201041669 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種飛灰穩定化方法以及水淬高爐石粉之 應用，尤指一種以水淬高爐石粉取代波特蘭水泥，並使用水 及重金屬螯合劑為添加劑，穩定化處理含重金屬的焚化爐飛 灰之技術。 【先前技術】 垃圾經焚化廠所焚化處理後，會後剩餘非揮發性、無機性 之固體物殘渣（residues)，這些殘渣一般分為底灰（bottom ash )、鍋爐灰（b〇iler ash )及空氣污染防治系統灰（air _uti〇n eontmlsystemash，簡稱為APCash)，然有許多含重金屬物質 之垃圾於焚化處理過程中，會因為重金屬可能直接的揮發、重 金屬被融化或經反應形成新物種等，焚化過程中重金屬物質會 因.揮發作用（vaP〇rizati〇n) 2.揚起作用（entrainment)及 3.蒸氣之冷凝及凝結作用等（c〇ndensati〇n) 一部份重金屬與無 機化σ物（Si、A卜Ca、Fe等化合物）結合形麟^查以底灰 型式排出至灰渣貯坑’另—部份重金相進人氣相中以氣膠 (aeiOsol)蒸汽型態存在，然後會被熱回收裝置及空氣汙染防 治設備，截留伴隨或附著於飛灰之上。 歧中含有的有害重金屬物質，若未經處理，重金屬物質 可μ出而㈣土壤及地下水形成二次公害，重金屬污染的特 色在於其存在麵之錢性，轉性隨著存在之義不同而有 201041669 所差異，-般重金屬例如：銅、鋅、錯、鎳、鉻、锡及采等對 生物體有級與慢性毒性之分，此外；鈹、鉻、錯、錦及辞等 已被證明有致雜。所以要將歧最終處置之前，必須針對這 些有害物質進行處理’以統成生態魏的孩影響。針對飛 灰重金屬的穩定化處理，法規巾明定：飛灰除再细外，應採 穩定化法、熔融法或其他經巾央主管制許可之處理方法處 理。 飛灰經穩定化處爾所生成_為「衍生物」，飛灰完成 處理之標料触物親過有詩g廢棄物認定縣戴奥辛 有害事業廢棄物總毒性t4濃度標準及喊四有毒重金屬毒 性特性溶出程序溶出標準，始得進行最終處置。 南溫溶融處理： 熔融處理讀展，最嫉要是輕將焚化灰針之重金屬 封入紐巾，以·齡化之縣。赌研究魏，灰雜融 後除無害化外，更可達贼4、減容雜__之目的，其 (eaasi(VAi办）之主成分 類似，故很容易得到玻璃質熔渣，苴在 刀 、牡M〇2之網目構造可將 重金屬氧化物封閉於熔渣中，使其不再 冉出，唯因其建造及處 理費用龐大，以國内經濟規模尚無法執行。 水泥固化處理： 蘭）水泥形成類似岩石 可將重金屬轉變成氫氧 水泥固化法係於飛灰中加入（波特 之塊狀物，由於水泥高鹼度的氫氧基， 201041669 化物等低溶解性物質，且水泥塊具有類似離子交換樹脂之功 能，可經由化學性或物理性結合截留重金屬。水泥之水硬性 (hydrauhcity)為最大特性，僅加水攪拌即可獲得高強度與耐 久性，為其最優異的特色，並且水合作用後產生粘結、吸附、 匣限、固定化等之作用功能。其主要原理可歸納為矽灰反應 (Pozzolanicreaction)及水合反應（Hydration)兩種，包括： 一、 石夕灰反應(Pozzolanic reaction)-又稱波特蘭反應。 波特蘭反應（Pozzolanic reaction)波特蘭材料 \) (Pozzolans)是一種矽質（石英質）或其鋁酸鹽混合物，本 身僅有微小的膠結力，但於潮濕及常溫下，將與氫氧化鈣 發生反應而產生具膠結力之石夕酸約水合物，此性質稱矽灰 ’ 性質’其反應稱矽灰反應。當波特蘭發生反應時，由於飛 、 灰本身之組成原已含有Si02、Al203、Ca0等金屬氧化物， 加以飛灰來自廢氣洗煙設備如採半乾式流程，其CaO之 含量更將因除酸添加而大幅提高，於含水環境下，將因解 ❹ 離釋出Ca+2’而與飛灰中之Si02、Al203產生化學反應， 形成矽酸鈣(C-A-H)、鋁酸鈣之水合物膠體(C-S-H)，並隨 時間逐漸硬化形成結晶狀態，以將飛灰中其餘重金屬等成 分包覆固著於結晶格中形成安定結構物。 二、 水合反應(Hydration) 水泥中矽酸鈣、鋁酸鈣、鐵酸鈣等主要組成於加水拌 合過程中，發生水合反應形成矽酸鈣、鋁酸鈣及鐵酸妈之 水合物膠體，並隨時間逐漸硬化形成結晶狀態，以將飛灰 5 201041669 中，、餘、’且成包覆m著於其結晶格中形成安定結構物達固 化物之最終強度。 此外，飛灰中原有之CaO於石夕灰反應後之剩餘量， 以及水泥固化過程中水合反應生成之以哪，尚提供大 量之驗度，除可協助歧巾所含重金屬生成不溶性金屬氣 氧化物沈澱外，麟轉賊回化物於高阳值環境中， 以供中和外來酸性溶液之淋洗，確保飛灰固化物結晶格中 重金屬氫氧化物沈獅之安定性。惟由於飛灰中尚含氯 鹽、硫酸鹽等無機性鹽類。水泥固化反應時，固化物受 CaO與氯鹽含量關係影響，當Ca〇含量低時，因固化作 用不足’將導致固化過程中膠體凝結時間延長及降低固化 物财久性’如t CaO與氣鹽含量均高時，因形成氣化鈣 化合物，易因吸濕而促使固化物膨脹崩解，固化物之安定 性堪慮。又波特蘭水泥+ 3Ca0 · Al2〇3成分易與硫酸鹽 產生反應*被條導朗壞，於長_埋後仍有重金屬再 溶出顧慮。在重金屬含量較高時，單獨制水泥固化其固 化衍生物可能無法達重金屬溶出試驗梘定。若加入大量水 泥’廢棄物減積效果降低’失圾處理原義與環保精神 濕式化學處理濕式化學處理主要包括「加酸萃取」及「廢 氣中和碳酸鹽化」兩種方法。加酸萃取：利用降低pH值 將重金屬自飛灰中溶出’溶出後萃取液再添加硫内納收8) 或硫氫化鈉(NaHS)使其生成不溶性硫心物後予以去除。 廢氣中和碳酸鹽化：利用廢氣中之c〇2溶於水生成碳酸 6 2〇1〇41669 或碳酸根，與飛灰中重金屬反應生成不溶性之碳酸鹽或氫 氧化物而將重金屬自飛灰中移除。自飛灰中萃取溶出的重 金屬加硫後濃縮沈殿於廢水污泥中，產生之廢水及污泥尚 待進一步的處理。此種處理方法在pH旳控制頗為重要， 又操作條件較為複雜’佔地空間亦大，僅於日本若干焚化 廠具應用案例’如日本東京都部份新設焚化廠因採搭配乾 濕混合型廢氣處理流程而搭配採用飛灰濕式化學處理 〇 法。添加化學藥劑法：因水泥固化衍生物易受氯鹽作用而 崩解，必須辅以其他化學添加劑以確保固化體内重金屬物 質長期不易溶出。一般用於飛灰重金屬安定化處理之化學 添加劑，主要為「無機系重金屬安定劑」及「有機系液體 螯合劑」兩大類。