200918193 九、發明說明 【發明所屬之技術領域】 本發明係有關降低重金屬類之處理材料，及降低重金 屬之處理方法，以及藉由該降低用處理材料之造粒化處理 材料之製造方法，及使用該造硫化處理劑之地盤材料。 【先前技術】 近年來，隨著自整備港灣及煤碳火力發電所等所排出 之廢棄物之煤灰飛灰及疏濬污泥（或土砂）處理量之增加 ’由於已存在之處理場已達飽和狀態，因而使這些大量白勺 疏濬土砂及煤灰飛灰的處理受到矚目，正強烈地尋求對環 境安全之有效利用方法。 目前已嘗試將疏濬土砂於進行脫水•固化處理後，{乍 爲粉碎後塡土木材及綠地用土壤等地盤材料使用，或於$ 行煆燒處理後，作爲花磚及磚塊等構造材料使用等。 該疏濬土砂大多來自天然之土砂，其因堆積場所之y 同’而含有來自家庭排水及工廠廢水所帶來的有害物質（ 重金屬類及人工合成化學物質等），重金屬類及人工合成 化學物質等進行處理時’有時會發生含有（溶出）超過環 境基準値之情形。 另外，目前亦正關注於將煤灰（底灰與飛灰）與樹脂 材料等固化劑混合後，作爲人工大理石及塊狀材料，以及 將其與水泥固化材料混合後，作爲路盤材料及回墳材料等 再生材料使用。 200918193 於該煤飛灰中，含有氟、硼、硒等有害無機質之重金 屬物質，而於將來自煤灰飛灰之再生材料使用爲道路材料 及回塡材料時，目前正尋求環境部所定之重金屬溶出試驗 値能夠符合環境基準値以內之方法。 關於煤灰等之再利用，已以含水土壤改良材料之技術 ，揭示於專利第3 243 804號公報等。 另外，含有害物質之土壤處理劑之技術，亦已揭示於 特開2005-232341號公報。 專利文件1 :專利第324 3 804號公報 專利文件2 :特開2 0 0 5 - 2 3 2 3 4 1號公報 然而於前述之專利第324 3 8 04號公報中，爲了使含水 土壤能夠再利用而使其強度增加，且賦予如沙粒般之流動 性，並非降低重金屬等之有害物質，做爲適合環境基準的 土壤之技術。 特開200 5 -23 23 4 1號公報因係將土壤中所含之毒性高 之六價鉻還原爲安定的三價鉻’限定爲六價鉻之技術，再 使用亞硫酸氫鈉與蛋白質者，並且因需要化學藥品之技術 ，而非降低六價鉻以外的氟、硼、硒等有害物質。 【發明內容】 本發明係以提供可同時降低如前述之廢棄物中所含之 多種類有害物質之處理技術爲課題。 爲解決前述課題’於本發明中’其特徵係以紅土做爲 降低重金屬類之處理材料之主成分’且特徵爲該紅土係國 -6- 200918193 頭融合土。 該紅土係分散分布於全日本各地，黏著力弱且易溶於 水中’另外，因粒子非常細小而不易沉澱，容易因降雨等 而流出。特別是於沖繩縣內稱作國頭融合土（ kunigami mahji soil)，其爲PH4〜6之酸性土壤，含豐富的鐵及鋁 ’以獨特的紅色土壤分布於廣大的範圍中。 將國頭融合土之礦物含有率（％)之測定例示於下。 採樣地地名： 所含礦物名稱 石川 宜野座 恩納 二氧化矽 69.0 72.0 72.0 氧化鋁 18.0 16.0 15.0 氧化鐵 9.0 7.0 7.3 矽鋁比 6.3 7.4 7.9 矽鋁鐵比 4.06 4.41 4.49 於本發明中如上所述，二氧化矽之含量以65.0〜75.0 %左右爲佳。 氧化鋁之含量以13.0〜20.0%左右爲佳，15.0〜20.0 更佳。 氧化鐵之含量以5.0〜12.0%左右爲佳，7.0〜12.0更 佳。 該重金屬類係指可能含有煤灰·垃圾燒成灰及土砂等 之無機質之重金屬類，特別於本發明中係指含於疏濬土砂 及煤灰飛灰中，於將其再利用時可能發生問題之重金屬。 根據環境部所訂於環境基準中可列舉之8種無機質重 200918193 金屬係水銀、錯、砷、六價鉻、硒、硼、氟、鎘。 本發明之特徵爲對於前述之降低用處理材料混合有結 晶化促進劑，作爲複合之降低重金屬類之處理材料。 該結晶化促進劑只要是具有以混合促進以化學反應產 生結晶化的作用者即可，可將該結晶化促進劑之原液經稀 釋後使用。 本發明之特徵係對於前述降低用處理劑與結晶化促進 劑，混合固化材料，試圖降低重金屬類。 該固化劑可使用水泥系固化材料等。以普通混凝土 (Normal Portlamd Cement)等爲佳。 本發明之特徵係對於前述降低用處理材料與該結晶化 促進劑，混合鼓風爐熔渣微粉末，做爲降低重金屬類之處 理材料。 該鼓風爐熔渣微粉末係將自製鐵所等之熔礦爐中所排 出礦渣之鼓風爐熔渣進行破碎，經微粉末化處理後者，其 品質比重爲2.80以上，比表面積爲5,000 cm2/g以上〜未 達 1 0,000cm2/g 者。 本發明係對於前述降低用處理材料，混合煤灰飛灰爲 特徵，做爲降低重金屬類之處理材料。 該煤灰飛灰係於火力發電所等燃燒爐中使煤碳燃燒後 所排放出之燃燒灰，一般因該灰中含有重金屬類等，而將 其進行廢棄處理。 於本發明其特徵係使用前述之任何一種處理材料（劑 )進行處理之做爲降低重金屬類之處理方法。 -8 - 200918193 因該處理材料（劑）係將其與含重金屬之土壤及廢液 ’或燃燒灰等含重金屬之廢棄物進行混合，藉由處理材料 (劑）中所具有之物理性以及化學性的吸附及封入（不溶 化）作用’使廢棄物中之重金屬類處於化學上的安定，及 於完成吸附後，以使其無法回復原狀而固化•不溶化之方 式，來進行降低處理。 本發明特徵爲相對於紅土，係混合0.05〜0.5重量％ 之結晶化促進劑、1〜2 5重量％之固化材料、1〜1 5重量 %之鼓風爐熔渣微粉末、30〜50重量％之煤灰飛灰，再加 入水分使水固體重量比成爲2 0〜2 3 %後，進行造粒處理。 加之，本發明係於進行降低重金屬處理後，再進行造粒處 理材料之製造爲方法。其中，水固體重量比定義爲所添加 水之重量，相對於紅土、煤灰飛灰、固化材料（普通的混 凝土）及鼓風爐熔渣微粉末之合計重量之比。 重金屬類因紅土所具有之離子，引起離子交換作用等 之後，而使離子被吸附處理。進而，重金屬類因固化材料 等而與紅土 一同被固化，而藉由無法溶出之被固定化（不 溶化）處理，實現降低重金屬類之處理。 煤灰之飛灰因具有稱作固化反應（自我硬化作用）之 長期性的硬化作用，而將該飛灰利用爲紅土的固化輔助材 料。另外，結晶化促進劑係可促進紅土之固化與重金屬之 不溶解化。 造粒處理係爲易於使用混合紅土與煤飛灰後之造粒處 理材料而對粒度進行調整之處理’可使用市售之造粒機械 -9- 200918193 。例如可使用北川鐵工所製之行動型混練造粒機等。以附 有震動裝置之造粒機更佳。 進行造粒處理之造粒用處理材料係以粒徑0.075mm〜 75mm之粗粒份爲98%，未達粒徑0.075mm之細粒份爲2 %左右爲佳。 本發明係具以下效果。 1 )可實現活用紅土吸附作用之降低重金屬類之處理 材料。 2 )可實現活用國頭融合土之降低重金屬類之處理材 料。 3 )可實現活用紅土吸附作用與固化材料，及鼓風爐 熔渣微粉末之固定•不溶化作用之具效果的降低重金屬類 之處理材料。 4 )可實現活用紅土吸附作用之降低重金屬類之處理 方法。 5 )可實現活用紅土吸附作用之降低重金屬類之處理 材料之製造方法。 6 )對於含重金屬之產業廢棄物，可實現無須特殊化 學藥品即可進行降低重金屬類之處理。 7 )可有效降低含重金屬之疏濬土砂，及煤灰等廢棄 物之重金屬類，且可將造粒處理材料做爲路盤材料及回塡 材料等地盤材料而進行再生利用。 【實施方式】 -10- 200918193 實施例 使用圖面針對本發明之實施方式加以說明。 〔試驗例1〕 於本試驗係使用含氟、硼、硒等重金屬類之煤灰飛灰 之污染水，及含六價鎘重金屬之水泥污染水，及使用於沖 繩縣內所採取之紅土之國頭融合土。 測定做爲試樣之煤灰飛灰之污染水及水泥污染水2胃 金屬含量，結果如下所述。所測定之重金屬之種類爲下述 之5種。 重金屬類之含量Og/L) 六價錦 晒 砸氟碑 水泥污染水 0.1940 煤灰污染水 0.0016 0.626 0.88 0.0008 上述之水泥污染水及煤灰污染水’係以純水稀釋1 /2 後做爲試樣液。 該紅土係使用於前述之針對國頭融合土礦物含有率（ % )之測定例中，於沖繩縣具志川市石川地區之農地所採 集之紅土。 於因紅土而降低重金屬類之確認試驗中，相對於稀釋 1 / 2後之前述之水泥污染水及煤灰污染水之重量’以紅土 重量分別爲 1) 0%，2) 17% ’3) 25% ’4) 33% 等 4 個 條件進行混合•攪拌後，再分別測定重金屬之3有量。 -11 - 200918193 圖1係其測定結果，（1 )係表示因紅土而降低重金 屬含有量之測定結果表，（2 )係表示因紅土而降低重金 屬含有量之效果圖。 根據該測定結果，六價鎘約爲原來之1/40，硒約1/7 ，硼約1/2，氟約1/5，砷約1/7，可知其含量均有顯著地 降低。 針對因紅土之吸附作用，於前述之分析結果顯示，二 氧化矽、氧化鋁、氧化鐵係重要之吸附要素。認爲這些成 分比例之矽鋁比或矽鋁鐵比，對重金屬類之吸附作用具有 極大之影響。 因廣義地解釋吸附現象係定義爲「存在於2相（固相 與液相、固相與氣相等）之界面物質被濃縮之現象」，本 試驗之吸附係於土壤粒子與污染水之界面產生吸附。 土壤粒子與污染水中所含之各種溶質間具代表性之吸 附係有下述等情形： 1)由於未離子化之有機化合物等分子，與於未帶電 粒子表面間之分子間作用力（凡得瓦力），溶質緊密地吸 附於粒子表面。 2 )由於以離子型態溶解後之溶質，與帶電粒子表面 間之庫侖作用力，一部分緊密黏著於粒子表面，剩餘的溶 質未與表面緊密結合而被拘束於界面附近。 紅土因其粒子微細而被分類爲黏土礦物。黏土中所含 之矽Si，鋁A1，鐵Fe等各種元素，於礦物粒子之邊緣部 位，與氧〇及氫Η結合後，形成Si - OH—，Al — OH—， -12- 200918193200918193 IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a method for reducing heavy metal treatment materials, a method for treating heavy metals, and a method for producing a granulation treatment material by using the treatment material for reduction, and The site material for the vulcanization treatment agent. [Prior Art] In recent years, with the increase in the amount of coal ash fly ash and dredged sludge (or soil sand) discharged from the self-reserving harbors and coal-fired thermal power stations, the existing treatment sites have reached Saturated state, and thus the treatment of these large amounts of dredged soil sand and coal ash fly ash has attracted attention, and an effective use of environmental safety is being strongly sought. At present, we have tried to use the dredged soil sand for dewatering and solidification treatment, and then use it as ground material such as smashed bauxite wood and green land, or as a structural material such as tiles and bricks after being burned. . Most of the dredged soil sand comes from natural earth sand, which contains harmful substances (heavy metals and synthetic chemicals) from household drainage and factory wastewater, heavy metals and synthetic chemicals, etc. due to the accumulation of the site. When processing, 'there may be cases where the content (dissolution) exceeds the environmental standard. In addition, attention is currently being paid to mixing coal ash (bottom ash and fly ash) with a curing agent such as a resin material, as an artificial marble and a block material, and mixing it with a cement solidified material, as a road plate material and returning graves. Recycled materials such as materials are used. 200918193 In this coal fly ash, it contains heavy metals such as fluorine, boron, selenium and other harmful inorganic substances. When using recycled materials from coal ash fly ash as road materials and recycled materials, it is currently seeking heavy metals as determined by the Ministry of the Environment. The dissolution test can be carried out in accordance with the environmental standards. Regarding the reuse of coal ash and the like, the technique of improving the material with water-containing soil is disclosed in Japanese Patent No. 3 243 804 and the like. Further, a technique of a soil treating agent containing a harmful substance is disclosed in Japanese Laid-Open Patent Publication No. 2005-232341. Patent Document 1: Patent No. 324 3 804 Patent Document 2: Japanese Patent Publication No. 2 0 0 5 - 2 3 2 3 4 1 However, in the aforementioned Japanese Patent No. 324 3 8 04, in order to enable the water-containing soil to be re- It is used to increase its strength and imparts fluidity like sand. It is not a technology that reduces harmful substances such as heavy metals and is suitable as an environmental reference. JP-A-200 5-23 23 4 No. 1 is based on the technique of reducing the highly toxic hexavalent chromium contained in the soil to a stable trivalent chromium, which is limited to hexavalent chromium, and