TWI263624B - Method for modifying reservoir sludge and construction material containing modified reservoir sludge - Google Patents

Abstract

The present invention relates to a method for modifying reservoir sludge and construction material containing modified reservoir sludge. The method of the present invention is suitable for modifying reservoir sludge of swelling clay; the method comprises the following steps: adding water and mixing; adding cation surfactant modifier; desiccating; drying; and grinding; the method is capable of producing hydrophobic granules with waterproof surfaces such as concrete and waterproof coating material for construction. By varying the proportion of aggregate of the waterproof granules in construction material, various compressive strengths can be obtained so as to be applied in different kinds of construction. In addition, since the granules made by the modified reservoir sludge is waterproof, the construction material having the same may possess a desirable waterproof property.

Description

1263624 九、發明說明： 【發明所屬之技術領域】 本^明是關於-種改f方法，以及„種營建卫_剩 ，特別疋指一種針對沉積在水庫底部之淤泥作改質，使冰 庫於泥資源能夠被利用作為#建工程材料之原料的水庫 泥的改質方法，以及含有該改質方法所製成之防水粒料:: 營建工程材料。 【先前技術】1263624 IX. Description of the invention: [Technical field to which the invention belongs] This method is related to the method of changing the f, and the cultivating of the cultivating _ residual, especially the modification of the sludge deposited on the bottom of the reservoir, so that the ice storage The mud material can be used as a reforming method for the reservoir mud which is the raw material of the construction materials, and the waterproof pellets prepared by the modification method:: construction engineering materials. [Prior Art]

水庫淤泥是一種質地細緻且富含黏土及有機物質的土 壤，為了使此種膨脹性黏土能夠再生利用，最常見的利用 方式’係將>於泥沉$殿、日京曬、造粒之後，再以i2〇〇〇c高溫 燒製成輕質骨材，在燒製的過程中由於骨材會膨脹，因此 ’此種骨材具有質輕、隔音及隔熱效果佳等優點。雖然前 述輕質骨材具有以上的優點，但實際運用在營建工程上時 卻具有下述疏失： φ 1·由水庫淤泥所製成之輕質骨材之所以具有質輕的特色，主 要原因在於：骨材具有多孔隙的特性，此種多孔隙微結構 會造成骨材吸水率高，以及強度變異性大等缺失，故當該 輕質骨材實際運用在營建工程上時，其耐久性及材質皆會 • 產生不確定，而多孔隙微結構也會讓骨材的防水性變差， ' 使得該輕質骨材在營建工程上的應用範圍受到限制。 2·已知水庫淤泥欲製成輕質骨材時，必需經過沉澱、晾曬（ 即脫水）、造粒以及高溫燒結等步驟，此等步驟不僅製造 過程繁瑣費時’高溫窯燒也需要特殊的設備及燒製技術， 5 I263624 因此二其製造成本高，推廣不易，此對於目前國内水庫沒 =造成之大量水庫齡泥而言助益不大，由於水庫於泥若 隨意去棄可能影響到環境生態，而已知的利用方式又具有 f本高、推廣不易、應用範圍受到限制等困難，因此，— 2 =對於水庫游泥的再生利用需求低，此亦會間接造成 :官理單位延宏浚渫工作，以及水庫使用壽命減短等缺 點° 分子二黏土的改質技術’大部份被應用在高 禝：材枓的製造上，例如蒙脫土 (montmoriIlonite)的改 ，、：製造方式係以改質劑對純化後之蒙脫土進行改質 的親油性，如此高分子單體方可進入蒙脫土 土可^分子之聚合作用，使奈米級之蒙脫 材料的力r分散於高分子母材中，以便提升高分子複合 =及熱學性能。此種已知的黏土改質技術及應用 確缺點是黏土需要經過一純化處理的步驟，才能 的效果，由於純化蒙脫土的成本較高，故改質後 受到限制。 科成本…導致其應用範圍 【發明内容】 本發明之目的係在提供一 厭水特性，而適合運用在營建二=會，脹’並具有 方法。 鈿材枓之水庫淤泥的改質 本發明之另-目的在於提供—種 營建工程材料係運用上述改質方1材料，上述 所1仵之防水粒料為原 6 1263624 料之一，藉由防水粒料的厥水 建構而成的結構物或防水塗層 使由“建工程材料 土巧具有較佳的防水效果。 本發明水庫齡泥之改質方 點土質之水庫齡泥，包含以下步驟“用來改質屬於膨脹 !·加水攪拌：於常溫下在水庫齡泥中加入H0。倍重量的水 ，亚攪拌使淤泥均勻地分散在水中。 、 2. 添加改質劑：依據水庫淤泥之陽 旦Reservoir silt is a soil with fine texture and rich in clay and organic matter. In order to make this kind of expansive clay recyclable, the most common way of utilization is to use it in the mud, the sun, and the granulation. Then, it is made into a lightweight aggregate by i2〇〇〇c high-temperature burning. Since the aggregate expands during the firing process, the bone material has the advantages of light weight, sound insulation and good heat insulation effect. Although the above-mentioned lightweight aggregate has the above advantages, the actual application in the construction project has the following negligence: φ 1· The light weight of the lightweight aggregate made of reservoir sludge has the characteristics of light weight, the main reason is The aggregate has the characteristics of multi-pores. The porous microstructure will cause high water absorption of the aggregate and large loss of strength. Therefore, when the lightweight aggregate is actually used in construction projects, its durability and The materials will all be inconsistent, and the porous microstructure will also make the waterproofing of the aggregates worse, which limits the application of the lightweight aggregates in construction projects. 2. Known that when the reservoir sludge is to be made into lightweight aggregates, it must be subjected to steps such as sedimentation, drying (ie dehydration), granulation and high-temperature sintering. These steps are not only complicated and time-consuming, but also require special equipment for high-temperature kiln burning. And the firing technology, 5 I263624 Therefore, its manufacturing cost is high, and it is not easy to promote. This is not helpful for the large amount of reservoir-aged mud that is not caused by the domestic reservoirs, and may be affected by the random disposal of the reservoir in the mud. Ecology, and the known utilization methods have difficulties such as high f, high promotion, and limited application scope. Therefore, —— 2 = low demand for reclaiming and reclaiming of reservoir mud, which will indirectly cause: the official unit Yan Hongwei Work, and shortcomings such as shortened service life of the reservoir. The modification technology of the molecular two clays is mostly applied to the manufacture of sorghum: the manufacture of materials, such as the modification of montmori Ilonite, and the manufacturing method. The modifier improves the oleophilicity of the purified montmorillonite, so that the polymer monomer can enter the montmorillonite soil to polymerize the molecules, so that the nanometer montmorillonite material The force r is dispersed in the polymer base material to enhance the polymer composite = and thermal properties. The known clay upgrading technique and application have the disadvantage that the clay needs to undergo a purification step, and the effect of purifying the montmorillonite is limited due to the high cost of purifying the montmorillonite. The present invention is directed to providing a water-repellent property, and is suitable for use in construction, inflation, and method. Modification of the sludge of the coffin 枓 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本The structural or waterproof coating of the granules of the granules makes the construction materials have better waterproof effect. The reservoir of the invention is modified from the mud of the reservoir, including the following steps. It is used for upgrading to expand! · Add water to stir: Add H0 to the mud of the reservoir at room temperature. The double weight of water, sub-stirred, allows the sludge to be evenly dispersed in the water. 2. Adding modifier: based on the mud of the reservoir

