之強度，外觀無變化 △:顯現出同等強度，外觀觀察到一部分劣化 X :觀察到部分破損Further, in the present invention, a chelating agent other than phosphoric acid may be used to remove the alkali non-alkaline cerium oxide by sulfuric acid or phosphoric acid to form a capped cerium oxide. A chelating agent other than phosphoric acid has a weak acidity, and when used alone, in order to remove an alkali, a large amount is required. In contrast, phosphoric acid not only removes alkali, but also has a protective effect when phosphoric acid is used alone, so that effective cerium oxide can be formed. Phosphoric acid compounds or chelating agents, together with cerium oxide, form a protective cerium oxide on concrete to prevent deterioration of concrete due to coexisting sulfuric acid or sulfate ions present in groundwater. Among the phosphoric acid compounds, sodium hexametaphosphate is a chelating agent, and a cerium oxide is formed on the surface of the concrete by chelation, but phosphoric acid or other phosphoric acid compound also forms a coating having the same effect, and therefore, in the present invention, The phosphoric acid compound is regarded as a chelating agent, and the cerium oxide solution containing this is referred to as a non-alkaline cerium oxide solution (covering a cerium oxide solution). Therefore, a chelating agent other than phosphoric acid is used in combination with phosphoric acid or barium sulfate to form a non-basic ceria solution. The use of phosphoric acid or phosphate as the non-alkaline cerium oxide solution is more effective than other chelating agents. The chelating agent used in the present invention has a chelate effect, and examples thereof include various acidic phosphates, neutral phosphates, and basic phosphates, and examples thereof include tetrapolyphosphate, hexametaphosphate, and tetrad. Phosphate, pyrophosphate, acidic hexametaphosphate, condensed phosphates such as acid pyrophosphate, etc., -22-8 1375742 The condensed phosphate is preferably a sodium salt. The phosphoric acid compound which forms a non-basic cerium oxide solution is preferred because it can form a particularly strong protective oxidizing agent. Further, the chelating agent may be, in addition to the above-mentioned phosphoric acid compound, ethylenediaminetetraacetic acid, nitrogen triacetic acid, gluconic acid, tartaric acid or a salt of such an acid, etc. In the present invention, the phosphoric acid compound may be used in a cerium oxide solution. In the presence of the surface, the most effective coating is formed on the concrete surface. Further, in the present invention, a hardener having no chelation effect can also be used. φ The curing agent may be a sulfide such as sulfuric acid, a chloride such as hydrochloric acid, an acid salt, a carbonate, a hydrogencarbonate, a carbonic acid gas, a carbonated water, an aluminate, a glyoxal or a vinyl carbonate. , polyacetate and the like. In addition, cement, lime, slag, etc. can be used alone as a hardener or in combination with other hardeners. In this case, a compound having a chelate effect such as the above-mentioned phosphate compound can be mixed with a hardener having no chelation effect, and the mixing ratio can be selected in accordance with the environment of the ground to be injected. Further, a non-alkaline cerium oxide solution may be injected into a peripheral portion of a structure such as a concrete structure, and a solution slurry of any alkali-based water glass injection or cement may be injected. The outer area. Of course, a polymer material having a gelation function such as an amine resin or an acrylate may be added. In the method of injecting a site of the present invention, specifically, when a non-alkaline ceria solution containing the above chelating agent as an active ingredient is injected into a land surrounded by a structure in the soil to improve the ground plate, The non-alkaline ceria solution is injected so that the content of the chelating agent in the ground is 36 g or more per lm2 of the surface of the structure in the soil, preferably 50 g to 1 000 g. By this, -23- 1375742 can suppress the influence of the water-soluble reaction product of the cerium oxide slurry to a minimum, and can suppress the environmental load of the water quality and maintain the concrete structure, and can be consolidated with good durability. When the content of the chelating agent in the above-mentioned site is less than 36 g, it may not be possible to sufficiently form the cerium oxide which does not invade the sulfate ion or the seawater, and the desired effect of the present invention cannot be obtained. Further, in the method of injecting the ground of the present invention, the ion content of the chelating agent in the non-basic ceria solution is set to be 3000 ppm or more, preferably 3000 ppm to 120,000 ppm, and the structure of the consolidated layer is separated from the soil. The thickness of the surface of the object is set to 1 cm or more, preferably 1 cm to 30 cm, in terms of a homogenous gel (Homo-Gel), whereby the same effects as described above can be obtained. When the ion content of the chelating agent in the above-mentioned site is less than 3000 ppm or the thickness of the above-mentioned consolidated layer is less than 1 cm, a bubble or an uninjected region is partially formed, so that groundwater penetrates from the portion, and the sulfate ion or seawater contacts the concrete structure. The desired effect of the present invention cannot be obtained. Further, in the method of injecting the ground of the present invention, in the non-basic ceria solution, at least the ceria solution component containing the chelating agent is brought into contact with the soil earlier than the cerium oxide solution component other than the chelating agent. The intermediate structure can also form a protective cerium oxide on the surface of the structure in the soil before the intrusion of the sulfate ion, thereby obtaining the same effect as described above. Further, in the site injecting method of the present invention, the cerium oxide concentration [SiO 2 ] (% by mass) of the non-basic cerium oxide solution satisfies 2% by mass of [Si02] S 50% by mass, and contains a phosphoric acid compound as The phosphorus ion concentration [P] (ppm) of the non-basic ceria solution of the chelating agent satisfies 3000 ppm S [P] S 1 20000 ppm, whereby the desired effect of the present invention can also be obtained. -24- 1375742 In the present invention, in order to produce a strong coating film, the concentration of cerium oxide is also important. Thereby, the effect of the water-soluble reaction product of the cerium oxide slurry can be suppressed to a minimum, and the environmental load of the water quality can be suppressed, the concrete structure can be maintained, and the durability can be consolidated. At this time, after the component containing the phosphoric acid compound in the non-basic ceria solution is injected into the land surrounding the building in the soil, it is preferred to use the sulfuric acid in the non-alkaline ceria solution. The compound is used as an active ingredient, and a component of φ is injected around the injection region containing the component of the phosphoric acid compound. The phosphorus ion concentration [P] (ppm) of the sulfuric acid compound component is set in the range of 0S [P] S3 00 00 ppm, thereby protecting the structure of the soil from sulfate ions and/or seawater. And the reaction product can be reduced more. Further, at this time, the non-alkaline cerium oxide solution is cerium oxide containing water glass, and the cerium oxide concentration [Si 〇 2] (% by mass) of the non-basic cerium oxide solution preferably satisfies 2% by mass S [ Si02] S 10% by mass. Thereby, the following effects can be obtained, that is, a sufficient amount of the cover cerium oxide to form a film on the surface of the concrete structure in combination with the chelating agent is formed. Further, at this time, the ratio of the phosphorus ion concentration [P] (ppm) containing the composition of the phosphoric acid compound in the non-basic ceria solution to the cerium oxide concentration [3102] (% by mass) is set as [P] /[SiO2] = 60 to 5000, whereby a more robust film can be formed by a metal ion blocking agent. Further, the thickness of the solidified layer containing the above-mentioned phosphate ions is 0.5 m or more from the surface of the structure in the soil, for example, lm or more, and is less than half the length of the injection region, whereby the effect of surely protecting the concrete can be obtained. . Further, in the present invention, in order to minimize the amount of the chelating agent used in the entire injection region, and to minimize the total amount of the sulfuric acid compound coexisting with the phosphoric acid compound, the structure and the injection in the soil are considered. The combination of the positional relationship of the regions containing the acidic reactants of the cerium oxide solution is important. Further, the cerium oxide solution is shielded from Ca or Mg ions on the surface of the concrete even in the presence of sulfuric acid or seawater, and a strong coating layer which enters the concrete surface is formed by the chelating reaction. The formation of cerium oxide having a protective effect of concrete is generally required to be non-alkaline, preferably acidic. When a base remains in the cerium oxide solution, the formation of the coating layer on the surface of the concrete is insufficient, and the protective effect of the concrete is lowered. Therefore, the site injecting method of the present invention uses a cerium oxide solution as a main component, a phosphoric acid compound, or a non-alkaline cerium oxide solution containing a phosphoric acid compound and a sulfuric acid compound as an active ingredient, and is applied by pH 値a site injection method in which a neutral to acidic region is formed to form a gelation property, or a non-alkaline ceria solution with a phosphoric acid compound as an active ingredient and a sulfuric acid compound as an active ingredient in the region of the injection site The non-alkaline cerium oxide solution is used to inject the site where the site is consolidated. In the method of injecting the ground of the present invention, it is possible to suitably