then using sodium bisulfite and protein. And because of the need for chemical technology, rather than reducing harmful substances such as fluorine, boron, and selenium other than hexavalent chromium. SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a treatment technique capable of simultaneously reducing a plurality of types of harmful substances contained in the waste as described above. In order to solve the above problems, the present invention is characterized in that red soil is used as a main component of a treatment material for reducing heavy metals, and it is characterized by the red soil system -6-200918193 head fusion soil. The laterite system is dispersed throughout Japan and has a weak adhesion and is easily soluble in water. In addition, since the particles are very small, they are not easily precipitated and are likely to flow out due to rainfall. Especially in Okinawa Prefecture, it is called kunigami mahji soil, which is an acidic soil of PH4~6, rich in iron and aluminum. It is distributed in a wide range with unique red soil. The measurement of the mineral content (%) of the country's fusion soil is shown below. Sampling place name: Mineral name Ishikawa Yoshino Enna ruthenium dioxide 69.0 72.0 72.0 Alumina 18.0 16.0 15.0 Iron oxide 9.0 7.0 7.3 矽 aluminum ratio 6.3 7.4 7.9 矽 aluminum to iron ratio 4.06 4.41 4.49 In the present invention, as described above, dioxide The content of bismuth is preferably about 65.0 to 75.0%. The content of alumina is preferably about 13.0 to 20.0%, more preferably 15.0 to 20.0. The content of iron oxide is preferably about 5.0 to 12.0%, more preferably 7.0 to 12.0. The heavy metal refers to heavy metals which may contain inorganic substances such as coal ash, garbage burned ash and earth sand, and particularly in the present invention, which are contained in dredged soil sand and coal fly ash, which may cause problems when reused. Heavy metal. According to the environmental standards set by the Ministry of the Environment, there are eight kinds of inorganic weights. 200918193 Metals are mercury, arsenic, hexavalent chromium, selenium, boron, fluorine and cadmium. The present invention is characterized in that a crystallization accelerator is mixed with the above-mentioned treatment material for reduction as a composite material for reducing heavy metals. The crystallization accelerator may be used as long as it has a function of causing crystallization by chemical reaction, and the stock solution of the crystallization accelerator may be diluted. The present invention is characterized in that the above-mentioned reducing treatment agent and crystallization accelerator are mixed with a solidified material in an attempt to reduce heavy metals. As the curing agent, a cement-based curing material or the like can be used. It is preferred to use ordinary concrete (Normal Portlamd Cement). The present invention is characterized in that the blast furnace slag fine powder is mixed with the refractory treatment material and the crystallization accelerator as a material for reducing heavy metals. The blast furnace slag micro-powder crushes the blast furnace slag discharged from the slag discharged from the smelting furnace such as the self-made iron, and the latter has a mass specific gravity of 2.80 or more and a specific surface area of 5,000 cm 2 /g or more. Less than 10,000cm2/g. The present invention is characterized in that the above-mentioned reducing treatment material is characterized by mixing coal ash fly ash as a treatment material for reducing heavy metals. The