離子界面活性劑，以進行陽 胃里’口入適當的陽 將，於m _子交換取代仙，目的在於 泥中谷易吸水之石夕層表面改質成厭水性。 3. 去除水份：利用過濾、脫水、供乾等加工流程，將 之水庫淤泥中的水份去除。 、交 4.研磨··將去除水份後的改_泥研磨成適當粒徑，即可製 得表面具有厭水特性的防水粒料。 /經表面改f而具有厭水特性的水庫於泥在製作成粒料 之後，由於該粒料表面已形成保護膜不易被水浸潤、裂解 、，因此，該粒料具有較佳之防水性能，而可將水庫游泥資 源化再利用，並作為營建工程材料。 可使用於本發明之典型陽離子型界面活性劑包含··有 機胺鹽類、第四級銨鹽類、三烷基苯甲銨鹽、烷基吡啶鹽 、及聚乙烯聚胺脂肪酸醯胺鹽等五類，其中有機胺鹽類為 例如正十二胺（d〇decylamine)之常見的第一級〜第三級脂肪胺 鹽；而第四級銨鹽類種類較多，市面上常見的有：孓甲基一 本甲土氣化牛月曰季叙（dimethyi benzyl hydrogenatedtallow quaternary ammonium，簡稱 2MBHT)、2_ 甲基 _2_氫化牛脂 7 1263624 季銨（dimethyl dihydrogenatedtallow quaternary ammonium ? 間稱2M2HT)、2-甲基-鼠化牛脂-2-乙基己基-季錢（dimethyl hydrogenatedtallow 2-ethylhexyl quaternary ammonium，簡 稱2MHTL 8)、甲基-牛脂-雙-2-羧基乙基-季錄（methyl tallow， bis-2-hydroxyethyl quaternary ammonium，簡稱 MT2EtOH) 等。因陽離子界面活性劑種類繁多，只要能符合經濟效益 者皆可適合用於本發明。本發明之營建工程材料，是取用 經表面厭水化處理後之防水粒料來作為原料之一，上述營 建工程材料乃例如：混凝土、防水塗層等等。當該營建工 程材料為混凝土時，其基本組成包括··膠結材（水泥及卜作 嵐材料等）、水、粗骨材、細骨材及混凝土摻料（強塑劑等） ，經由適當配比並充分拌合後，可以澆製成各種符合抗壓 強度及較佳防水效果之混凝土結構物。而若該營建工程材 料為防水塗層時，其基本組成包含··膠結材（水泥及卜作嵐 材料等）、水、細骨材及混凝土摻料（強塑劑等）。當該營建 工程材料為混凝土時，隨著防水粒料在混凝土中所佔全部 細骨材比例的不同’可產生不同的抗壓強度，故適合應用 在不同的工程中。 在本發明中當該營建工程材料為混凝土時，其基本組 成中的膠結材（水泥及卜作嵐材料等）、水、粗骨材、細骨材 、及混凝土摻料（強塑劑等）的比例為： 1 :(0.05 〜5):(0 〜1〇) ··〇〜！〇):(〇 〜〇2) 二其中該細骨材包含一般的細砂，以及由該改質方法所窜 传之防水粒料，此防水粒料佔細骨材的比例為卜_重量 8 1263624 %，較佳為20〜100重量％。The ionic surfactant is used to carry out the appropriate yang in the stomach, and the m_sub-exchange is substituted for the immortal. The purpose is to modify the surface of the stone layer which is easy to absorb water in the mud to become water-repellent. 3. Removal of water: The water in the reservoir sludge is removed by processing processes such as filtration, dewatering, and drying. 4. Grinding · Grinding the modified _ mud after removing the water into a suitable particle size, the water-repellent pellet having the surface having the water-repellent property can be obtained. / After the surface is changed to f, the reservoir having the water-repellent property is formed into pellets, and since the protective film on the surface of the pellet is not easily infiltrated and cracked by water, the pellet has better waterproof performance, and The reservoir mud resources can be reused and used as construction materials. Typical cationic surfactants useful in the present invention include organic amine salts, fourth ammonium salts, trialkyl benzammonium salts, alkyl pyridinium salts, and polyethylene polyamine fatty acid guanamine salts. Five types, wherein the organic amine salts are common first- to third-order fatty amine salts such as d-decylamine; and the fourth-order ammonium salts are more common, and are commonly found in the market: Dimethyi benzyl hydrogenated tallow quaternary ammonium (2MBHT), 2_methyl_2_hydrogenated tallow quaternary ammonium 间2M2HT, 2-A Dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium (2MHTL 8), methyl-tallow-bis-2-carboxyethyl- quaternary (methyl tallow, bis-2) -hydroxyethyl quaternary ammonium, referred to as MT2EtOH). Due to the wide variety of cationic surfactants, those skilled in the art can be suitably used in the present invention. The construction engineering material of the present invention is obtained by taking the water-repellent granules which have been subjected to surface dehydration treatment as a raw material, and the above-mentioned construction engineering materials are, for example, concrete, waterproof coating and the like. When the construction material is concrete, its basic composition includes · cement (cement and concrete materials, etc.), water, coarse aggregate, fine aggregate and concrete admixture (strong plasticizer, etc.), After thorough mixing, it can be poured into various concrete structures that meet the compressive strength and better waterproof effect. If the construction material is a waterproof coating, its basic composition includes · cement (cement and concrete materials), water, fine aggregate and concrete admixture (strong plasticizer, etc.). When the construction material is concrete, the proportion of all the fine aggregates in the concrete can produce different compressive strength, so it is suitable for use in different projects. In the present invention, when the construction material is concrete, the proportion of the cementitious material (cement and concrete material, etc.), water, coarse aggregate, fine aggregate, and concrete admixture (strong plasticizer, etc.) in the basic composition is For: 1 :(0.05 〜5):(0 〜1〇) ··〇~! 〇): (〇~〇2) Second, the fine aggregate contains general fine sand, and the waterproof pellets rumored by the modification method, the ratio of the waterproof pellets to the fine aggregate is _weight 8 1263624%, preferably 20 to 100% by weight.