use the liquidification countermeasure project, the anti-deterioration or the repairing work of the structure in the soil, and obtain the structure of the protective soil from the sulfate ion or chlorine contained in the groundwater in the ground. The effect of the influence of ions. In particular, the present invention is suitable for prevention of repair or liquidation of a subterranean structure having a hollow portion and in which the component of the injection liquid is wetted together with the groundwater or flows into the hollow portion. In the present invention, it is preferred that the cement slurry is injected into the earth structure of the concrete structure or the like before the non-alkaline ceria solution is injected into the earth -26-1375742. In the ground around the face of the side. Here, the term "concrete surface" refers to the surface of the concrete structure that is in contact with the ground. In the present invention, since the water-soluble reaction product eluted when the consolidated ground using the non-alkaline ceria solution is contacted with groundwater or the like is a problem object, at least a part of the structure in the soil exists under the groundwater surface. The case of φ is a prerequisite. Further, in the case where one of the wall surfaces constituting the structure of the soil faces the ground surface and the other surface faces the atmosphere, in addition to the above-described structure having the hollow portion, a part of the structure including the hollow portion is also constructed in the soil and is constructed on other parts as described later. The mourning of the structure. In the present specification, the concrete structure is basically described. However, the so-called soil structure of the present invention also includes a structure composed of metal or the like as described above. In this case, as in the case of the concrete structure, By applying the present invention, the desired effect can be obtained. The soil structure such as a concrete structure to which the present invention can be applied includes a tunnel having a hollow portion, a subway, a mountain tunnel, a shield, a wire, or a telephone line, a gas pipe, a water pipe, and the like. The common ditch of the basic equipment, as well as the lower part of the laying site. The specific example is shown below. Fig. 2 is a view showing a state in which a non-alkaline cerium oxide solution is injected into a ground plate and consolidated in the construction of a common trench. It is shown that a non-alkaline cerium oxide solution having a chelation effect is injected into the peripheral region 8 of the concrete structure 10 scheduled to be constructed after excavation via the injection pipe 6, and a chelation effect is set in the peripheral portion region. The case of the weak (or no chelation effect) non-alkaline -27-1375742 cerium dioxide slurry injection zone 9. Further, Fig. 3 is a view showing a method of injecting a non-alkaline ceria solution into a ground around the underground structure. At this time, as shown in the figure, the surface of the underground structure 10 facing the atmosphere can be drilled, and an injection hole is provided in the underground structure 10, and injection is performed through the injection hole. That is, in order to prevent the groundwater containing groundwater 24 of S042 or seawater, or the concrete 10 of the tunnel constructed in the volcanic deposit, or to repair the common trench or underground tunnel of the decay, the hole is drilled from the inside of the tunnel 25. And in the region 8 of the ground (restriction system region) around the underground structure 10, a non-alkaline cerium oxide solution having a chelating effect (covering the cerium oxide solution) is injected. Further, since the concrete 10 in the ground surface may be deteriorated due to the sulfate ions or chloride ions contained in the ground water or the injection liquid, the non-alkaline cerium oxide solution is injected into the surface of the concrete 10 contacting the side of the ground plate. In the surrounding site, to prevent or repair the deterioration of concrete. Further, before the injection of the non-basic cerium oxide solution, the cement slurry may be first injected into the ground of the concrete 10 which is in contact with the surface on the side of the ground. Since the injection can be performed from the injection system 28 through the liquid supply pipe 27 to the injection pipe 6 provided in the tunnel, the injection can be performed while maintaining the function of the tunnel. The injection system 28 can use the following multiple injection devices, which are provided with a plurality of injection tubes for injecting the ground injection material into the ground of each injection site, and a plurality of liquid feedings for connecting the injection tubes to each other. a tube, a plurality of single-plunger pumps that inject a material into the material through the liquid supply tube and transport the liquid to each injection site and inject the injection material into the ground through the injection tube, and switch the material of the ground plate at each injection site. Flow path -28- 1375742 Several flow path switching valves, flow and pressure measuring devices for measuring the flow rate and/or pressure of the material injected into the ground for liquid transport, and for controlling such a single plunger Centralized management of pumps, flow path switching valves and flow and pressure measuring devices. In the apparatus, the single plunger pump can be operated, and the single plunger pump and the flow rate and pressure measuring device are controlled by the centralized management device, and the flow path of the ground injection material is switched while the ground is continuously injected. The material is injected into a plurality of injection sites. Further, by designing the liquid supply pipe 27 such that φ is long, the injection can be controlled even in a remote place. Therefore, even in infrastructures such as subways, sewers, and telephone lines, site improvement can be performed while maintaining such functions. Figure 26 in the figure is a car. Fig. 4 and Fig. 5 are views showing an example of a method of reinforcing the ground according to simultaneous injection of a multi-point site. In the figure, Fig. 31 is an injection pipe provided at each injection point (injection point) of a target site to which a non-alkaline ceria solution is to be injected into a ground plate. In the fourth and fifth figures, six single-piston pumps U1 to U6 are disposed, and each of the single-Φ plunger pumps is provided with a power source 35, and is connected to the liquid supply pipe 33 and the liquid supply pipe 34, respectively. The material storage tank 32 and the injection pipe 31 at each injection point are injected. Further, the injection pipe 31 is connected to each of the respective liquid supply pipes 33 disposed via the flow path switching valve 38. Figure 37 is the flow and pressure measuring device, 39 is the monitoring disk '40 is the single plunger pump drive indicating system, 41 is the flow indicating system, and 42 is the filling valve opening and closing system. Therefore, in this method, under the collective management by the centralized management device 36, the 36 single-piston pumps U1 to U6 can be simultaneously and continuously injected non-alkaline via a total of 6x6 = 36 injection pipes 31. The cerium oxide solution, -29- 1375742, can be used to dramatically increase the weight and workability of the device. Further, by continuously operating the flow path switching valve 38 at each injection point, it is possible to selectively and continuously supply liquid to any of the injection tubes 31 on each of the Y-axis. Further, the plurality of liquid supply tubes 33 in the Y-axis direction and the liquid supply tubes 34 in the respective X-axis directions are arranged in a square shape in plan view, and are provided at the intersections of the liquid supply tube 33 and the liquid supply tube 34. The injection pipe 31 is injected, whereby the injection pipe 31 can be arbitrarily selected. Therefore, the injection of the injection material can be performed corresponding to the presence of the ground or the structure in the ground, and the rigorous site improvement can be performed. The more narrow the interval between the injection sites, the more efficiently and surely the soil in a given range can be locked, and the number and spacing of the injection sites can be appropriately determined by considering the properties or economics of the target site. In general, the interval between the injection pipes is preferably set in a range of 〇5m to 4.0m in accordance with the properties of the ground plate or the like. However, when the soil of a predetermined area is restrained and locked, as shown in Fig. 5, it is preferable to set the injection site at least at three places. When the injection system is used, as shown in the figure, even if a plurality of injection holes are provided in a predetermined injection area, the operation route or the injection groove can be disposed in the hollow portion and the hollow portion can be used at the same time, and can be managed from a specific concentration. The chamber or the ground is used for the injection operation. Fig. 6 is a view showing a method of injecting a non-alkaline ceria solution into a base site around a house. In the base site (restriction system area) around the structure (residential) 13, a non-alkaline cerium oxide solution (covering cerium oxide solution) 8 having a chelating effect is injected to improve the site. In addition, the structure is not contacted. The site of the object 13 (open system) was injected with a non-alkaline ceria solution 9 having a weak chelation effect of *30 - 1375742 (or no chelation effect). * In the improved site, the ground with the flow of groundwater and the diffusion of ions is used as the open area, and there are structures, impervious sites, and sites modified by the injected materials. A site that does not cause the diffusion of ions, or a site that diffuses slowly, as a confinement region, in the confinement region, the possibility of contact with the structure in the long term, so that the implantation has a chelation