coal ash fly ash is used in a combustion furnace such as a thermal power plant to burn the ash discharged after burning the coal, and the ash is generally disposed of because it contains heavy metals. The present invention is characterized in that it is treated by any of the above-mentioned treatment materials (agents) as a treatment method for reducing heavy metals. -8 - 200918193 Because the treated material (agent) is mixed with heavy metal-containing waste such as heavy metal-containing soil and waste liquid or burning ash, the physical and chemical properties of the treated material (agent) Sexual adsorption and encapsulation (insolubilization) action makes the heavy metals in the waste chemically stable, and after the adsorption is completed, it can be cured by insolubilizing and insolubilizing. The present invention is characterized in that 0.05 to 0.5% by weight of a crystallization accelerator, 1 to 25% by weight of a curing material, 1 to 15% by weight of a blast furnace slag fine powder, and 30 to 50% by weight of a red clay are mixed. The coal ash is fly ash, and water is added to make the water solid weight ratio 20 to 23%, and then granulation treatment is carried out. Further, the present invention is a method for producing a granulation treatment material after performing a heavy metal reduction treatment. Here, the water solid weight ratio is defined as the ratio of the weight of the added water to the total weight of the laterite, the fly ash fly ash, the solidified material (common concrete), and the blast furnace slag fine powder. The heavy metals are subjected to adsorption treatment after the ions of the red soil cause ion exchange or the like. Further, the heavy metals are solidified together with the red clay by the solidified material or the like, and are treated by immobilization (insolubilization) which cannot be eluted, thereby realizing the treatment for reducing heavy metals. The fly ash of coal ash is used as a curing auxiliary material for laterite because it has a long-term hardening action called a curing reaction (self-hardening action). Further, the crystallization accelerator promotes the solidification of red clay and the insolubilization of heavy metals. The granulation treatment is a treatment for adjusting the particle size by easily using the granulation treatment material after mixing the laterite and the coal fly ash. A commercially available granulation machine -9-200918193 can be used. For example, an action type kneading granulator manufactured by Beichuan Iron Works can be used. It is better to use a granulator with a vibrating device. The granulation treatment material to be subjected to the granulation treatment is 98% of coarse particles having a particle diameter of 0.075 mm to 75 mm, and preferably about 2% of fine particles having a particle diameter of 0.075 mm. The present invention has the following effects. 1) It is possible to realize a treatment material for reducing heavy metals which is adsorbed by red clay. 2) It is possible to realize the treatment of reducing heavy metals by using the national fusion soil. 3) It can realize the treatment of reducing heavy metals by using the red clay adsorption and solidification materials, and the fixed/insolubilizing effect of the blast furnace slag micropowder. 4) It can realize the treatment method of reducing heavy metals by the adsorption of laterite. 5) A method for producing a treatment material for reducing heavy metals which is adsorbed by red clay can be realized. 