在本發明中’當防水粒料的使用量佔全部細骨材的 50〜100重量％時，所製得之混凝土的流動性良好，其28天 的抗壓強度可達110 kgf/cm2，此時可應用在例如：免夯實 路基填方工程之控制性低強度材料。當該防水粒料之使用 量介於全部細骨材的40〜50重量％時，其28天抗壓強度可 升至170 kgf/cm2,此時調製的混凝土適合運用在例如：消 波塊、安全島、人行道、排水溝等等非結構混凝土工程上 。當防水粒料之使用量佔全部細骨材的4〇重量％以下時， 其28天杬壓強度可升至21〇 kgf/cm2 ,此時已符合結構混凝 土之強度要求，可應用在一般土木建築的工程上。 由於製得之混凝土結構物在符合各種不同營建工程之 工作性與抗壓強度要求，亦具有良好的剛性及防水特性， 因此’若能大量運用在混凝土的卫程上，必能大量消耗水 庫=泥，同時促進水庫清於工作之進行，以減少水庫於積 ^心如此在保護環境生態之同時，亦可延長水庫的使用 本發明營建工程材料若為一般塗佈在建築物表面上 防水塗層時，其基本組成包含：作為膠結劑之水泥及卜 2材料等、水、細骨材與混凝土摻料（強塑劑等），其中該 7月材亦包含有―般的細石少，以I經該改質方法所製成之 火粒料，上述防水粒料在全部細骨材中的使用量，只要 I:重量％即具有防水的效果。亦即，以防水粒料㈣代, 般營建工程材料中細骨材的量只要大於1重量％，即可在: 9 1263624 會影響強度與工作性（亦即與一般標準防水塗層具有相當性 質），達到較低之吸水比並符合CNS規範的要求。 【實施方式】 【實施例1】 參閱圖1，本發明之實施例！首先取1〇〇〇公克之阿公 店水庫淤泥，然後測得該水庫淤泥之陽離子交換當量為 20meg/100g，之後加入5〇〇〇毫升的水稀釋攪拌，再添加” 公克的正十二胺（dodecyl amine)為陽離子界面活性劑以進行 改質，上述改質劑的添加量是以下述公式計算而得，其中 正十一胺的分子式為C! 2¾ 7N，分子量18535* 於泥陽離子交換當量僮1000 x於泥纖改質劑陽離子價數 之後在常溫下將水庫淤泥與陽離子界面活性劑攪拌8 小時以上’即可完成陽料交換取代作用，然後將改質後 水庫於泥過濾、脫水’再經烘乾至怪重後，研磨成粒握通 過ASTM 100號篩（15〇/Zm)之防水粒料，即可進行下列的熱 重分析及水中浸置試驗。 ' ⑴熱重分析結果1作完成之營建工程材料，其原先石夕層 間親水性變成厭水性，由附件i的試驗結果得知 庫於泥未進行改質時，其秒層間易於吸水，於附 近產生較大之重量損失，故其重量對時間微分之曲線中 ，於10CTC附近出現最大峰值。而由附件2之本發明實 施例1所製得之改質後水庫淤泥(即防水粒料)的熱重分 10 1263624 析結果可發現，水庫淤泥改質前後熱重分析圖形之明顯 改變’改f後水庫齡泥之熱重損失最大峰值出現於300 °C附近’此為所使用改質劑產生重量損失時之溫度，而 100C附近由於水所造成之熱重量損失極少，導致其熱微 分曲線僅有-微小峰值，表示改質後水料泥石夕層間吸 水量已大幅減少，甚至可視為已幾乎不吸水。 ⑺水中浸置試驗：由附件3左侧圖形的顯示可知，未改質 水料泥因擁有親水之秒層間表面，因此，當其置放在 水中h會產生膨潤行為’進而裂解成微小顆粒。而由附 件3右側圖形顯示可知，改質後水庫淤泥中矽層間生成 厭水之表面，使微小粒徑之改質水料泥易浮於水面上 ’而較大粒徑之改質水料泥則沒人水中，且於其外觀 表面形成保護膜’不會被水浸潤而裂解，所以，改質後 水庫於泥於水中可視為一外觀形狀穩定之粒料。、 由以上試驗結果得知，每 ⑼山… 只例1之經改質水庫於泥的石夕 1間由於表面幾乎完全不吸水，成為—外部表面僅微量吸 L穩絲料。由於其遇水不產生膨脹行為，因此，依該 所製得之防水粒料’可以部份或全部取 材料中的細骨材。 7 【實施例2】 細^用實施例1所製成之防水粒料來取代混凝土中的部份 卜作嵐材料等）、水、粗骨材、一二括·勝結材(水泥及 等)等，經由適當配比並均拌::r製混咖^ j仟口、澆製，可以形成工程用 11 1263624 的結構物。 在本實施例中，係取用_重量％由實施例丨所製成之 防水粒料來取代傳統混凝土中的細砂，未添加粗骨材，上 述防水粒料與膠結材（水泥）的重量比4 2·4:丨，水與膠結材 (水泥财量比為L25 : i，然後添加7 5%水泥重量之混凝 土摻料（強塑劑）’經標準拌合順序後，測得水泥砂㈣流動 度為1〇〇%，此砂漿澆製成結構物時，其28天抗壓強度為 5/·3 kgf/Cm2’上述抗壓強度符合例如：夯實路基填方工程 等之控制性低強度材料的低強度及高流動性要求。 【貫施例3】 本發明之實施例3係使用40重量％由實施例丨所製得 之防水粒料，以及60重量％的細砂混合形成混合細骨材， 上述細骨材與膠結材（水泥）的重量比為24 : 1，水與膠結材 (水泥）的重量比為〇·75 : 1，然後添加25%水泥重量的混凝 土摻料（強塑劑），經標準拌合順序後，測得之水泥砂漿的流 動度為90%，此砂漿澆製而成的結構物的28天抗壓強度為 172_5 kgf/cm2。其抗壓強度符合非結構性混凝土強度要求 (140 210 kgf/cm2) ’故適合應用在例如：消波塊、安全島、 人行道及排水溝等結構物的製造上。在本實施例中未添加 粗骨材，但在本發明的營建工程材料中亦可加入粗骨材。 【實施例4】 本發明實施例4是取用20重量％由實施例1所製得之 防水粒料，並且將該防水粒料與80重量％的細砂混合形成 細骨材，未添加粗骨材，上述細骨材與膠結材（水泥）之重量 12 1263624 1 5水與膠結材（水泥）的重量比為〇·6:1，然後在 該等混合物中添加1.6%水泥重量的混凝土摻料（強塑劑）， 經標準掉合順序後，測得之水泥砂漿的流動度為1 00%，且 該砂敷所建構的結構物其28天抗壓強度為291.8 kgf/cm2。 此結構物由於符合結構性混凝土強度要求（210 kgf/cm2以上） ’故一般土木建築結構設施皆可使用。In the present invention, when the amount of the waterproof pellets is 50 to 100% by weight of the entire fine aggregate, the prepared concrete has good fluidity, and the 28-day compressive strength can reach 110 kgf/cm2. It can be applied, for example, to a controlled low-strength material that is free of compact roadbed filling. When the waterproof pellet is used in an amount of 40 to 50% by weight of the total fine aggregate, the 28-day compressive strength can be increased to 170 kgf/cm 2 , and the prepared concrete is suitable for use in, for example, a wave-eliminating block. Non-structural concrete works such as safety islands, sidewalks, drains, etc. When the use of waterproof pellets accounts for less than 4% by weight of all fine aggregates, the 28-day rolling strength can be increased to 21〇kgf/cm2, which has met the strength requirements of structural concrete and can be applied to general civil engineering. The engineering works. Since the concrete structure obtained meets the requirements of workability and compressive strength of various construction projects, it also has good rigidity and waterproof characteristics. Therefore, if it can be used in a large number of concrete guards, it will be able to consume a large amount of reservoirs. Mud, at