effect Non-alkaline dioxide φ 矽 solution can inhibit the influence on the structure. In particular, when the site contains a large amount of sulfate ions or chloride ions, or when the periphery of the structure is modified with a sulfuric acid-based injection material to form a closed region in the vicinity of the structure, a chelate effect is provided in the vicinity of the structure. It is effective to inject the area of the alkaline cerium oxide solution. Figure 7 is a diagram showing a method of injecting a non-alkaline ceria solution into a site near a road or a stadium runway. A non-alkaline ceria solution (covering cerium oxide solution) 8 having a chelation effect # is injected to the unconsolidated region 18 below the site near the road 14 (restricted land) to improve the floor. In addition, the same is true when the road 14 is equivalent to the concrete structure of the embankment. Further, a non-alkaline ceria solution 9 having a weak chelation effect (or no chelation effect) is injected into the lower site (open system region). Fig. 8 is a view showing a method of injecting a non-alkaline ceria solution into a base plate of a tank. A non-alkaline cerium oxide solution (covering cerium oxide solution) 8 having a chelation effect is injected into a ground (restricted lands) directly below the groove-like structure 15 such as a groove to improve the ground (immediately under the improved area) ). Further, a non-alkaline cerium oxide solution having a weak chelate effect (or no chelation effect) is injected into the ground layer of the layer -31 - 1375742 (open system region) which is not in contact with the outer periphery of the structure 15 and the like. 9 (external improvement zone). In the figure, Figure 8a is a non-alkaline cerium oxide solution having a chelating effect (covering a cerium oxide solution), 16 is a liquidized layer, and 17 is a non-liquidized layer. [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to the Examples. (Reaction product) (Experimental Example 1) Sulfuric acid as an acidic neutralizing agent, sulfuric acid and a chelating agent doped with a chelating agent, respectively, were diluted with water and added to 62 ml of a cerium oxide solution (water glass). The blending amount was adjusted to 400 ml in total, and the gel time and pH were measured. The concentration of cerium oxide at this time was adjusted so that the preparation liquid became 6% by mass. The results are shown in Figures 9 and 10. Here, the chelating agent is 75% phosphoric acid and the sulfuric acid is 75% sulfuric acid. Fig. 9 is a graph showing the relationship between the amount of each sulfur acid and the gel time of sulfuric acid, sulfuric acid and a chelating agent doped with a chelating agent. Further, Fig. 10 is a graph showing the relationship between the respective pHs of sulfuric acid, sulfuric acid and a chelating agent doped with a chelating agent, and (2 (TC) gel time, which is based on the following Example 1 (mixing 1, blending 4, According to Fig. 10, it can be seen that the relationship between pH and gel time is the same when sulfuric acid alone and sulfuric acid and chelating agent doped with a chelating agent are the same, -32- 8 1375742 The longer the low gel time, the gel time between 10 and 10 minutes is obtained near pH 3. In addition, when only phosphoric acid is used as the hardener, at the same pH, the cerium oxide solution must be used as compared with the case of using sulfuric acid. Add a large amount (refer to Fig. 9 and Fig. 10). The relationship between gelation time and pH is the same regardless of phosphoric acid or sulfuric acid (see Fig. 10). On the other hand, the gelation time is adjusted. Phosphoric acid is easier to carry out than sulfuric acid (see Fig. 9). In contrast, although the adjustment of the gelation time by sulfuric acid is difficult, even if the amount of addition of φ is small, the pH can be greatly changed. Cerium oxide concentration, same pH, same gel time The amount of sulfuric acid used per unit volume of the injection site can be less than that when phosphoric acid is used. Therefore, the amount of the water-soluble reaction product can be reduced, and the cost can be suppressed to be low. (Solution of the reaction product) (Experimental Example 2) Among the chemical components injected into the ground, the component φ which does not constitute the gel and the component which remains unreacted are enclosed in the gel or exist in the gap between the gel and the soil particles, or are attached thereto. The surface remains in the solidified material. When the solidified material is exposed to groundwater, the reaction product other than the gelled cerium oxide penetrates into the groundwater and diffuses. The following shows the reaction. An example in which a product is dissolved from a solid. (Measurement conditions) A non-alkaline cerium oxide solution is mixed with Fengpu sand to prepare a sample having a diameter of 5 cm X and a height of 1 〇cm and is treated with 1 〇 of water. Maintenance. 2 After 8 days, -33- 1375742 measures the components dissolved in water. The following Table 3 shows the use of sulfuric acid (1 shown in Table 4 below) and the use of phosphoric acid as a chelating agent (4th below) The preparation shown in the table 5), determination The result of the dissolution rate of the added amount. [Table 3] Formulation 1 Preparation 5 Dissolution rate (%) 44.2 43.8 p〇43·, S〇42' dissolved in the curing water of the consolidated standard sand after 28 days of infiltration About 40 to 50% «In addition, almost no SiO 2 is eluted, and Na is almost completely dissolved. When actually injected into the site, it is known that the chemical component of the component which is not a gel among the components of the liquid, that is, water The sodium or water-soluble reaction product of the glass is relatively early dissolved and diluted by the groundwater, and the diffusion proceeds relatively quickly in the open direction of the groundwater, but in a closed site, these components are liable to remain. It is known that since the amount of the acidic neutralizing agent added is small in sulfuric acid, the reaction product eluted from the fixed sand of the cerium oxide solution is also less likely to be used in the case of using sulfuric acid. From the above test results, it is found that when the injection region around the concrete structure or the like is consolidated, the cerium oxide solution containing the chelating agent is injected into the concrete structure in order to reduce the water-soluble reaction product and prevent deterioration of the concrete. In the vicinity of the body, and in a region away from the concrete structure, etc., by a non-alkaline cerium oxide solution containing sulfuric acid, or a phosphoric acid compound and/or a metal ion blocking agent is less oxidized than near the concrete. It is effective to use a solution to carry out the consolidation. In fact, since a large solidified body is formed in the ground, the dissolution of the reaction product, as the solidified body becomes larger or the water repellency of the ground plate becomes smaller, becomes a long-term -34 - 1375742, and further, if the structure is If the object is covered, it will affect the underground structure or water quality for a long period of time. (Example 1) In order to observe the effect of the phosphoric acid compound in the non-basic ceria solution on the concrete structure having a hollow portion, the experimental apparatus shown in Fig. 11 was used to observe the concrete cement. The effect of mortar. First, a cylindrical cement mortar sample 1 having a diameter of 5 cm and a height of 10 cm and having a cavity 5 having a diameter of 1 cm inside is placed in a container having a volume of 500 cm 3 (diameter m = 7 cm, height 13 cm), which is equivalent to a cement mortar sample. 1 The chelating non-alkaline cerium oxide 2A having the same volume and having a thickness of 1 cm is filled on the outer periphery of the cement mortar sample 1 to be gelated, and then filled with non-chelating non-alkaline cerium oxide 2B. It gels around it. The cement mortar test body 1, the chelated non-alkaline ceria consolidated body 2A, and the non-chelating non-alkaline ceria are consolidated by paraffin 4 so that the effect on the cement mortar is only on the side. The upper part of the body 2B was closed tightly, and the influence on the cement mortar sample after one year was observed. In addition, in order to observe the influence of the liquid chemicals 2A, 2B on the concrete structure in the presence of groundwater, the above-mentioned consolidation is placed in a closed container 3 having a diameter of n = 20 cm, and is filled with 2000 ml of the curing water 19 for coagulation. Around the glue and evaluate the effect on the concrete after one year. The liquid medicines 2A and 2B which are filled in the container shown in Fig. 11 are used in the combination shown in the following Table 5, and the formulae shown in the following Table 4 are used, and sulfuric acid alone, phosphoric acid alone, sulfuric acid and Phosphoric acid was separately formulated as a hardener in a cerium oxide solution, and the gelation time was set to 1 day. In the following Table 4 -35-1375742, the sand dioxide solution uses No. 3 water glass, the sulfuric acid uses 75% sulfuric acid, and the chelating agent uses 75% phosphoric acid. Further, in the following Table 5, the chelating agent in the curing agent is a phosphoric acid which is a phosphate compound. The effect of the cured cement mortar 1 in the closed state was evaluated by the appearance of the cured product and the uniaxial compressive strength of the hollow cement mortar to determine the chelating concentration (phosphorus ion concentration). The following Table 5 shows the results after one year. The impact on the cement mortar test body is compared with the cement mortar after water curing in the same curing period, and is evaluated in the following manner. Further, the results of measuring the pH of the consolidated body 2A after one year are also shown together in Table 5 below. 〇: The same or above strength is exhibited, and the appearance is unchanged. △: The same strength is exhibited, and a part of the appearance is observed to be deteriorated. X: Partial damage is observed.