6) For industrial wastes containing heavy metals, it is possible to reduce the treatment of heavy metals without special chemical chemicals. 7) It can effectively reduce heavy metals such as dredged soil sand containing heavy metals and wastes such as coal ash, and the granulation treatment materials can be recycled as site materials such as road disc materials and recycled materials. [Embodiment] -10-200918193 Embodiment An embodiment of the present invention will be described using the drawings. [Test Example 1] In this test, contaminated water of coal ash fly ash containing heavy metals such as fluorine, boron, and selenium, and cement contaminated water containing heavy metals of hexavalent cadmium, and red soil used in Okinawa Prefecture were used. The national head merges with the soil. The content of the contaminated water of the coal ash fly ash and the cemented water of the cement 2 as the sample were measured, and the results were as follows. The types of heavy metals measured were the following five. Heavy metal content Og/L) Six-price Jin Tan 砸 fluoride monument cement contaminated water 0.1940 Coal ash polluted water 0.0016 0.626 0.88 0.0008 The above-mentioned cement contaminated water and coal ash polluted water ' is diluted with pure water 1 /2 and then tested Sample solution. This red clay system is used in the above-mentioned measurement example of the mineral content (%) of the country-integrated soil, and is collected in the agricultural land of the Ishikawa area of the Shirakawa-shi, Okinawa Prefecture. In the confirmation test for reducing heavy metals due to red clay, the weight of cement contaminated water and coal ash contaminated water after the dilution of 1/2 is 1% by weight of red clay, 0), 2) 17% '3) 25% '4) 33% and other conditions were mixed and stirred, and then the amount of heavy metals was measured. -11 - 200918193 Fig. 1 shows the results of the measurement. (1) shows the measurement results of the reduction of the heavy metal content by red soil, and (2) shows the effect of reducing the heavy metal content by the red clay. According to the measurement results, hexavalent cadmium is about 1/40 of the original, selenium is about 1/7, boron is about 1/2, fluorine is about 1/5, and arsenic is about 1/7, and it is known that the content thereof is remarkably lowered. According to the adsorption effect of red clay, the above analysis results show that cerium oxide, aluminum oxide and iron oxide are important adsorption factors. It is considered that the ratio of bismuth to aluminum or bismuth to aluminum in these proportions has a great influence on the adsorption of heavy metals. The broad explanation of the adsorption phenomenon is defined as "the phenomenon that the interface material existing in the two phases (solid phase and liquid phase, solid phase and gas phase, etc.) is concentrated", and the adsorption of this test is produced at the interface between soil particles and contaminated water. Adsorption. Representative adsorption systems between soil particles and various solutes contained in contaminated water have the following conditions: 1) Intermolecular forces between the surface of uncharged particles due to molecules such as unionized organic compounds (Where The solute is closely adsorbed on the surface of the particle. 2) Due to the Coulomb interaction between the solute dissolved in the ionic form and the surface of the charged particles, a part of the solute adheres to the surface of the particle, and the remaining solute is not tightly bound to the surface and is restrained near the interface. Laterite is classified as a clay mineral due to its fine particles. Various elements such as yttrium Si, aluminum A1, and iron Fe contained in the clay are combined with oxonium and hydroquinone at the edge of the mineral particles to form Si - OH -, Al - OH -, -12 - 200918193