the same time, promote the clearing of the reservoir in order to reduce the reservoir in the heart. While protecting the environment and ecology, it can also extend the use of the reservoir. The construction engineering materials of the present invention are generally coated on the surface of the building. At the time, the basic composition includes: cement as a cementing agent and material, water, fine aggregate and concrete admixture (strong plasticizer, etc.), wherein the July material also contains a small amount of fine stone, In the fire pellets produced by the modification method, the amount of the above-mentioned waterproof pellets used in all the fine aggregates has a water-repellent effect as long as I:% by weight. That is to say, in the case of waterproof pellets (4), the amount of fine aggregates in the construction materials is more than 1% by weight, and it can be used in: 9 1263624, which will affect the strength and workability (that is, it has the same properties as the general standard waterproof coating). ), achieving a lower water absorption ratio and meeting the requirements of the CNS specification. [Embodiment] [Embodiment 1] Referring to Figure 1, an embodiment of the present invention! First, take 1 gram of the Agongdian reservoir sludge, and then measure the cation exchange equivalent of the reservoir sludge is 20meg/100g, then add 5 liters of water to dilute and stir, then add "grams of n-dodecylamine ( Dodecyl amine) is a cationic surfactant for modification. The amount of the above modifier is calculated by the following formula, wherein the molecular formula of n-undecamine is C! 23⁄4 7N, molecular weight 18535* in the mud cation exchange equivalent 1000 x after the cation price of the mud modification agent, the reservoir sludge and the cationic surfactant are stirred at room temperature for more than 8 hours to complete the replacement of the positive material exchange, and then the modified reservoir is filtered and dehydrated in the mud. After drying to a weird weight, the grind is passed through a waterproof pellet of ASTM No. 100 sieve (15〇/Zm), and the following thermogravimetric analysis and water immersion test can be carried out. ' (1) Thermogravimetric analysis results 1 The construction materials of the completed construction materials have changed the hydrophilicity of the original Shixi layer into water repellency. It is known from the test results of Annex i that when the mud is not modified, the second layer is easy to absorb water and is relatively large in the vicinity. The weight loss, so the weight-to-time differential curve shows the maximum peak near 10 CTC. The thermal weight of the modified reservoir sludge (ie, waterproof pellet) prepared by the inventive example 1 of Annex 2 is 10 1263624 The results show that the thermogravimetric analysis of the reservoir before and after upgrading is obviously changed. 'The maximum peak value of the thermal weight loss of the reservoir age mud appears near 300 °C'. This is the weight loss of the modifier used. Temperature, while the thermal weight loss caused by water near 100C is very small, resulting in only a small peak of the thermal differential curve, indicating that the amount of water absorption between the layers of water and mud has been greatly reduced after the modification, and it can be regarded as almost no water absorption. (7) Water immersion test: It can be seen from the display on the left side of Annex 3 that the unmodified water slurry has a hydrophilic second interlayer surface, so when it is placed in water, it will swell and then cleave into fine particles. From the graphic display on the right side of Annex 3, it can be seen that the surface of the reservoir has a water-repellent surface