其中，無機系重金屬安定劑一般使用硫 化氫系列藥品形成重金屬硫化物沉澱以防止重金屬溶 出，另外，磷酸鹽系列藥品，為粉末狀或液體狀之重金屬 ◎ 女疋劑’經混練後將形成如pb5(p〇4)3〇H等低溶解度積之 女疋化物質。有機性液體螯合劑多為含硫續之驗性藥劑， 擁有二硫代氨基甲酸官能基與烷基構造之聚合物。根據分 子中烧基屬高分子或低分子，歸類為高分子系液體聲合劑 與低分子系液體螯合劑。螯合劑安定化之原理乃利用分子 Θ含硫縣部分的親電子性與重金屬發生配位鍵結或離 子鍵結反應，生成不溶性反應物，將重金屬固定防止溶 出，其成品雖不具抗壓強度，但安定重金屬之效果良好。 、.’示&上述焚化爐飛灰處理技術之比較，由於採「水泥固化 7 201041669 (so_cati〇n) +螯合劑安定化（satbilizati〇n)」來進行飛灰 穩定化處理’建造及操作成本她於其它方式為低，目前國= 設計的飛灰處理穩定化設備亦多為合併使用水化與添加 化學藥劑法，即细化學藥継重金屬㈣結合性將重金屬安 定化，降低重金屬⑽解性與移動性，並輔以添加水泥節省使 用高價_之縣。崎由於焚化衫_半乾式除污系統， 飛灰性質雜水泥，飾加少量水泥及少量藥舰可使飛灰固 化、硬化、安定化，減低重金屬的移動性與飛灰微粒的逸散性， 即可使飛灰SHt體符合法規TCLP溶出鮮要求。於穩定化 處理中添加水泥’主要運用原裡切灰反應（Pozzolanic reaCtl〇n)及水合反應（Hydrati〇n):矽灰反應（pozz〇ianic reaction)-又稱為波特蘭（波索蘭）反應，波特蘭反應之 化學反應式：Si〇2 + Ca〇 + CaS〇4 + Fe2〇3 + + h2〇—3201041669 VI. Description of the invention: [Technical field of invention] The present invention relates to a method for stabilizing fly ash and the application of water quenched blast furnace powder, in particular to replacing Portland cement with water quenched blast furnace powder, and using water and heavy metals The chelating agent is an additive that stabilizes the technology of incinerator fly ash containing heavy metals. [Prior Art] After the waste is incinerated by the incineration plant, non-volatile and inorganic solid residue (residues) remain. These residues are generally classified into bottom ash and boiler ash (b〇iler ash). And air pollution control system ash (air _uti〇n eontmlsystemash, referred to as APCash), but many heavy metal-containing wastes in the incineration process, because heavy metals may be directly volatilized, heavy metals are melted or reacted to form new species, etc. In the process of incineration, heavy metals will be affected by volatilization (vaP〇rizati〇n) 2. Entrainment and 3. Vapor condensation and condensation (c〇ndensati〇n) Part of heavy metals and mineralization The σ substance (Si, A, Ca, Fe, etc.) is combined with the shape of the lining to be discharged into the ash storage pit in the bottom ash type. The other part of the heavy metal phase enters the human gas phase and exists in the vapor form of the aeiOsol. It will then be trapped or attached to the fly ash by the heat recovery unit and the air pollution control equipment. Harmful heavy metal substances contained in the dissimilarity, if untreated, heavy metal substances can be produced and (4) soil and groundwater form secondary pollution. The characteristic of heavy metal pollution lies in its existence, and the transmutation has different meanings. 