Fe - 〇H -等離子吸附基（表面氫氧基），而成爲負離子 Μ — OH -之形態。此處形態之記號μ係矽Si，鋁A1，鐵 Fe之金屬（Metal)元素。 此時磷酸離子、砷酸離子、鎘酸離子、硒酸離子、硼 酸離子等含氧陰離子，於黏土礦物粒子之邊緣部位，取代 表面氫氧基之氫氧化物離子Μ — OH -，而進行直接配位 。該反應稱作配位子之變換反應，六價鎘及硒等負的含氧 陰離子，於礦物粒子之表面形成表面錯體（配位子交換） 而被吸附。 由上述結果可推測，於紅土中所含之氧化鋁、氧化鐵 與重金屬離子間因產生配位子變換反應而對吸附作用具有 極大之影響。 其次，針對本發明之使用降低重金屬之處理材料等之 造粒材料之製造方法，使用圖面加以說明。 圖2係根據本發明造粒處理材料之製造方法之流程圖 S - 1 )原料混合步驟 將相對於做爲原料之1 〇〇重量％之紅土’取〇.1重量 %之結晶化促進劑、10重量％之普通混凝土 ’ 1〇重量％ 之鼓風爐熔渣微粉末、50.0重量％之煤灰飛灰’再與這些 物質之合計重量之約20重量％之調整水進行混合。 -13- 1 - 2 )混合攪拌步驟 200918193 於造粒裝置中以一定速度進行攪拌，使原料充分混合 。造粒裝製係使用北川鐵工所製之行動型造粒機。將攪拌 之迴轉速度定於100〜200轉/分鐘，攪拌15分鐘。 S — 3 )造粒步驟 於混合攪拌步驟中將原料充分混合後，使用造粒機所 附之震動裝置，於加上震動3分鐘同時進行攪拌，再將完 成製品排出。因倂用震動處理而被混合.震動過之原料， 會成爲球狀而被排出。其粒徑約爲1mm〜70mm左右。 S — 4 )熟化步驟 將造粒處理材料由3天至一星期以自然乾燥而進行熟 化。 充分進行熟化•乾燥後即完成粒狀處理材料。粒徑約 爲1mm〜7 0mm左右，成爲多孔質赤褐色之施行降低重金 屬類之處理之材料。 〔試驗例2〕 其次，實施根據前述方法所製造，以確認造粒處理材 料符合環境基準値爲目的之重金屬類之溶出試驗。 本溶出試驗係以前述8種無機質重金屬類爲對象。試 驗以環境部公告第46號爲準則而實施，其試驗結果如圖3 所示之重金屬溶出試驗結果一覽表。 於造粒處理材料之溶出試驗果中，鎘、鉛、砷、總水 -14- 200918193 銀此4種金屬均爲計量下限値以下，記作ND。六價鎘、 硒、硼於2個提供試驗檢體中之1個爲計量下限値以下， 各別之殘留量約爲環境基準値之1/2.3，1/10，1/1〇〇。進 而’氟之2個提供試驗檢體之平均値相較於環境基準値約 被降低1 / 5。 由前述結果可知，使用紅土、煤灰飛灰、結晶化促進 劑、固化材料（普通混凝土）、鼓風爐熔渣微粉末之造粒 處理材料符合環境基準値，確認其係對地盤環境爲安全的 地盤材料。 〔試驗例3〕 本試驗係假設造粒處理材料受到因酸雨等酸性水，及 因地盤污染之強鹼性水等之影響，而以管柱通水試驗，檢 討因酸性液、中性液.、鹼性液之重金屬再溶出之可•否。 且此處中性液係爲與酸性液與鹼性液進行比較而使用。 做爲管柱通水試驗之對象的有六價鎘、硒、砷、硼此 4種。通水液使用pH4之硝酸液、pH7之純水、PH12之氫 氧化鈉溶液。管柱係以氯乙烯管柱製成，將做爲試驗材料 之造粒處理材料塡充於其中，並自設置於管柱上方之儲水 桶，以維持通水液爲完全飽和之狀態對管柱進行滴注。 通水條件係如圖4所示之通水條件表，將液固比設定 爲 0.1、0.2、0.5、1、10，通水時間爲 2(h) '4(h)、 10(h) ' 20 ( h ) 、200(h)，通水量爲 l〇〇(ml)、 200 (ml) 、500 (ml) 、1,000 (ml) 、l〇,〇〇〇(ml)各 5 -15- 200918193 階段。定義通水試驗中液固比爲相對於塡充於管柱中之試 驗材料之重量之通水液之重量， 液固比=通水之重量/試驗材料重量 （1 )式 而求出。（1)式中通水液之比重爲1時，可求出相 對於通水時間之通水容量。使通水液自管柱上端’以1分 鐘約0.8 3 ml/min之一定的速度進行滴注。 根據上述通水條件之試驗結果，如圖5所示之管柱通 水試驗結果表。 於造粒處理材料之通水試驗中，六價鎘、硒、砷此3 種重金屬相對於酸性、中性、鹼性之通水液幾乎均爲計量 下限値以下，記作ND。另外針對硼對酸性亦與鹼性液爲 環境基準値之約1 /8，以及顯示對中性液係極微量之約1 /9 ，可見其充分符合環境基準値。 自前述之通水試驗，確認造粒處理材料係對酸性水及 鹼性水爲化學上安定的材料。其可推測爲係由於降低用處 理材料（紅土）、結晶化促進劑、普通混凝土、鼓風爐熔 渣微粉末，對重金屬類安定地吸附，或使其被固化•不溶 化所致。 因應此目的所使用之降低重金屬類之處理材料（劑） ’例如可藉由將其與來自整備港灣設施所排放出之疏濬土 砂’及自火力發電所所排出之含重金屬之廢棄物進行混合 ’而可顯著減輕重金屬之含有量（溶出量），因完全符合 環境基準値，而可安全地將其再利用爲以路盤材料爲始之 回塡材料，及綠地用之土壤等地盤材料。 -16- 200918193 【圖式簡單說明】 [0 1〕對水泥污染水及煤灰飛灰之污染水，因紅土 而降低重金屬類之確認試驗結果之分析一覽表。 〔圖2〕根據本發明造粒化處理材料之製造方法之流 程圖。 〔圖3〕於造粒處理材料之重金屬溶出試驗結果一覽 表。 〔圖4〕於管柱通水試驗之通水條件一覽表。 〔圖5〕管柱通水試驗結果之一覽表。 【主要元件符號說明】 S ~ 1 :原料混合步驟 S — 2 :第1混合步驟’第2混合步驟 S — 3 :造粒步驟 S — 4 :熟化步驟 -17-Fe - 〇H - plasmon adsorption group (surface hydroxyl group), which becomes the form of negative ion Μ - OH -. Here, the symbol of the form is 矽Si, aluminum A1, and the metal element of iron Fe. At this time, an oxyanion such as a phosphate ion, an arsenate ion, a cadmium acid ion, a selenate ion, or a boric acid ion is directly substituted at the edge of the clay mineral particle to replace the hydroxide ion Μ - OH - of the surface hydroxyl group. Coordination. This reaction is called a ligand conversion reaction, and a negative oxygen-containing anion such as hexavalent cadmium or selenium is adsorbed by forming a surface disorder (coordination exchange) on the surface of the mineral particles. From the above results, it is presumed that the coordination reaction between alumina, iron oxide and heavy metal ions contained in the laterite has a great influence on the adsorption. Next, a method for producing a granulated material using a treatment material for reducing heavy metals or the like according to the present invention will be described with reference to the drawings. 