between the layers of the sludge, so that the modified water slurry of the small particle size is easy to float on the water surface. The quality water sludge is not in the water, and a protective film is formed on the surface of the appearance. It will not be cracked by water infiltration. Therefore, after the modification, the reservoir can be regarded as a shape-stable pellet in the mud. As a result, it is known that each (9) mountain... Only the modified reservoir of Example 1 is almost completely non-absorbent due to the surface of the mud in the Xixi 1 - the external surface is only slightly absorbed by the L-stabilized silk material. Therefore, the waterproof pellets prepared according to the same may be partially or completely taken from the fine aggregates in the material. 7 [Example 2] The waterproof pellets prepared in Example 1 were used to replace the concrete in the concrete. Some of the materials, water, coarse aggregates, one and two, and the winning materials (cement and etc.), etc., are properly mixed and mixed:: r mixed coffee ^ j mouth, pouring, can be formed The structure of 11 1263624 is used for engineering. In the present embodiment, the water-repellent pellets prepared in the embodiment 丨 are used in place of the fine sand in the conventional concrete, and the coarse aggregate is not added, and the weight of the above-mentioned waterproof pellet and the cemented material (cement) is taken. Compared with 4 2·4: 丨, water and cement (the cement ratio is L25: i, then add 75% cement weight of concrete admixture (strong plasticizer)' after the standard mixing sequence, the cement sand is measured (4) The fluidity is 1%. When the mortar is poured into a structure, its 28-day compressive strength is 5/·3 kgf/cm2. The above compressive strength meets the controllability of, for example, compacted roadbed filling works. Low strength and high fluidity requirements of the strength material. [Example 3] Inventive Example 3 uses 40% by weight of the water-repellent pellets obtained from the examples, and 60% by weight of fine sand to form a mixture. Fine aggregate, the weight ratio of the above-mentioned fine aggregate to cement (cement) is 24:1, the weight ratio of water to cement (cement) is 〇·75: 1, and then 25% cement weight of concrete admixture is added ( Strong plasticizer), after the standard mixing sequence, the measured fluidity of the cement mortar is 90%, this The 28-day compressive strength of the slurry-cast structure is 172_5 kgf/cm2. Its compressive strength meets the requirements of non-structural concrete strength (140 210 kgf/cm2), so it is suitable for applications such as: wave-blocking, safety In the manufacture of structures such as islands, sidewalks, and drains, coarse aggregates are not added in the present embodiment, but coarse aggregates may also be added to the construction materials of the present invention. [Embodiment 4] Embodiment 4 of the present invention 20% by weight of the water-repellent pellet obtained in Example 1 was taken, and the waterproof pellet was mixed with 80% by weight of fine sand to form a fine aggregate, and no coarse aggregate was added, and the above-mentioned fine aggregate and cemented material were obtained. The weight of (cement) 12 1263624 1 5 The weight ratio of water to cement (cement) is 〇·6:1, then 1.6% cement weight of concrete admixture (strong plasticizer) is added to the mixture, and the standard is dropped. After the sequence, the measured fluidity of the cement mortar is 100%, and the 28-day compressive strength of the structure constructed by the sand dressing is 291.8 kgf/cm2. This structure meets the requirements of structural concrete strength (210). Kgf/cm2 or more) 'The general civil engineering structure It can be used.