⑧ -36- 1375742 [第4表] \ 全量400m 1 全溶液中的 螯合離 (ppm) 全溶液中的 S〇4濃度 (ppm) 注入液 的pH (20t：) 二氧化 矽溶液 硬化劑 水 調配1 62ml 硫酸(無螯合） 8.5ml 殘餘 0 26,150 3.02 調配2 62ml 硫酸(有螯合劑） 9ml 殘餘 1,890 25,670 3.01 調配3 62ml 硫酸(有螯合劑） 10ml 殘餘 3,000 27,400 2.60 調配4 62ml 硫酸(有螯合劑） 12ml 殘餘 17,230 18,460 2.64 調配5 62ml 螯合劑 19ml 殘餘 55,000 0 3.01 調配6 104ml 硫酸(有螯合劑） 28.5ml 殘餘 30,000 50,000 2.81 調配7 104ml 螯合劑 34.5ml 殘餘 100,000 0 3.11 調配8 62ml 硫酸(有螯合劑） ※l 14ml 8g 殘餘 12,600 43,070 2.40 調配9 膠體二 氧化矽 10ml 水玻璃 52ml 硫酸(有螯合劑） 10ml 殘餘 14,360 15^80 3.12 調配10 62ml 硫酸(有螯合劑） 3ml 殘餘 3,000 8,100 11.40 調配11 ※之 10ml 螯合劑 3ml 殘餘 8,700 0 3.21 調配12 ※3 20.7ml 螯合劑 6.5ml 殘餘 18,800 0 2.988 -36- 1375742 [Table 4] \ Full amount 400m 1 Chelation in total solution (ppm) S〇4 concentration in whole solution (ppm) pH of infusion solution (20t:) Ceria solution hardener water Formulation 1 62ml Sulfuric acid (no chelation) 8.5ml Residue 0 26,150 3.02 Formulation 2 62ml Sulfuric acid (with chelating agent) 9ml Residue 1,890 25,670 3.01 Blending 3 62ml Sulfuric acid (with chelating agent) 10ml Residual 3,000 27,400 2.60 Blending 4 62ml Sulfuric acid Mixture) 12ml Residue 17,230 18,460 2.64 Blend 5 62ml Chelating agent 19ml Residual 55,000 0 3.01 Blending 6 104ml Sulfuric acid (with chelating agent) 28.5ml Residual 30,000 50,000 2.81 Blending 7 104ml Chelating agent 34.5ml Residual 100,000 0 3.11 Blending 8 62ml Sulfuric acid Mixture) ※l 14ml 8g Residual 12,600 43,070 2.40 Formulation 9 Colloidal cerium oxide 10ml Water glass 52ml Sulfuric acid (with chelating agent) 10ml Residue 14,360 15^80 3.12 Blending 10 62ml Sulfuric acid (with chelating agent) 3ml Residual 3,000 8,100 11.40 Blending 11 ※ 10ml chelating agent 3ml residual 8,700 0 3.21 compounding 12 ※3 20.7ml chelating agent 6.5ml residual 18,800 0 2.98

※工）使用六偏磷酸鈉作爲螯合劑 ※2)調配11 :二氧化矽濃度1質量％ ※3 )調配12 :二氧化矽濃度2質量％ -37- 1375742 [第5表] \ 固結體 2Α 固結體 經過1年後的模樣 固結體2A 固結體2B 固結體全量 密閉養護 水中養護 磷酸 離子量 (mg) 硫酸 離子量 (mg) 磷酸 離子量 (mg) 硫酸 離子量 (mg) 磷酸 離子置 (mg) 硫酸 離子量 (mg) 總離 子量 (mg) 2Β 水泥砂 漿試體 的劣化 凝膠的 PH ※4 水泥砂 漿試體 的劣化 比較例1-1 ^S3 I 調配1 X 11.16 X 0 4,927 0 14,780 0 19,707 19,707 比較例1-2 調配2 調配1 △ 9.82 Δ 356 4,836 0 14,780 356 19,616 19,972 實施例1-1 調配3 調配1 Δ 7.92 〇 565 5,162 0 14,780 565 19,942 20,507 實施例1-2 調配4 調配1 〇 7.41 〇 3*246 3,478 0 14,780 3^46 18*258 2U〇4 實施例1-3 調配5 調配1 〇 7.08 〇 10,362 0 0 14,780 10,362 14,780 25,142 實施例 調配6 調配1 〇 7.42 〇 5,652 9,420 0 14,780 5,652 24,200 29,852 實施例1-5 調配7 調配1 〇 732 〇 18,840 0 0 14,780 18,840 14,780 33,620 實施例1·6 調配8 調配1 〇 7.44 〇 2*374 8,114 0 14,780 2^74 22,894 25*268 實施例1-7 調配9 調配1 〇 7.30 〇 2,705 2,898 0 14,780 2,705 17,678 20383 實施例1*8 調配3 調配2 Δ 7.80 〇 565 5,162 1,068 14,509 1,633 19,671 2\β04 實施例1-9 調配3 調配3 〇 7.77 〇 565 5,162 1,969 15,486 2,534 20,648 23,182 實施例1-10 調配4 調配4 〇 7.38 〇 3^46 3,478 9,738 10,434 12,984 13,912 26,896 比較例1-3 調配10 調配1 X 11.50 X 565 1,526 0 14,780 565 16306 16,871 實施例丨-11 調配11 調配1 △ 9.91 Δ 1,639 0 0 14,780 1,639 14,780 16,419 實施铜1-12 調配12 調配1 〇 7.62 〇 3,541 0 0 14,780 3^42 14,780 18,322※Working) using sodium hexametaphosphate as a chelating agent ※2) Preparation 11: cerium oxide concentration 1% by mass *3) Preparation 12: cerium oxide concentration 2% by mass -37- 1375742 [Table 5] \Consolidation 2Α Consolidated body after 1 year of solidified body 2A Consolidated body 2B Consolidated body Fully enclosed in conserving water Conservation phosphate ion amount (mg) Sulfate ion amount (mg) Phosphate ion amount (mg) Sulfate ion amount (mg) Phosphate ion (mg) Sulfate ion amount (mg) Total ion amount (mg) 2Β PH of deteriorated gel of cement mortar sample *4 Deterioration of cement mortar sample Comparative Example 1-1 ^S3 I Blending 1 X 11.16 X 0 4,927 0 14,780 0 19,707 19,707 Comparative Example 1-2 Preparation 2 Preparation 1 △ 9.82 Δ 356 4,836 0 14,780 356 19,616 19,972 Example 1-1 Preparation 3 Preparation 1 Δ 7.92 〇565 5,162 0 14,780 565 19,942 20,507 Example 1-2 Blending 4 Blending 1 〇7.41 〇3*246 3,478 0 14,780 3^46 18*258 2U〇4 Example 1-3 Blending 5 Blending 1 〇7.08 〇10,362 0 0 14,780 10,362 14,780 25,142 Example Alignment 6 Dispensing 1 〇7.42 〇 5,652 9,420 0 14,780 5,652 24,200 29,852 Examples 1-5 With 7 rations 1 〇 732 〇 18, 840 0 0 14,780 18,840 14,780 33,620 Example 1·6 Preparation 8 Preparation 1 〇7.44 〇2*374 8,114 0 14,780 2^74 22,894 25*268 Example 1-7 Preparation 9 Preparation 1 〇7.30 〇 2,705 2,898 0 14,780 2,705 17,678 20383 Example 1*8 Formulation 3 Formulation 2 Δ 7.80 〇565 5,162 1,068 14,509 1,633 19,671 2\β04 Example 1-9 Preparation 3 Preparation 3 〇7.77 〇565 5,162 1,969 15,486 2,534 20,648 23,182 Example 1-10 Preparation 4 Preparation 4 〇7.38 〇3^46 3,478 9,738 10,434 12,984 13,912 26,896 Comparative Example 1-3 Preparation 10 Preparation 1 X 11.50 X 565 1,526 0 14,780 565 16306 16,871 Example 丨-11 Preparation 11 Preparation 1 △ 9.91 Δ 1,639 0 0 14,780 1,639 14,780 16,419 Implementing copper 1-12 Blending 12 Blending 1 〇7.62 〇3,541 0 0 14,780 3^42 14,780 18,322

※斗）容器內部之凝膠化物的pH 從上述第5表中可得知下列內容。 比較例1-1中，密閉養護與水養護，於1年後該pH均達 1 1以上，水泥砂漿試體1的一部分產生損壞。比較例1-2中 ，密閉養護與水養護，於1年後均觀察到外觀的一部分劣 化，凝膠的pH達到10。另一方面，實施例1-2~實施例1-7 及實施例1 -9中，密閉養護與水養護，於養護後之水泥砂 槳試體1的表面均可觀察到白色被覆，1年後（3年後亦相 同）之凝膠的pH値幾乎保持中性値，單軸壓縮強度相對於 -38- 1375742 經過時間之上升，亦得到較比較例1 -1之經離子交換水養 • 護後的水泥砂漿試體1更爲上升之結果。 - 實施例1-1、實施例1-8，爲在固結體2A中添加有形成 罩護二氧化矽之最少量的螯合劑者，密閉養護時，水泥砂 漿試體1的表面可觀察到白色被覆，且未觀察到強度的劣 化，但在混凝土表面觀察到若干劣化。水養護時，未觀察 .到混凝土的劣化。比較例1 -3，爲密閉養護與水養護兩者 φ 均在鹼側形成凝膠化者，在混凝土表面幾乎未形成白色被 覆，且於1年後亦觀察到劣化。 從該結果中，可得知在實施例1-1~實施例1-9中，由 於白色被膜的作用使混凝土中的鹼未溶出，同時可防止 S042·對混凝土之侵入。相對於此，在無螯合劑之比較例1-1、1_2中，混凝土中的鹸溶出而產生劣化（中性化）。從 該結果中，可得知螯合濃度未達3000 ppm時，白色被覆的 形成不足’無法抑制混凝土的劣化。此外，從比較例1 -3 # 中，可得知在鹼區域中，即使螯合濃度爲3 000 ppm以上， 白色被覆幾乎未形成或是白色被覆的形成不足，在硫酸的 存在下無法抑制混凝土的劣化。從上述內容中，可得知作 爲罩護二氧化矽溶液之效果，在使用去除鹼之非鹼性二氧 化矽溶液時乃爲顯著。此外’在實施例1-11中使用二氧化 矽濃度1質量％的調配1 1作爲固結體2A，在實施例1-12中使 用二氧化矽濃度2質量％的調配12作爲固結體2A，其結果 在實施例1 -1 1中’混凝土表面僅形成少許白色被覆，並觀 察到凝膠的PH1升’相對於此，在實施例1-12中，形成有 -39- 1375742 白色被覆，未引起凝膠的pH上升，且未觀察到混凝土的劣 化。從該結果中，可得知罩護二氧化矽的形成與螯合濃度 與二氧化矽濃度兩者相關，二氧化矽濃度較佳爲2質量％以 上。 從上述內容中’可得知本發明之罩護二氧化矽的混凝 土保護效果，在上述條件下即使放置在含有S042·之藥液或 養護水中，該本身亦可長時間保護混凝土，並可在經由地 下水將S042·稀釋10倍〜100倍而最終消滅爲止，均可保護 混凝土 β 此外，凝膠中的硫酸離子溶出於地下水中，並於地下 水中擴散而充分稀釋反應生成物的濃度，如此幾乎不會產 生混凝土的劣化。然而，因實際上地盤條件的不同，有時 存在著未產生此般S〇42·對地下水中之溶出或擴散之情形或 是未花費如此長的時間之情形。相對於此，本發明中，即 使在如此情形下，亦可藉由罩護二氧化矽來防止混凝土的 劣化。此外，在火山堆積物中的隧道等，即使在地下水中 存在有30000 ppm的高濃度S042_，亦可藉由罩護二氧化矽 來抑制混凝土的劣化。 再者，於以上的實驗中，在藥液2A、2B中養護水泥砂 漿試體1而使水泥砂漿試體1劣化時，養護水亦呈pH 10以上 或11以上之高鹼性。此可視爲由於劣化而使水泥砂漿試體 1中的Ca2 +溶出於外側之故。然而，在含有3 000 ppm以上 的螯合劑（磷離子）之藥液2A (非鹼性二氧化矽溶液）中 ，可得知即使高濃度的硫酸離子共存於凝膠中，養護水亦 -40- 1375742 呈中性値而未觀察到水泥砂漿試體1的劣化。此外’由此 • 可知，當藉由以含有3000 ppm以上的磷離子之非鹼性二氧 •- 化矽溶液所形成的凝膠化物或固結體來被覆混凝土時，即 使地下水或地盤中存在有高濃度的硫酸離子，亦具有保護 混凝土之效果。因此，當藉由含有具有螯合效應之30 00 ppm以上的磷離子之非鹼性二氧化矽溶液（罩護二氧化矽 溶液）來被覆混凝土的周邊時，即使在封閉狀態下不存在 .0 地下水的稀釋，亦可藉由硫酸離子來防止混凝土的劣化。 當周圍具有地下水等的水時，凝膠中的S042·，會隨著時間 的經過，往較混凝土結構物等更遠的區域之開放區域的方 向擴散，而被稀釋至不會對混凝土造成不良影響。 此外，從上述第5表及第11圖中，可從水泥砂漿試體1 的表面積與藥液2A、2B中的磷酸系化合物濃度及硫酸離子 濃度中’求取每單位表面積之磷酸離子量及硫酸離子量。 該結果如下列第6表所示。 -41 - 1375742 [第6表] \ 固結體2A中之 每單位面積的 磷酸離子量 (g/m2) 固結體整體之 每單位面積的 磷酸離子量 (g/m2) 固結體整體之 每單位面積的 硫酸離子量 (g/m2) 比較例1-1 0.0 0.0 1255.2 比較例1-2 22.7 22.7 1249.4 實施例1-1 36.0 36.0 1270.2 實施例1-2 206.8 206.8 1162.9 實施例1-3 660.0 660.0 941.4 實施例1*4 360.0 . 360.0 1541.4 實施例1-5 1200.0 1200.0 941.4 實施例1~6 151.2 151.2 1458.2 實施例1-7 172.3 172.3 1126.0 實施例1-8 36.0 104.0 1252.9 實施例1-9 36.0 161.4 1315.2 實施例1-10 206.8 827.0 886.1 比較例1-3 36.0 36.0 1038.6 實施例1-11 104.4 104.4 941.4 實施例1-12 225.6 225.6 941.4 上述實施例1-1〜實施例1-12中’在混凝土結構物等之 周邊部的地盤或是建構挖掘後的混凝土結構物等之地盤的 地盤改良中，從上述第表及第11圖來看，可得知所使 用之藥液2A中的硬化劑，在水泥砂漿試體1之每單位面積 36g/m2的螯合劑量以上時，可在試體表面形成堅固的防護 層以保護混凝土。