2 is a flow chart S-1 of a method for producing a granulation treatment material according to the present invention. The raw material mixing step is to take 1% by weight of a crystallization accelerator relative to 1% by weight of the red clay as a raw material. 10% by weight of ordinary concrete '1% by weight of blast furnace slag fine powder, 50.0% by weight of coal ash fly ash' is mixed with about 20% by weight of the adjusted water of the total weight of these substances. -13- 1 - 2 ) Mixing and stirring step 200918193 Stir at a constant speed in the granulator to mix the raw materials. The granulation system uses a mobile granulator manufactured by Beichuan Iron Works. The stirring speed of the stirring was set at 100 to 200 rpm, and the mixture was stirred for 15 minutes. S - 3) Granulation step After the raw materials are thoroughly mixed in the mixing and agitating step, the vibrating device attached to the granulator is used, and the mixture is shaken for 3 minutes while stirring, and the finished product is discharged. Because it is mixed with vibration treatment, the material that has been shaken will be spherical and discharged. Its particle size is about 1mm~70mm. S - 4) Maturation step The granulation treatment material is aged by natural drying from 3 days to one week. Fully matured and dried to complete the granular material. The particle size is about 1 mm to about 70 mm, and it is a porous reddish brown material which is subjected to treatment for reducing heavy metals. [Test Example 2] Next, a dissolution test of a heavy metal produced by the above method to confirm that the granulated material was in compliance with environmental standards was carried out. This dissolution test is based on the above-mentioned eight inorganic heavy metals. The test was carried out in accordance with the Ministry of the Environment Bulletin No. 46, and the test results are shown in the list of heavy metal dissolution test results shown in Figure 3. Among the dissolution test results of the granulation treatment materials, cadmium, lead, arsenic, and total water -14-200918193 silver were all below the lower limit of measurement, and were recorded as ND. One of the two test samples provided by hexavalent cadmium, selenium and boron is below the lower limit of measurement, and the respective residual amount is about 1/2.3, 1/10, 1/1 of the environmental reference. Further, the average enthalpy of the two test samples provided by 'fluorine' was reduced by about one-fifth compared to the environmental standard. From the above results, it is known that the granulation treatment materials using red clay, coal fly ash, crystallization accelerator, solidified material (general concrete), and blast furnace slag micropowder meet the environmental standards, and confirm that it is a safe site for the site environment. material. [Test Example 3] This test assumes that the granulation treatment material is affected by acid water such as acid rain and strong alkaline water contaminated by the site, and the water is passed through the column to review the acid solution and the neutral solution. The heavy metal of the alkaline liquid can be dissolved again. Here, the neutral liquid is used in comparison with an acidic liquid and an alkaline liquid. As the object of the column water test, there are four kinds of hexavalent cadmium, selenium, arsenic and boron. The water solution is a nitric