由附件4的實驗結果得知，本發明所調配之營建工程 材料中’當細骨材中所含之防水粒料的比例越低時，其抗 壓強度越佳’但即使採用100重量％之防水粒料來取代未經 改質之水庫淤泥，其抗壓強度仍然優於未經改質之水庫於 泥而由附件5的實驗數據可以瞭解，隨著防水粒料在細 骨材中使用量的不同，其產生之抗壓強度亦會不同，而適 合運用在不同的領域上。 【實施例5】 本發明貫施例5是將實施例丨所製成之防水粒料應用 泥防水劑之吸水比的標準，掣成 干表成尺寸為16x 4x 4cm的試骨 ，同時依前述標準，製作ψ —砂、、隹& _ ^ 1丁干表作出一軚準試體，上述標準試體j 膠結材（水泥）:水：細砂的比例為1:〇.485:2.4。 在防水塗層上，上述防水塗層包含有：膠結材（水泥）、水及 細骨材’且未添加混凝土摻料（強塑劑等），三者間的比例為 1.0.6.2.4 ’其中細骨材中包含有2〇重量％由實施例1所製 传之防水粒料，其餘為普通的細砂。之後參考㈣3加水 將该等試體成型經48小時脫模後 濕度95%以上之養護櫃内養護 於溫度23·0± 1.7它 19天，再於常溫室内養護 13 1263624 7天後進行吸水試驗。根據以下公式計算1、5、24小時吸 水量及吸水比： 吸水量=吸水後質量（g)_乾重量（g) 吸水比=添加改質水庫淤泥水泥砂漿之吸水量 標準試體水泥砂裝之吸水量 經實驗結果證實，標準試體水泥砂漿之吸水量平均值 為29g，添加防水粒料之水泥砂漿的吸水量平均值為3g， 因此本發明實施例5所調製的營建工程材料之吸水比平均 值為0.103，合乎規範吸水比為0.5以下之要求。 而由附件6左侧圖形顯示可知，當水滴在混合有未經 改質之水庫淤泥的試體上時，水分子會滲透到試體内，其 防水效果較差，而由附件6之右側圖形的顯示可知，當水 滴落在由本發明防水粒料所製得之試體上時，水滴可形成 圓珠狀地附著在試體的外部表面及内部斷面，由此可見， 本發明之水庫淤泥的改質方法確實可以製造出具有極佳防 水=果的防水粒料，附# 7為防水粒料之防水機制示意圖 田该防水粒料運用在例如：防水塗層之營建工程材料上 時’亦具有良好的防水效果。 &、惟以上所述者，僅為本發明之較佳實施例而已，當不 月b以此限定本發明會々 範圍及發明說二= = 屬本發明專利涵蓋之範圍内。早心化與修飾，皆仍 【圖式簡單說明】 圖1是本發明改質方法之一 。 平又1 土戶、Μ例的流程示意圖 14 1263624 附件1 : 一種未經改質之水庫於泥的熱重分析曲線圖。 附件2 :係本發明實施例1之改質後水庫淤泥的熱重分 析曲線圖。 附件3 :未經改質之水庫淤泥與實施例1之改質後水庫 ;於泥的水中浸置試驗比對圖形。 附件4 :是一抗壓強度及流動度的對照表，說明營建工 私材料各組成之比例與結構物之抗壓強度及砂漿流動度的It is known from the experimental results of Annex 4 that in the construction engineering materials formulated by the present invention, the lower the proportion of the waterproof pellets contained in the fine aggregate, the better the compressive strength', but even if 100% by weight is used. Waterproof pellets replace the unmodified reservoir sludge, and its compressive strength is still better than that of the unmodified reservoir in the mud. It can be understood from the experimental data of Annex 5, with the use of waterproof pellets in fine aggregates. The difference in compressive strength is different, and it is suitable for use in different fields. [Example 5] The fifth embodiment of the present invention is a standard for applying the water-repellent ratio of the water-repellent granules of the water-repellent granules prepared in the example 掣 to a test piece having a size of 16 x 4 x 4 cm, and Standard, making ψ - sand, 隹 & _ ^ 1 Ding dry table to make a quasi-test body, the above standard test body j cement (cement): water: fine sand ratio of 1: 〇.485: 2.4. On the waterproof coating, the above waterproof coating comprises: cement (cement), water and fine aggregates and no concrete admixture (strong plasticizer, etc.), the ratio between the three is 1.0.6.2.4 ' The fine aggregate contains 2% by weight of the waterproof pellets produced by the first embodiment, and the rest is ordinary fine sand. After that, reference is made to (4) 3 water addition. The test pieces are molded in a curing cabinet with a humidity of 95% or more after 48 hours of demoulding. The temperature is maintained at 232.0 ± 1.7 for 19 days, and then maintained in a constant greenhouse for 13 days. According to the following formula, calculate the water absorption and water absorption ratio for 1, 5, 24 hours: water absorption = mass after water absorption (g) _ dry weight (g) water absorption ratio = water content of added modified reservoir sludge cement mortar standard test cement sand The water absorption amount was confirmed by experimental results, the average water absorption amount of the standard test cement mortar was 29 g, and the average water absorption amount of the cement mortar added with the waterproof pellet was 3 g, so that the water absorption of the construction engineering materials prepared in Example 5 of the present invention was The ratio is 0.103, which meets the requirement of a water absorption ratio of 0.5 or less. From the graph on the left side of Annex 6, it can be seen that when the water droplets are mixed on the test body with the unmodified reservoir sludge, the water molecules will penetrate into the test body, and the waterproof effect is poor, and the pattern on the right side of the attachment 6 It can be seen that when water droplets fall on the test piece prepared by the waterproof pellet of the present invention, the water droplets can be attached to the outer surface and the inner cross section of the test piece in a ball shape, thereby showing that the reservoir sludge of the present invention The upgrading method can indeed produce waterproof pellets with excellent waterproof=fruit, and #7 is the waterproof mechanism of waterproof pellets. The waterproof pellets are used in, for example, construction materials for waterproof coatings. Good waterproof effect. The above is only the preferred embodiment of the present invention, and the scope of the present invention and the invention are not included in the scope of the present invention. Both early hearting and modification are still [Simplified illustration of the drawings] Fig. 1 is one of the methods for upgrading the present invention. Diagram of the process of Ping and 1 Tu households and villages 14 1263624 Annex 1 : Thermogravimetric analysis curve of a non-modified reservoir in mud. Attachment 2: is a thermogravimetric analysis curve of the modified reservoir sludge of Example 1 of the present invention. Annex 3: Unmodified reservoir sludge and the modified reservoir of Example 1; immersed in the mud water to test the comparison pattern. Annex 4: is a comparison table of compressive strength and fluidity, indicating the proportion of each component of the construction and construction materials and the compressive strength of the structure and the fluidity of the mortar.