此外，該値相當於混凝土之每單位面積 lm2爲4.3L ’相當於固結土（形成爲固結砂時）（Dr = 60% 、間隙率0.43、間隙充塡率100% .調配4的二氧化矽溶液 -42- 1375742 所形成之固結厚度lcm/cm2)的注入量。因此，可得知在 實際的注入中，相對於混凝土結構物lm2，將含有3 000 . ppm~ 1 00000 ppm的磷離子之非鹼性二氧化矽溶液以均質凝 膠換算爲lcm以上的固結厚度來注入，則可防護混凝土免 受地下水中的S042·離子或凝膠中的S042·離子之影響。 進一步來說，將含有3000 ppm以上的磷離子之二氧化 矽溶液注入於混凝土結構物等，來形成混凝土表面每lm2 φ 含有36g以上的磷酸離子之固結層，則可保護混凝土。此 外，若將此般含有磷酸離子之固結土層在混凝土表面形成 〇.5m以上，則可防護混凝土。在實際的注入中，亦可從沿 著混凝土壁面鑽孔之注入孔將非鹼性二氧化矽溶液注入於 地盤中，或是從混凝土壁面鑽孔並將非驗.性二氧化矽溶液 注入於混凝土背面的地盤中，以將罩護二氧化矽形成於混 凝土面。 •(實施例2 ) 接下來進行下列實驗，亦即確認出螯合系非鹼性二氧 化矽溶液的凝膠將存在於周邊之S042·對混凝土所造成的影 響予以阻隔之效果。如第12圖所示，於密閉容器20中製作 出虛擬地盤（高30cmx寬50cmx長105cm)，於該虛擬地盤 中，製作出厚度l〇cm的固結區域22及厚度40cm的固結區 域23，合計75L的固結區域，在混凝土區域21中，在未接 觸於固結區域22之一面上設置厚度5 cm的中空部5。此外， 固結區域23中，將養護水19充塡於未接觸於固結區域22之 -43- 1375742 —面。改良層使用豐浦砂，並調整至Dr = 60 %。此外，間 隙率設爲0.43。使用於固結區域22及固結區域23之藥液如 下列第7表所示。 [第7表] 固結區域22的藥液 固結區域23的藥液 比較例2-1 酸性二氧化矽溶液(僅使用硫酸反應劑） (實施例1的調配1) 比較例2-2 罩護二氧化矽溶液 (實施例1的調配3) 比較例2-3 罩護二氧化矽溶液 (實施例1的調配4) 實施例2-1 罩護二氧化矽溶液 (實施例1的調配3) 酸性二氧化矽溶液(僅使用硫酸反應劑） (實施例1的調配1) 實施例2-2 罩護二氧化砍溶液 (實施例1的調配4) 酸性二氧化矽溶液(僅使用硫酸反應劑） (實施例1的調配1) 比較例2-4 酸性二氧化矽溶液 (僅使用硫酸反應劑） (實施例1的調配1) 罩護二氧化矽溶液 (實施例1的調配3) 在此，可得知非鹼區域中之注入地盤的強度是由二氧 化矽濃度所單一決定。此外，注入地盤的改良時，係針對 改良目的來決定二氧化矽濃度及固結範圍。因此，在此將 注入區域中的二氧化矽濃度及固結範圍，於比較例2-1〜2-3及實施例2-1〜2-2中設爲一定。此外，爲了確認罩護二氧 化矽先與從混凝土所溶出之Ca + +或Mg + +反應來形成罩護二 氧化矽，以防止後續硫酸離子對混凝土層之侵入的情形， 係將僅使用硫酸反應劑之酸性二氧化矽溶液（實施例2的 調配1 )注入厚度40cm於混凝土層附近的固結區域22，並 將罩護二氧化矽溶液（實施例2的調配4 )注入厚度10cm於 固結區域23，來作爲比較例2-4。 對混凝土之影響試驗，係於1年後從混凝土層使試體 -44- 1375742 (直徑5cmxlOcm)成形並測定該強度’並與在同—養護 期間於水中進行養護之混凝土水泥砂漿的強度進行比較， 以觀察到強度降低者爲X，強度相同者爲〇。 比較例2-1~2-4、實施例2-1~2-2之硬化劑的總離子量 與混凝土強度之比較，係如下列第8表所示。總離子量’ 爲間隙率設爲0.43時之注入於改良層75L之藥液32_25L中 的硫酸離子與磷酸離子之總和。*Purpose) The pH of the gelled material inside the container The following contents can be found from the above Table 5. In Comparative Example 1-1, the sealing curing and water curing showed that the pH reached 1 or more after one year, and a part of the cement mortar sample 1 was damaged. In Comparative Example 1-2, in the closed curing and water curing, a part of the appearance was deteriorated after one year, and the pH of the gel reached 10. On the other hand, in Example 1-2 to Example 1-7 and Example 1-9, in the closed curing and water curing, white coating was observed on the surface of the cement sand sample 1 after curing, one year. After the pH (the same after 3 years), the pH of the gel remained almost neutral, and the uniaxial compression strength increased with respect to the elapsed time of -38 to 1375742, and the ion exchanged water of Comparative Example 1-1 was also obtained. The cement mortar test body 1 after the protection is more as a result. - In Example 1-1 and Example 1-8, in order to add the minimum amount of chelating agent for forming the cerium oxide to the consolidated body 2A, the surface of the cement mortar sample 1 can be observed during the closed curing. White was coated, and no deterioration in strength was observed, but some deterioration was observed on the concrete surface. When water is cured, it is not observed. Deterioration to concrete. In Comparative Example 1-3, both the closed curing and the water curing φ were gelled on the alkali side, and almost no white coating was formed on the concrete surface, and deterioration was observed after one year. From the results, it was found that in Examples 1-1 to 1-9, the alkali in the concrete was not eluted by the action of the white film, and the intrusion of S042· into the concrete was prevented. On the other hand, in Comparative Examples 1-1 and 1_2 in which the chelating agent was not used, the cerium in the concrete was eluted and deteriorated (neutralized). From the results, it was found that when the chelating concentration was less than 3,000 ppm, the formation of white coating was insufficient, and deterioration of concrete could not be suppressed. Further, from Comparative Example 1-3, it was found that in the alkali region, even if the chelating concentration was 3 000 ppm or more, the white coating was hardly formed or the formation of the white coating was insufficient, and the concrete could not be suppressed in the presence of sulfuric acid. Deterioration. From the above, it is known that the effect as a capping cerium oxide solution is remarkable when a non-alkaline cerium oxide solution for removing alkali is used. Further, in the examples 1 to 11, the formulation 1 of the cerium oxide concentration of 1% by mass was used as the consolidated body 2A, and in the example 1-12, the formulation 12 having the concentration of cerium oxide of 2% by mass was used as the consolidated body 2A. As a result, in Example 1-1, 'only a little white coating was formed on the surface of the concrete, and a pH of 1 liter of the gel was observed. In contrast, in Examples 1-12, a white coating of -39-1375742 was formed. The pH of the gel was not raised, and deterioration of the concrete was not observed. From this result, it is understood that the formation of the capping cerium oxide is related to both the chelating concentration and the cerium oxide concentration, and the cerium oxide concentration is preferably 2% by mass or more. From the above, it can be known that the concrete protection effect of the cover cerium oxide of the present invention can protect the concrete for a long time even if it is placed in the chemical liquid or the maintenance water containing S042· under the above conditions. It is possible to protect the concrete β by diluting S042· from 10 to 100 times with groundwater and finally destroying it. In addition, the sulfate ions in the gel dissolve in the groundwater and diffuse in the groundwater to sufficiently dilute the concentration of the reaction product. There is no deterioration of concrete. However, due to the difference in the actual site conditions, there are cases in which such a situation does not occur in the dissolution or diffusion of groundwater or it does not take such a long time. On the other hand, in the present invention, even in such a case, deterioration of concrete can be prevented by covering the cerium oxide. In addition, in a tunnel such as a volcanic deposit, even if there is a high concentration of S042_ of 30,000 ppm in the groundwater, the deterioration of the concrete can be suppressed by covering the cerium oxide. Further, in the above experiment, when the cement mortar sample 1 was cured in the chemical liquids 2A and 2B to deteriorate the cement mortar sample 1, the curing water was also highly alkaline having a pH of 10 or more or 11 or more. This can be regarded as the dissolution of Ca2+ in the cement mortar test body 1 due to deterioration. However, in the liquid 2A (non-alkaline cerium oxide solution) containing more than 3,000 ppm of a chelating agent (phosphorus ion), it is known that even if a high concentration of sulfate ions coexist in the gel, the curing water is also -40 - 1375742 was found to be neutral and no deterioration of cement mortar test piece 1 was observed. In addition, it is known that when concrete is coated by a gel or solid formed by a non-alkaline dioxins-containing cerium solution containing more than 3000 ppm of phosphorus ions, even if it exists in groundwater or in the ground. It has a high concentration of sulfate ions and also has the effect of protecting concrete. Therefore, when the periphery of the concrete