201041669 Differences, such as: copper, zinc, wrong, nickel, chromium, tin and mining, etc. are classified as chronic and chronic toxicity to organisms; in addition, bismuth, chromium, error, brocade and rhetoric have been proven miscellaneous. Therefore, before the final disposal of the disambiguation, it is necessary to deal with these harmful substances to influence the children of the ecological Wei. For the stabilization treatment of fly ash heavy metals, the regulations are clearly defined: the fly ash should be treated in a stabilizing method, a melting method or other treatment methods approved by the central authority of the towel. The fly ash is produced by the Stabilization Department. It is a "derivative". The fly ash finishes the processing of the standard material. The contact with the poison g waste identifies the county's Dyoxin hazardous business waste total toxicity t4 concentration standard and shouts four toxic heavy metal toxicity. The characteristic dissolution procedure elutes the standard and is ready for final disposal. South-temperature melt treatment: The melt treatment read exhibition, the most important thing is to lightly seal the heavy metal of the incinerated ash needle into the towel, to the county of aging. Gambling research Wei, after the ash fusion, in addition to harmless, but also to the thief 4, reduce the amount of __ the purpose, its (eaasi (VAi)) the main components are similar, it is easy to get vitreous slag, kneeling The mesh structure of Knife and Mu M2 can seal heavy metal oxides in the slag, so that it can no longer be thrown out. Due to its huge construction and processing costs, it cannot be implemented in the domestic economy. Cement curing treatment: Lan The cement forms a rock similar to the conversion of heavy metals into oxyhydrogen cement. The solidification method is added to the fly ash (the bulk of the porter, due to the high alkalinity of the cement, the low solubility of the 201041669 compound, and the cement block) It has the function of similar ion exchange resin, and can retain heavy metals through chemical or physical combination. The hydrauhcity of cement is the biggest characteristic, and only high water strength and durability can be obtained by adding water, which is the most excellent feature, and After hydration, it has the functions of bonding, adsorption, limitation, immobilization, etc. The main principles can be summarized as Pozzolanic reaction and Hydration, including: 1. Pozzolanic reaction - also known as Portland reaction. Pozzolanic reaction Portland material\) (Pozzolans) is a mixture of enamel (quartz) or its aluminate. It has only a small cementation force, but in the wet and normal temperature, it will react with calcium hydroxide to produce a cementitious oxalic acid hydrate. This property is called ash ash 'kininess' and its