acid solution of pH 4, pure water of pH 7, and a sodium hydroxide solution of pH 12. The pipe string is made of a vinyl chloride column, and is filled with a granulation treatment material as a test material, and is installed in a water storage tank above the pipe column to maintain the water supply liquid in a fully saturated state. Make a drip. The water passing condition is shown in the water passing condition table shown in Fig. 4. The liquid-solid ratio is set to 0.1, 0.2, 0.5, 1, 10, and the water passing time is 2 (h) '4 (h), 10 (h) ' 20 ( h ), 200 (h), water flow is l〇〇 (ml), 200 (ml), 500 (ml), 1,000 (ml), l〇, 〇〇〇 (ml) each 5 -15- 200918193 stage. The liquid-solid ratio in the water-passing test is defined as the weight of the water-passing liquid relative to the weight of the test material filled in the column, and the liquid-solid ratio = the weight of the water passing through / the weight of the test material (1). When the specific gravity of the water-passing liquid in the formula (1) is 1, the water-passing capacity with respect to the water passing time can be obtained. The water-passing liquid was allowed to drip from the upper end of the column at a constant speed of about 0.8 3 ml/min for 1 minute. According to the test results of the above-mentioned water passing conditions, the results of the pipe water passing test results shown in Fig. 5 are shown. In the water passing test of the granulation treatment material, the three heavy metals of hexavalent cadmium, selenium and arsenic are almost below the lower limit of measurement with respect to the acidic, neutral and alkaline water-passing liquid, and are recorded as ND. In addition, it is about 1 / 8 of the environmental reference for boron and the alkaline solution, and about 1 / 9 of the very small amount of neutral liquid. It can be seen that it fully meets the environmental standard. From the above-described water passing test, it was confirmed that the granulation treatment material is a chemically stable material for acidic water and alkaline water. It is presumed to be due to the reduction of the treatment material (red earth), the crystallization accelerator, the ordinary concrete, the fine powder of the blast furnace slag, the stable adsorption of heavy metals, or the solidification/insolubilization. The treatment materials (agents) for reducing heavy metals used for this purpose can be mixed, for example, by mixing them with the dredged soil sand discharged from the warehousing facilities and the heavy metal-containing waste discharged from the thermal power station. The content of heavy metals (dissolved amount) can be significantly reduced, and it can be safely reused as a material for backtracking from the material of the road surface, and as a material for the green soil. -16- 200918193 [Simplified description of the drawings] [0 1] A summary of the analysis results of the confirmed test results for heavy metals in the contaminated water of cement contaminated water and coal fly ash. Fig. 2 is a flow chart showing a method of producing a granulation treatment material according to the present invention. [Fig. 3] A summary of the results of the heavy metal dissolution test on the granulation treatment material. [Fig. 4] A list of water passing conditions in the water passing test of the column. [Fig. 5] A list of the results of the water passing test of the column. [Description of main component symbols] S ~ 1 : Raw material mixing step S - 2 : 1st mixing step '2nd mixing step S - 3 : Granulation step S - 4 : ripening step -17-