is covered by a non-alkaline cerium oxide solution (covering cerium oxide solution) containing a phosphorus ion having a chelating effect of 30 00 ppm or more, even if it is not in a closed state, .0 The dilution of groundwater can also prevent the deterioration of concrete by sulfate ions. When there is water such as groundwater around, the S042· in the gel will diffuse in the direction of the open area of a region farther than the concrete structure over time, and will be diluted until it does not cause damage to the concrete. influences. Further, from the above-described fifth and eleventh graphs, the amount of phosphate ions per unit surface area can be determined from the surface area of the cement mortar sample 1 and the concentration of the phosphate compound and the sulfate ion concentration in the chemical solutions 2A and 2B. The amount of sulfate ions. The results are shown in Table 6 below. -41 - 1375742 [Table 6] \ Amount of phosphate ion per unit area in the consolidated body 2A (g/m2) Amount of phosphate ion per unit area of the entire consolidated body (g/m2) Amount of sulfate ion per unit area (g/m2) Comparative Example 1-1 0.0 0.0 1255.2 Comparative Example 1-2 22.7 22.7 1249.4 Example 1-1 36.0 36.0 1270.2 Example 1-2 206.8 206.8 1162.9 Example 1-3 660.0 660.0 941.4 Example 1*4 360.0 . 360.0 1541.4 Example 1-5 1200.0 1200.0 941.4 Example 1 to 6 151.2 151.2 1458.2 Example 1-7 172.3 172.3 1126.0 Example 1-8 36.0 104.0 1252.9 Example 1-9 36.0 161.4 1315.2 Example 1-10 206.8 827.0 886.1 Comparative Example 1-3 36.0 36.0 1038.6 Example 1-11 104.4 104.4 941.4 Example 1-12 225.6 225.6 941.4 In the above Examples 1-1 to 1-12, 'in the concrete structure In the improvement of the site of the site of the periphery of the object or the construction of the site of the excavated concrete structure, the hardener in the liquid chemical 2A used can be known from the above table and FIG. a chelating agent per unit area of 36 g/m 2 of cement mortar test body 1 Or more, can form a solid protective layer to protect the surface of the concrete test specimen. In addition, the 値 corresponds to concrete ll2 per unit area of 4.3L 'corresponding to consolidated soil (formed as consolidated sand) (Dr = 60%, clearance rate 0.43, clearance filling rate 100%. The amount of deposition of the yttrium oxide solution -42 - 1375742 formed by a consolidation thickness of 1 cm/cm 2 ). Therefore, it can be understood that in the actual injection, a non-alkaline cerium oxide solution containing 3 000 ppm to 100,000 ppm of phosphorus ions is consolidated into a solid gel in an amount of 1 cm or more with respect to the concrete structure lm2. The thickness is injected to protect the concrete from S042· ions in the groundwater or S042· ions in the gel. Further, by injecting a cerium oxide solution containing 3,000 ppm or more of phosphorus ions into a concrete structure or the like to form a consolidated layer of phosphoric acid ions per lm2 φ of 36 g or more on the concrete surface, the concrete can be protected. In addition, if the consolidated soil layer containing phosphate ions is formed on the concrete surface to be more than 5 m, the concrete can be protected. In the actual injection, the non-alkaline cerium oxide solution can also be injected into the ground plate from the injection hole drilled along the concrete wall surface, or the concrete wall surface can be drilled and the non-injective cerium oxide solution can be injected into the concrete hole. In the ground plate on the back of the concrete, the cerium oxide is formed on the concrete surface. • (Example 2) Next, the following experiment was carried out, that is, the effect of the gel of the chelate-based non-alkaline antimony-oxide solution on the influence of the surrounding S042· on the concrete was confirmed. As shown in Fig. 12, a virtual ground disk (30 cm high and 50 cm wide and 105 cm long) was produced in the sealed container 20, and a consolidation region 22 having a thickness of 10 cm and a consolidation region 23 having a thickness of 40 cm were produced in the virtual disk. In a total area of 75 L, in the concrete region 21, a hollow portion 5 having a thickness of 5 cm was provided on one surface not in contact with the consolidation region 22. Further, in the consolidation region 23, the maintenance water 19 is filled with the surface of the -43-1375742 which is not in contact with the consolidation region 22. The modified layer was made with Fengpu sand and adjusted to Dr = 60%. In addition, the gap ratio is set to 0.43. The chemical liquid used in the consolidation region 22 and the consolidation region 23 is shown in Table 7 below. [Table 7] Chemical solution of the chemical solution consolidation region 23 of the consolidation region 22 Comparative Example 2-1 Acidic cerium oxide solution (only a sulfuric acid reagent was used) (Preparation 1 of Example 1) Comparative Example 2-2 Cover Protective cerium oxide solution (mixing 3 of Example 1) Comparative Example 2-3 Covering cerium oxide solution (mixing 4 of Example 1) Example 2-1 Covering cerium oxide solution (mixing 3 of Example 1 Acidic cerium oxide solution (only using sulfuric acid reagent) (Formulation 1 of Example 1) Example 2-2 Covering the oxidizing chopping solution (mixing 4 of Example 1) Acid cerium oxide solution (using only sulfuric acid reaction) (Protection 1 of Example 1) Comparative Example 2-4 Acidized cerium oxide solution (only sulfuric acid reagent was used) (Preparation 1 of Example 1) Covering cerium oxide solution (mixing 3 of Example 1) Thus, it can be seen that the strength of the injection site in the non-alkali region is determined solely by the concentration of cerium oxide. In addition, when the injection site is improved, the cerium oxide concentration and the consolidation range are determined for the purpose of improvement. Therefore, the cerium oxide concentration and the consolidation range in the implantation region were constant in Comparative Examples 2-1 to 2-3 and Examples 2-1 to 2-2. In addition, in order to confirm that the cerium oxide is first reacted with Ca + + or Mg + + dissolved from the concrete to form a protective cerium oxide to prevent the intrusion of subsequent sulfate ions into the concrete layer, only sulfuric acid will be used. The acidic cerium oxide solution of the reactant (mixing 1 of Example 2) was injected into the consolidation region 22 having a thickness of 40 cm in the vicinity of the concrete layer, and the cerium oxide solution (mixture 4 of Example 2) was injected into the thickness of 10 cm. The junction region 23 was used as Comparative Example 2-4. The impact test on concrete was carried out after 1 year from the concrete layer to form the test body -44-1375742 (diameter 5cmxlOcm) and measure the strength' and compare the strength of the concrete cement mortar which was cured in the water during the same-maintenance period. , to observe that the strength is reduced to X, and the same intensity is 〇. The total ion amount of the hardeners of Comparative Examples 2-1 to 2-4 and Examples 2-1 to 2-2 was compared with the concrete strength as shown in Table 8 below. The total ion amount ' is the sum of the sulfate ion and the phosphate ion injected into the chemical solution 32_25L of the modified layer 75L when the gap ratio is 0.43.