reaction is called ash ash reaction. When Portland reacts, the composition of fly and ash itself already contains metal oxides such as SiO2, Al203, Ca0, etc., and the fly ash comes from exhaust gas washing equipment, such as semi-dry process, and its CaO content will be removed. The addition of acid greatly increases the chemical reaction between SiO2 and Al203 in the fly ash due to the release of Ca+2' in an aqueous environment to form a colloidal colloid of calcium citrate (CAH) and calcium aluminate. (CSH), and gradually hardens to form a crystalline state with time, so that the remaining heavy metals in the fly ash are coated and fixed in the crystal lattice to form a stable structure. Second, hydration reaction (Hydration) Cement calcium citrate, calcium aluminate, calcium ferrite and other major components in the process of mixing water, hydration reaction to form calcium citrate, calcium aluminate and ferric acid hydrate hydrate, And gradually harden to form a crystalline state with time, in the fly ash 5 201041669, the remainder, and the coating is formed in the crystal lattice to form a stable structure to the final strength of the cured product. In addition, the remaining amount of CaO in the fly ash after the reaction of the stone ash, and the hydration reaction during the solidification of the cement, provide a large number of tests, in addition to assisting the formation of insoluble metal gas oxidation of heavy metals contained in the scarf In addition to the precipitation of the material, the thief is turned into a high-yang environment to provide a neutralization of the external acidic solution to ensure the stability of the heavy metal hydroxide schist in the crystal lattice of the fly ash solidified material. However, the fly ash still contains inorganic salts such as chloride salts and sulfates. When the cement is solidified, the cured product is affected by the relationship between CaO and chloride content. When the content of Ca〇 is low, the curing effect is insufficient, which will lead to prolonged colloidal setting time and reduce the longevity of the cured product during the curing process, such as t CaO and gas. When the salt content is high, the formation of the vaporized calcium compound tends to cause the cured product to expand and disintegrate due to moisture absorption, and the stability of the cured product is unpredictable. Portland cement + 3Ca0 · Al2〇3 is easy to react with sulfate. * It is badly barred. After heavy _ burial, there are still heavy metals and dissolution concerns. When the heavy metal content is high, the solidification of the solidified derivative by cement alone may not reach the