在工程上的應用領域。 卜建工程材料所 之抗壓強度的關係，以及其Application areas in engineering. The relationship between the compressive strength of Bujian Engineering Materials and its

說明水庫於 附件7 : 防火粒料防水機制示意圖。 15 1263624 附件1 :一種未經改質之水庫淤泥的熱重分析曲線圖Explain the reservoir in Annex 7: Schematic diagram of the waterproof mechanism of fireproof pellets. 15 1263624 Annex 1: Thermogravimetric analysis of an unmodified reservoir sludge

-1 -—^-^IMSWA-1 -—^-^IMSWA

16 1263624 附件2 :係本發明實施例1之改質後水庫淤泥的熱重分析曲線圖 Μ ft16 1263624 Annex 2: Thermogravimetric analysis curve of the modified reservoir sludge of Example 1 of the present invention Μ ft

500 mi 700 Temperature (*C)500 mi 700 Temperature (*C)

17 1263624 附件3 :未經改質之水庫淤泥與實施例1之改質後水庫淤泥的水 中浸置試驗比對圖形17 1263624 Annex 3: Water-immersed test comparison pattern of unmodified reservoir sludge and modified reservoir sludge of Example 1

未改質水庫淤泥Unmodified reservoir mud

1263624 附件4 :是一抗壓強廣另、、六番疮 及/爪動度的對照表，說明混凝土中所含 經改質水庫於泥之粒料、水灰比、細粒料及水泥比和混凝土結構 物中之抗壓強度，以及砂襞的流動度間的關係 材料來源 取代細骨材 量 s/c (砂與水泥比） w/(c+p) (水膠比） 強塑 劑 流動 度 抗壓強 度 未改質水庫淤泥 100% 2.40 2.50 - 105 33.1 改質水庫淤泥 100% 2.40 1,25 7.5 100 56.3 改質水庫淤泥 80% 2.40 1.15 7.5 95 86.5 改質水庫淤泥 50% 2.40 0.85 5 95 139.2 改質水庫淤泥 40% 2.40 0.75 2.5 90 172.5 改質水庫淤泥 3 0% 2.40 0.65 2.5 85 215.2 改質水庫於泥 20% 2.40 0.60 1.6 100 291.8 19 1263624 附件5 ·是一抗塵強度的對照表，說明混凝土所含經改質水庫 於泥之粒料與混凝土結構物中之抗壓強度的關係，以及其在工程 上的應用領域1263624 Annex 4: is a comparison table of the pressure resistance, the six acne and the claw movement, indicating the ratio of the pellets, water-cement ratio, fine-grain and cement ratio of the modified reservoir in the concrete. The relationship between the compressive strength in concrete structures and the fluidity of sand slabs. The source of materials replaces the amount of fine aggregates s/c (sand to cement ratio) w/(c+p) (water-to-binder ratio). Degree of compressive strength is not modified reservoir sludge 100% 2.40 2.50 - 105 33.1 Modified reservoir sludge 100% 2.40 1,25 7.5 100 56.3 Modified reservoir sludge 80% 2.40 1.15 7.5 95 86.5 Modified reservoir sludge 50% 2.40 0.85 5 95 139.2 Modified Reservoir Silt 40% 2.40 0.75 2.5 90 172.5 Modified Reservoir Sludge 3 0% 2.40 0.65 2.5 85 215.2 Modified Reservoir in Mud 20% 2.40 0.60 1.6 100 291.8 19 1263624 Annex 5 · is a comparison table of dust resistance, Explain the relationship between the compressive strength of the modified slurry in the concrete and the concrete structure, and its application field in engineering.

材料來 取代細骨 抗壓強 要求強 營建材料 源 材量 度 度 應用 改質水庫淤泥 100% 56.3 控制性低強度 材料 改質水庫淤泥 80% 86.5 10 0以下 i 改質水庫於泥 50% 139.2 改質水庫於泥 40% 172.5 140-210 非結構混凝土 改質水庫於泥 3 0% 215.2 21 0以上 結構混凝土 改質水庫於泥 20% 291.8Material to replace the fine bone pressure resistance requirements Strong construction materials source material measurement application of modified reservoir sludge 100% 56.3 Controlled low-strength material upgraded reservoir sludge 80% 86.5 10 0 below i modified reservoir in mud 50% 139.2 upgrading Reservoir in mud 40% 172.5 140-210 Unstructured concrete upgrading reservoir in mud 3 0% 215.2 21 0 or more Structural concrete upgrading reservoir in mud 20% 291.8

20 1263624 附件6 :是兩種試體的防水試驗比對圖形，說明水庫淤泥在改 質前及改質後作出試體時的防水狀態20 1263624 Attachment 6: It is the waterproof test comparison chart of the two test pieces, indicating the waterproof state of the reservoir sludge before and after the modification.