\ 硫酸及磷- 酸離子量(g) 總離 子量 (g) 混凝 土 強度 由酸性二氧化矽溶液 所形成之固結區域 (僅使用硫酸反應劑） 由非鹼性二氧化矽溶 液所形成之固結區域 硫酸離子(g) 硫酸離子(g) 磷酸離子(g) 比較例2-1 843 — — 1843 X 比較例2-2 — 884 464 1348 〇 比較例2-3 — 595 1530 2125 〇 實施例2-1 675 177 19 871 〇 實施例2-2 675 119 111 905 〇 比較例2-4 675 177 19 871 X imsm_____ 如上述表中所示，比較例2-1、比較例2-4中’觀察到 ® 混凝土的強度降低，尤其在混凝土層的龜裂部分觀察到表 面剝離之較大劣化，於混凝土表面並未觀察到白色結晶。 比較例2-2及比較例2-3中’未觀察到強度降低’於混凝土 表面觀察到白色結晶。此外’實施例2 · 1及實施例2 -2中， 在混凝土結構物的附近設置有由非鹼性二氧化矽溶液所形 成之固結區域者，未觀察到混凝土的強度降低’於混凝土 表面觀察到白色結晶。再者，可得知總離子量與比較例2 · 2及比較例2 - 3相比更少。亦即’實施例2 -1中’將注入區域 區分爲距離混凝土結構物較近之區域與距離混凝土結構物 -45- 1375742 較遠之區域，並分別藉由調配3的非鹼性二氧化矽溶液與 調配1的非鹼性二氧化矽溶液予以固結，藉此’與僅藉由 調配3將整體的固結區域予以固結者相比’更可減少整體 的反應生成物。如此，藉由在混凝土結構物的附近設置有 由非鹼性二氧化矽溶液所形成之固結區域，可防止硫酸對 混凝土之影響，此外，可減少總離子量。 此外，當比較實施例2-1與比較例2-4之結果，即使以 調配有同量的硫酸離子與磷酸離子之注入材料來注入同範 圍的地盤，在比較例2-4中仍觀察到混凝土的強度降低。 此外，混凝土表面的白色結晶，在實施例2-1中可觀察到 ，但在比較例2-4中未觀察到。從該結果中，可考量爲當 將以螯合劑作爲有效成分之非鹼性二氧化矽溶液注入於遠 離混凝土層之地盤時，在混凝土層表面形成罩護二氧化矽 之前，硫酸離子侵入而引起混凝土的劣化。 從上述內容中，可得知本發明中，藉由使以螯合劑作 爲有效成分之非鹼性二氧化矽溶液在其他離子之前先接觸 於混凝土層，可形成罩護二氧化矽，而能夠防止後續所滲 透之離子滲透於混凝土層。 【圖式簡單說明】 第1圖係顯示於具有中空部之混凝土結構物與硫酸固 結層之間形成摻入有螯合劑之非鹼性二氧化矽溶液的固結 層，並將罩護二氧化矽形成於混凝土結構物的表面或劣化 、龜裂部分之地盤之說明圖。 -46-\ Sulfuric acid and phosphorus - Acid ion amount (g) Total ion amount (g) Concrete strength The solidified area formed by the acidic cerium oxide solution (using only the sulfuric acid reagent) is formed by the non-alkaline cerium oxide solution. Knot region sulfate ion (g) sulfate ion (g) phosphate ion (g) Comparative Example 2-1 843 - 1843 X Comparative Example 2-2 - 884 464 1348 〇 Comparative Example 2-3 - 595 1530 2125 〇 Example 2 -1 675 177 19 871 〇Example 2-2 675 119 111 905 〇Comparative Example 2-4 675 177 19 871 X imsm_____ As shown in the above table, in Comparative Example 2-1 and Comparative Example 2-4, 'observed ® The strength of the concrete is reduced, especially when the surface peeling is largely deteriorated in the cracked portion of the concrete layer, and no white crystals are observed on the concrete surface. In Comparative Example 2-2 and Comparative Example 2-3, 'no decrease in strength was observed', white crystals were observed on the concrete surface. Further, in 'Examples 2 and 1 and 2 to 2, a consolidation region formed of a non-alkaline ceria solution was provided in the vicinity of the concrete structure, and no decrease in the strength of the concrete was observed. White crystals were observed. Further, it was found that the total ion amount was less than that of Comparative Example 2-2 and Comparative Example 2-3. That is, in the 'Example 2-1', the injection area is divided into a region closer to the concrete structure and a region far from the concrete structure -45-1375742, and the non-alkaline cerium oxide is prepared by mixing 3 respectively. The solution is consolidated with the non-alkaline cerium oxide solution of Formulation 1, whereby the overall reaction product can be reduced by 'comparing with the consolidation of the entire consolidated region only by Formulation 3. Thus, by providing a consolidation region formed of a non-alkaline ceria solution in the vicinity of the concrete structure, the influence of sulfuric acid on the concrete can be prevented, and in addition, the total ion amount can be reduced. Further, when the results of Comparative Example 2-1 and Comparative Example 2-4 were compared, even if the same amount of the ground material was implanted with the same amount of the sulfate ion and the phosphate ion implantation material, it was observed in Comparative Example 2-4. The strength of concrete is reduced. Further, white crystals of the concrete surface were observed in Example 2-1, but were not observed in Comparative Examples 2-4. From this result, it can be considered that when a non-alkaline ceria solution having a chelating agent as an active ingredient is injected into a site far from the concrete layer, the sulfate ion is invaded before the formation of the cerium oxide is formed on the surface of the concrete layer. Deterioration of concrete. From the above, it can be understood that in the present invention, by preventing the non-alkaline ceria solution having a chelating agent as an active ingredient from contacting the concrete layer before other ions, the cerium oxide can be formed and prevented. Subsequent permeated ions penetrate the concrete layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a consolidated layer formed by forming a non-alkaline cerium oxide solution doped with a chelating agent between a concrete structure having a hollow portion and a sulfuric acid consolidation layer, and An illustration of the formation of ruthenium oxide on the surface of a concrete structure or a site of a deteriorated or cracked portion. -46-

Claims (1)

1375742 第100117229號專利申請案中文申請專利範圍修正本 民國101年8月；U日修正以 七、申請專利範圍： 1. 一種地盤注入工法，是將以螯合劑作爲有效成分之 非鹼性二氧化矽溶液，注入於：將既存或預定建造的使用 混凝土的土中結構物周圍予以包圍之地盤中之地盤注入工 法，並且 前述土中結構物的至少一部分是存在於地下水面下， 構成該土中結構物之壁面之中，一面面向地盤且另一面面 向大氣之地盤注入工法，其特徵爲： 注入pH 1 0以下的前述非鹼性二氧化矽溶液，以使前述 地盤中之前述螯合劑的含量於前述土中結構物的表面每 lm2爲36g以上，在前述土中結構物的表面形成具有對該表 面形成防護被膜的固結層，並且藉此在該土中結構物的附 近部設置改良地盤。 2. 如申請專利範圍第1項所述之地盤注入工法，其中 將前述非鹼性二氧化矽溶液中之前述螯合劑的離子含量設 爲3 00 0 ppm以上，並且將固結層距離前述土中結構物表面 的厚度，以均質凝膠（Homo-Gel)換算設爲lcm以上》 3 ·如申請專利範圍第1或2項所述之地盤注入工法，其 中將固結層距離前述土中結構物表面的厚度設爲0.5 m以上 〇 4.如申請專利範圍第1或2項所述之地盤注入工法，其 中至少使含有前述螯合劑之二氧化矽溶液成分，較該螯合 1375742 劑以外的二氧化矽溶液成分更先接觸於前述土中結構物 5. 如申請專利範圍第1或2項所述之地盤注入工法，其 中前述非鹼性二氧化矽溶液的二氧化矽濃度[Si02](質量 % )係滿足下列式， (A) 2質量％$[81〇2]各50 質量 ％; 其中該非鹼性二氧化矽溶液包含磷酸化合物作爲前述 螯合劑，且該非鹼性二氧化矽溶液的磷離子濃度[P]( ppm )滿足下列式， (B) 3 000 ppm S [P] $ 1 20000 ppm。 6. 如申請專利範圍第5項所述之地盤注入工法，其中 在將前述非鹼性二氧化矽溶液中含有前述磷酸化合物之組 成分，注入於包圍前述土中建造物周圍之地盤中後，再把 以前述非鹼性二氧化矽溶液之中的硫酸化合物作爲有效成 分之組成分，注入於該含有磷酸化合物組成分的注入區域 周圍時，將該含有硫酸化合物組成分的磷離子濃度[P]( ppm)設爲由下列式表示之範圍內， (C ) 0 S [P] S 3 0000 ppm。 7. 如申請專利範圍第5項所述之地盤注入工法，其中 前述非鹼性二氧化矽溶液係含有水玻璃的二氧化矽，該非 鹼性二氧化矽溶液的二氧化矽濃度[Si 02](質量％ )滿足 下列式， (D) 2 質量 ％$[3丨〇2]$10質量％。 8. 如申請專利範圍第5項所述之地盤注入工法，其中 前述非鹼性二氧化矽溶液中含有前述磷酸化合物之組成分 -2- 1375742 的磷離子濃度[P] ( PPm )與二氧化矽濃度[Si02](質量 )，係滿足下列式， [P]/[Si〇2] = 60〜5000。 9. 如申請專利範圍第1或2項所述之地盤注入工法， 中係使用在前述土中結構物之液狀化對策工程、防劣化 修補工程。 10. 如申請專利範圍第9項所述之地盤注入工法，其 從前述土中結構物之面向大氣之該側的面，並由設置在 土中結構物內之注入孔，注入前述非鹼性二氧化矽溶液 進行前述土中結構物之液狀化對策工程、防劣化或修補 程。 1 1.如申請專利範圍第1或2項所述之地盤注入工法 其中在注入前述非鹼性二氧化矽溶液之前，先將水泥系 料（Grout )，注入於前述土中結構物之接觸於地盤之 側的面之周圍的地盤中。 12.如申請專利範圍第1或2項所述之地盤注入工法 其中在使用多點地盤同時注入方式，亦即從前述土中結 物之面向大氣之該側的面，經由設置在該土中結構物內 具有吐出口之複數個注入孔同時注入於複數個注入地點 注入方式，注入前述非鹼性二氧化矽溶液時， 所使用的注入設備，係具備：從集中注入機具經由 數條注入管路所連接之複數條注入管、將前述非鹼性二 化矽溶液以液體輸送送至前述複數個注入地點並且將該 鹼性二氧化矽溶液注入於該複數個注入地點之複數個單 % 其 或 中 該 來 工 漿 該 ， 構 且 之 複 氧 非 柱 -3- 1375742 塞泵、測量前述複數個注入地點中之前述非驗 溶液的流量及/或壓力之流量及壓力測量裝置 地管理前述複數個單柱塞泵之集中管理裝置， 使前述複數個單柱塞泵動作，一邊根據來 及壓力測量裝置的資訊，由前述集中管理裝置 數個單柱塞泵的動作，一邊對前述複數個注入 入或選擇性地注入前述非鹼性二氧化矽溶液。 