metal dissolution test. If a large amount of cement is added, the waste reduction effect is reduced. The original meaning of waste disposal and the spirit of environmental protection Wet chemical treatment The wet chemical treatment mainly includes two methods of "adding acid extraction" and "air gas neutralization and carbonation". Acid extraction: The pH of the heavy metal is eluted from the fly ash. After the dissolution, the extract is further added with thioena (8) or sodium thiohydride (NaHS) to form an insoluble sulfur core and then removed. Neutralization and carbonation of exhaust gas: using carbon dioxide in the exhaust gas to form carbonic acid 6 2〇1〇41669 or carbonate, reacting with heavy metals in fly ash to form insoluble carbonate or hydroxide and heavy metal from fly ash Removed. The heavy metal extracted from the fly ash is sulphurized and then concentrated in the wastewater sludge, and the wastewater and sludge generated are still to be further processed. This kind of treatment method is very important in pH旳 control, and the operating conditions are more complicated. The space occupied is also large. It is only used in several incineration plants in Japan. For example, some incineration plants in Tokyo, Japan, are equipped with dry and wet hybrid types. The exhaust gas treatment process is combined with the fly ash wet chemical treatment method. Adding chemical agents: Since cement-cured derivatives are easily disintegrated by the action of chloride salts, they must be supplemented with other chemical additives to ensure that heavy metal substances in the solidified body are not easily dissolved in the long-term. It is generally used as a chemical additive for the stabilization of fly ash heavy metals. It is mainly used in two categories: "inorganic heavy metal stabilizer" and "organic liquid chelating agent". Among them, inorganic heavy metal stabilizers generally use hydrogen sulfide series drugs to form heavy metal sulfide precipitates to prevent heavy metal dissolution. In addition, phosphate series drugs are powdery or liquid heavy metals ◎ female mites' will be formed as pb5 after mixing (p〇4) 3〇H and other low solubility products of female deuterated substances. The organic liquid chelating agent is mostly a sulfur-containing test agent, and has a dithiocarbamic acid functional group and an alkyl structure polymer. According to the polymer or low molecule in the molecule, it is classified into a polymer liquid sounding agent and a low molecular liquid chelating agent. The principle of chelating agent stabilization is to use the electrophilicity of the molecular sulphur-containing sulphur-containing part to