21 1263624 附件7 :防水粒料防水機制示意圖21 1263624 Annex 7: Schematic diagram of waterproof mechanism of waterproof pellets

骨材Aggregate

-►水泥漿體-►Cement paste

II HZl·-►改質水庫淤泥II HZl·-► modified reservoir sludge

22twenty two

Claims (1)

12( 12( ί94102128唬^請案之申請專利 十、申請專利範圍： =本0^泠| 1. 一種水庫於泥之改質方法，用來改質賢Hu 泥，句.冬LV 止$ . #工貝t水庫 淤泥，包含以下步驟· 加水授拌：於常溫下在水庫於泥中加水稀釋· 質劑：依據水料泥之陽離子當量，加人陽 界面活性劑進行_子錢取代仙，㈣ ，且改質劑的添加量係以下列公式計算而得；、’''、十—私 ^§) 改質劑分子量X改貝劑除離子價數 去除水份：去除改質後之水庫於泥中的水份，·及 ⑺研磨：將去除水份後之水料泥研磨成較小粒徑， 如具有厭水特性之防水粒料。 " 2. 依據申請專利範圍第}項所述水庫於泥之改質方法，其中，加 水攪拌之加水量為該水庫淤泥的丨〜丨㈨倍。 口 3. 依據中請專利範圍第1項所述水料泥之改質方法4中，去 除水分的步驟包含：過濾、、脫水及烘乾。 4· 一種營建工程材料， • 已5有膝結材、水、細骨材及混凝土摻料 ， 、其特徵在於：該細骨材中包含有1〜100重量％由第】項言主 求項所製成之防水粒料。 月 5·依據申請專利範圍第4項所述之營建工程材料，其中，該防水 粒料之含量佔全部細骨材的5 〇〜丨0 0重量％。 6,依獅請專利範圍第4項所述之#建工程材料，其中，該防水 23 1263624 粒料之含置佔全部細骨材的4〇〜5〇重量％。 7 ·依據申请專利範圍第4工音说、十，々& 国弟4項所述之營建工程材料，复 粒料之含量佔全部4 〃 6亥防水 3里佔王邛細骨材的I〜40重量％。 8 ·依據申凊專利範圍第4至7百由 並中，㈣ 項中任—項所述之營建工程材料， /、肀膠、、、°材、水、細骨材及混凝土摻料的比為·· 1:(0.05〜5):(1 〜1〇):(0 〇〇1〜〇 2)。 9.依據中請專利範圍第8項所述之營建工移材料，更包含與膠結 材之比值為〇, 1〜1 〇的粗骨材。 10·-種營建工程材料，包含有：膠結材、水及細骨材； 其特徵在於：該細骨材中含有1〜100重量％由第1項請求 項所製成之防水粒料。 U·依據中請專利_第1Q項所述之營建工程材料，其中，膠結 材：水··細骨材=1:0·6:2·4。 2412( 12( ί94102128唬^Request for patent application ten, the scope of application for patent: = this 0^泠| 1. A method of upgrading the reservoir in mud, used to upgrade the sage Hu mud, sentence. Winter LV stop $. #工贝特水库泥泥, including the following steps: Add water to mix: at room temperature, dilute water in the mud in the reservoir. Qualitative: According to the cation equivalent of water mud, add human cation surfactant to replace xianzi, (4), and the amount of modifier added is calculated by the following formula;, ''', ten-private^§) modifier molecular weight X modified sheller in addition to ion valence to remove water: remove the modified reservoir Moisture in the mud, and (7) Grinding: The water slurry after removing the water is ground to a smaller particle size, such as a waterproof pellet having a water-repellent property. " 2. According to the scope of the patent application The method for upgrading the reservoir in the mud, wherein the amount of water added to the water is 丨~丨(9) times the sludge of the reservoir. 3. According to the method 4 of the modification of the water sludge according to the first item of the patent scope, The steps of removing moisture include: filtration, dehydration and drying. • Has 5 knees, water, fine aggregates and concrete admixtures, characterized in that the fine aggregate contains 1 to 100% by weight of the waterproof pellets made by the main item of the first item. According to the construction materials mentioned in item 4 of the patent application scope, the content of the waterproof pellets accounts for 5 〇~丨0 0% of the total fine aggregates. The construction materials mentioned in the item, wherein the waterproof 23 1263624 pellets account for 4〇~5〇% by weight of all the fine aggregates. 7 · According to the 4th working tone of the patent application scope, ten, 々 & The construction materials of the four brothers mentioned in the national brothers, the content of the complex pellets accounted for 1 to 40% by weight of the total of 4 〃 6 hai waterproof 3 占. 8 · According to the application scope of patents 4 to 7 The ratio of the construction materials, /, rubber, steel, water, fine aggregate and concrete admixture mentioned in (4) of the items is (1) (0.05~5): (1 ～1〇): (0 〇〇1~〇2) 9. According to the construction work shift material mentioned in item 8 of the patent scope, the ratio of the material to the cement material is included. 〇, 1~1 粗 of coarse aggregate. 10·- kinds of construction materials, including: cement, water and fine aggregate; characterized by: 1 to 100% by weight of the fine aggregate by the first item Waterproof pellets made from the requirements. U. According to the construction materials mentioned in the patent _1Q item, the cement material: water··fine aggregates=1:0·6:2·4. 24