性二氧化矽 、以及總括 自前述流量 來控制該複 地點同時注 1375742 * 另 ι(丨丨）ι 1—二v 3專由請萁 ιοί s y 14 a ·>_ΐ. _.ν +.二< -r- 一7义.二；、夕」：Η 第]圖 601375742 Patent application No. 100117229 Patent application scope revised in the Republic of China in August, 101; U-day amendments to seven, the scope of application for patents: 1. A site injection method, is a non-alkaline dioxide with a chelating agent as an active ingredient a sputum solution injected into a method of injecting a site in a site surrounded by a structure of an existing or predetermined concrete structure, and at least a portion of the structure in the soil is present under the surface of the groundwater to constitute the soil Among the wall surfaces of the structure, one surface facing the ground and the other side facing the atmosphere, the method is: injecting the non-alkaline cerium oxide solution having a pH of less than 10 to the content of the chelating agent in the aforementioned ground. The surface of the above-mentioned soil structure is 36 g or more per lm2, and a consolidated layer having a protective film on the surface is formed on the surface of the structure in the soil, and an improved ground is provided in the vicinity of the structure in the soil. . 2. The site injecting method according to claim 1, wherein the ion content of the chelating agent in the non-basic ceria solution is set to be more than 300 ppm, and the consolidated layer is separated from the soil. The thickness of the surface of the intermediate structure is set to be 1 cm or more in terms of Homo-Gel conversion. 3 · The method of injecting the ground according to claim 1 or 2, wherein the consolidated layer is separated from the above-mentioned soil structure The thickness of the surface of the object is set to be 0.5 m or more. 4. The method of injecting the ground according to claim 1 or 2, wherein at least the composition of the cerium oxide solution containing the chelating agent is more than the chelating solution of 1,371,742 The cerium oxide solution component is further contacted with the above-mentioned soil structure. 5. The site injecting method according to claim 1 or 2, wherein the non-alkaline cerium oxide solution has a cerium oxide concentration [Si02] ( The mass %) satisfies the following formula: (A) 2% by mass of each of 50% by mass of the mass spectrometer; wherein the non-basic cerium oxide solution comprises a phosphoric acid compound as the chelating agent, and the non-basic cerium oxide solution Phosphorus ion concentration Degree [P] (ppm) satisfies the following formula, (B) 3 000 ppm S [P] $ 1 20000 ppm. 6. The site injecting method according to claim 5, wherein the component containing the phosphoric acid compound in the non-basic ceria solution is injected into a site surrounding the building in the soil, Further, when a component containing the sulfuric acid compound in the non-basic ceria solution as an active ingredient is injected around the injection region containing the phosphate compound component, the phosphorus ion concentration of the component containing the sulfuric acid compound is [P ] (ppm) is set to the range expressed by the following formula, (C) 0 S [P] S 3 0000 ppm. 7. The method of injecting a site according to claim 5, wherein the non-alkaline cerium oxide solution is cerium oxide containing water glass, and the cerium oxide concentration of the non-basic cerium oxide solution [Si 02] (% by mass) satisfies the following formula, (D) 2 mass%$[3丨〇2]$10 mass%. 8. The method of injecting a site according to claim 5, wherein the non-basic ceria solution contains a phosphorus ion concentration [P] (PPm) of the composition of the phosphate compound -2- 1375742 and a dioxide oxidation The enthalpy concentration [Si02] (mass) satisfies the following formula, [P]/[Si〇2] = 60~5000. 9. For the site injection method described in the first or second aspect of the patent application, the liquidation countermeasures and the deterioration prevention repair works for the structures in the soil are used. 10. The method of injecting a site according to claim 9, wherein the non-alkaline is injected from a surface of the soil structure facing the atmosphere and an injection hole provided in the structure in the soil. The cerium oxide solution is subjected to the liquefaction countermeasure engineering, the anti-deterioration or the repairing process of the above-mentioned soil structure. 1 1. The method of injecting a site according to claim 1 or 2, wherein before injecting the non-alkaline ceria solution, the cement material (Grout) is injected into the structure of the soil. In the ground around the face on the side of the site. 12. The method of injecting a site according to claim 1 or 2, wherein the multi-point site is simultaneously injected, that is, from the side of the soil in the surface facing the atmosphere, by being disposed in the soil. a plurality of injection holes having a discharge port in the structure are simultaneously injected into a plurality of injection points, and when the non-alkaline ceria solution is injected, the injection device used is: from a concentrated injection device through a plurality of injection tubes a plurality of injection pipes connected to the road, and the non-alkaline antimony telluride solution is transported by liquid to the plurality of injection sites and the alkaline ceria solution is injected into the plurality of injection sites at a plurality of Or a re-oxygen non-column-3- 1375742 plug pump, a flow rate and/or a pressure measuring device for measuring the flow rate and/or pressure of the non-test solution in the plurality of injection locations, and managing the aforementioned plural The centralized management device of the single plunger pump operates the plurality of single plunger pumps, and according to the information of the pressure measuring device, A plurality of processing means of a single action piston pump, on the one side or a plurality of injection into the non-selectively injected silicon dioxide alkaline solution. Sulphur dioxide, and the total flow from the aforementioned flow to control the complex site simultaneously note 1757742 * Another ι (丨丨)ι 1 - two v 3 by 萁ιοί sy 14 a ·>_ΐ. _.ν +. <-r-一七义.二;,夕::Η] Figure 60 S16^S 1375742 第3圖S16^S 1375742 Figure 3 X 36 1375742 第5圖X 36 1375742 Figure 5 A 31A 31 第6圖Figure 6 13757421375742 191375742191375742 40cm PH ▽ 20 數小W40cm PH ▽ 20 small W 數卜分Μ 鹼11: 1375742 第14圖Number of distillates 碱 Alkali 11: 1375742 Figure 14 VV