form a coordination bond or an ionic bond reaction with a heavy metal to form an insoluble reactant, fix the heavy metal to prevent dissolution, and the finished product does not have compressive strength. However, the effect of stable heavy metals is good. , ''show & comparison of the above-mentioned incinerator fly ash treatment technology, due to the use of "cement solidification 7 201041669 (so_cati〇n) + chelating agent stabilization (satbilizati〇n)" for fly ash stabilization treatment" construction and operation The cost is low in other ways. At present, the design of the fly ash processing stabilization equipment is mostly combined with the use of hydration and chemical addition methods, that is, the combination of fine chemicals and heavy metals (4) to stabilize the heavy metals and reduce the heavy metal (10) solution. Sex and mobility, supplemented by adding cement to save the use of high prices _ county. Because of the incineration shirt _ semi-dry decontamination system, fly ash mixed cement, a small amount of cement and a small amount of drug ship can make the fly ash solidify, harden, stabilize, reduce the mobility of heavy metals and the escape of fly ash particles, The fly ash SHt body can meet the requirements of the TCLP dissolution requirements. Adding cement to the stabilization process 'mainly using the original ash cutting reaction (Pozzolanic reaCtl〇n) and hydration reaction (Hydrati〇n): ash ash reaction (pozz〇ianic reaction) - also known as Portland (Posolan Reaction, the chemical reaction of the Portland reaction: Si〇2 + Ca〇+ CaS〇4 + Fe2〇3 + + h2〇-3
CaO Al2〇3 · 3 CaS〇4 · 32 H20 + 2 CaO · Si02 · 1.17 H20 + 3CaO Al2〇3 · 3 CaS〇4 · 32 H20 + 2 CaO · Si02 · 1.17 H20 + 3
CaO · Al2〇3 · 6H2〇 + 4 CaO · Al2〇3 . Fe2〇3 + ... 波特蘭材料（Pozzolans )是一種矽質（石英質）或 紹酸鹽混合物。本身僅有微小的膠結力，但潮濕及常溫 下，將與氫氧化鈣發生反應而產生具膠結力之矽酸鈣水合 物’此性質稱石夕灰性質其反應稱為矽灰反應，當波索蘭發 生反應時’飛灰中的Si02、Al203與水泥中氫氧化鈣反應產 生晶狀的鈣鋁鹽類（C-A-H)以及鈣矽膠體（C-S-H)，以 填塞混凝土 ©化時微小孔隙’提高強度，減少固化體透水 201041669 性並提高耐久性。 由於焚化爐飛灰本身組成原 已含有 Si02、Al2〇3、CaO 等金屬氧化物，成份與水泥類似，且因半乾式洗煙塔喷入大量 消石灰’故CaO含量極高，於含水環境，將因解離釋出 Ca ，而與飛灰中的Si〇2、A1203產生化學反應形成矽酸妈、 減辦之水合物膝體，並隨時間逐漸應化形成結晶狀態，以將 飛灰中其餘重金屬等包覆gj著於結晶格巾形成安定結構物。水 〇 合反應（Hydrati〇n )水泥中矽酸鈣、鋁酸鈣、鐵酸鈣等 主要組成於加水拌合過程中，發生水合反應形成矽酸約、 嫌妈及鐵_之水合物膠體，並隨時間逐漸應化形成結晶狀 態，以將飛灰中其餘組成包覆固著於結晶格中形成安定結構 物。 ' 凊參閱第二圖所不，關於水泥固化之石夕灰反應及水合反 應反應機制； 此外，飛灰中原有CaO於矽灰反應後之剩餘量，以及水泥 ° ®化過程中水合反應生成之Ca (〇H) 2，尚提供大量之鹼度， 除可協助飛灰巾所含重金屬生成不溶性金屬氫氧化物沉殿外 (以鉛為例：PbCl2 + Ca ( 〇H ) 2_>PbC〇3i + CaCl2 )，並得維 持飛灰固化物於高PH值環境中，以供中和外來酸性溶液之淋 洗，破保飛灰固化物結晶格中重金屬再溶出顧慮。 然而由於飛灰巾尚含氯鹽、硫酸鹽等無機性細，將導致 固化過程中膠體凝結時間延長及降低固化物耐久性，如當 與氯鹽含量均高時，因形成氯化舞化合物，易因吸濕而促使固 9 201041669 化物膨脹崩解；而固化物若與所接觸的硫酸鹽起化學變化，會 造成固化物部份體積膨脹，以及強度逐漸損失與重量因膨脹而 減小，造成固化物品質劣化的現象，於長期衍埋後仍有重金屬 再溶出顧慮。 【發明内容】 本發明係種-魏灰穩定財法，係以熔煉鋼鐵時 所生之水淬兩爐石粉為飛灰固化料，以飛灰每i⑽重量份中加 入3至20重量份之水淬高爐石粉，其餘為水份，達到至 160重量份為固化飛灰之方法。 本發明基於廣義之同-發明，設計—種水淬高爐石粉之應 用，係以熔煉鋼鐵時所生之水淬高爐石粉，為飛灰固化之用 途’且飛灰每励重量份中加入3至2〇重量份之水淬高爐石 粉，其餘為水份作為飛灰之固化用途。 由於飛灰本身組成原已含有Si〇2、Al2〇3、Ca〇等金屬 氧化物’成份與水泥類似，穩定化處理時以水淬高爐石粉取代 水泥添加做為固化麵料，效用與高爐水泥_，可獲得更加 優良之處理品質並達到環保減廢及節省成本之效益。 、本發明之發_機，主要係以「高爐_」為鋼鐵廠煉鐵 過程所生產之!彳絲，早射以棄置方式處理，高爐爐逢若以 水泮方式冷卻，料潛在之水雖縣魏，適娜加混凝土 中會增加混耻之_強度觸久性；將水淬練石研磨所成 201041669 之細粉即為「水淬高爐石粉」。本發明所稱之「水淬高爐石」， 或是「水淬高爐石粉」，其兩者成分係屬相同。本發明中縱若 有以「水淬高爐石粉」為名詞，其實際涵義亦包括「水碎高爐 石」。 更具體說明以水淬高爐石取代水泥為飛灰穩定化處理之 固化劑其原理、優點及效益說明如下： 一、 水淬高爐石粉之波特蘭反應 Ο 「水淬高爐石」（quenching blast-fUmace slag ):將熔 融爐石以淬火方式（quenching)急速冷卻，使其形成含 很少礦物結晶的粒狀玻璃質材料，淬火方式可完全用水 ' 或混合水與空氣，以這種方式所形成的冷卻爐石含有與 * 波特蘭水泥（Portland cement)相同化學成份的主要氣化 物，但其中含有的石灰（lime ’ CaO)與二氣化矽（別〇2) 的成份比例較高，將此種水淬爐石磨至直徑45μιη小於之 〇 細粉後即為水淬高爐石粉（ground granulated blast ilimace slag ’ GGBFS)，當水淬高爐石與活性物質如氫氧化妈 (calcium hydroxide ’ Ca(OH)2)化合時形成類似水泥熟 料之水化物C-S-H膠體’具有與波特蘭水泥相同的水硬 性與凝結性，因此可作為水硬性枯結性材料，可用以取 代水泥成為飛灰穩定化處理之固化劑。 二、 水淬高爐石粉比水泥具更佳的處理效果 以水淬高爐石粉取代水泥為飛灰穩定化處理之固化 201041669 劑，由於顆粒較小，以水淬高爐石粉為波特蘭材料取代 水泥之衍生物將會有較緻密的槳體結構與較低之孔隙 率，此效應對衍生物強度耐久性等性質均直接造成正面 影響’而波特蘭材料反應消化CH產生C-S-Η的結果， 亦使的衍生物勢於成熟穩定所使用之時間拉長，故衍生 物可在長期下’仍此依其環境及内部之濕度、孔P+'等條 件，進行反應，而使得材料微觀結構可更臻於緻密，能 獲得比水泥更佳的結晶格包覆效果’並獲得更好的強 度’使飛灰穩定化處理後其衍生物重金屬溶出更為降低。 三、抗氣鹽、硫酸鹽等無機性鹽類侵蝕 如前所述所所言，歧巾尚含㈣、硫酸鹽等無機 性鹽類’將導朗化顧中频凝結時間延長及降低衍 生物耐久性’除⑽含量高時’因形成氯倾化合物， 易因吸濕而促使固化物膨脹崩解，於長期衍埋後仍有重 金屬再溶出顧餅n面雜鹽舰（sulfateattack) 為很常見的現象’硫酸鹽侵⑽指硬固衍生物與硫酸鹽 起化學變化，造成固化物部份體積膨脹，以及強度逐漸 損失與重量因膨脹而減小，造成固化物品質劣化的現 象，以水淬高爐石粉取代時，可將水泥水化物中的氮氧 化舞含量減低至僅2%〜3%，遠低使用一般水泥混凝土 時，硬化水化物中的約25%氫氧化紛量，因此，即使 在波水泥中含有較高的域三約（以）或爐石中含 有較南的活性氧化_，仍可以添加高量爐石的方式， 201041669 作為抵抗硫酸鹽侵餘的抗硫水泥。 另外由於水淬爐石粉於飛灰衍生物中之孔隙，增加衍生物 之緻密，可增進衍生物之耐久性，亦可提升飛灰穩定化處理之 品質。並降低衍生物水化熱、提高衍生物晚期抗壓強度與耐久 性等優點，同時亦有避免高爐石棄置所可能造成的環境污問題 等益處。 Ο 【實施方式】 以下藉由圖式說明本發明之實施例’俾使貴審查委員對於 本案有更進一步之瞭解。 ' 請參閱第一圖所示’本發明係關於一種飛灰固化之方法以 . 及水淬高爐石粉之用途’係以熔煉鋼鐵時所生之水淬高爐石粉 為飛灰固化料’以飛灰每100重量份中加入3至20重量份之 水淬高爐石粉，其餘為水份，達到14〇至16〇重量份為固化飛 〇 灰之方法。本發明較佳之實施例，該水淬高爐石之重量份較佳 為 10-15 。 按’爐石除了為溶練鋼鐵時所生的副產物之外’由於其含 有氧化矽(Si〇2)、氧化鋁（A12〇3)以及氧化鐵（Fe2〇3)等成份， 依據其冷卻方式的不同，可分為水淬爐石與氣冷爐石，雖然氣 冷爐石亦可採用，但本發明以水淬爐石為較為優選，主要係高 爐熔渣快速水冷，爐石短時間崩裂成粒狀，且晶體破碎活性大 增且具膠結性，對於飛灰能夠提供一膠結而生固化之特性。因 13 201041669 此其與水泥之成份與屬性在研磨之下相當，都可以使得飛灰處.· 理在固化之後_ M至丨6倍之固化娜脹達賴定飛灰 之環保作用。 本發明除了在方法上提供水淬碰石粉作為取代水泥在 飛灰固化過程，對於飛灰固化之方法提供一種新的素材，亦對 於該爐石尋找—種新用途，對於節省經濟成本上有—助益。 晴參閱第二®所示，—般市售水泥平均每公，约新台帶 2500元，而水淬高爐石粉平均每公雜約新台幻元且 爐石粉係由熔煉鋼鐵時所生_產物，與水泥需再經開採加工 後所取得，職生的另—魏污染影響，對針對環保工程更具 其意義，且具產業之進步性。 八 水淬高爐石粉為具有尖銳角及不規則外形的粒狀材料，約 有數個mm的尺寸大小，將其研磨成粒徑小於#及、於 細度約為50〇m2/kg Blaine，比重約為2 9的細粉時，即形成「欠 淬高爐騎」（GGBFS)，歸難；轉雜场的化學7 份主要為氣切（SiQ2)、氣倾（Al2⑹、 等四種成份所組成，其中氣切⑶⑻屬於 k基成伤’其餘三_屬於驗基成份，與波特蘭t型水泥化風 成份比較如表： 千CaO · Al2〇3 · 6H2〇 + 4 CaO · Al2〇3 . Fe2〇3 + ... The Portland material (Pozzolans) is a mixture of enamel (quartz) or sulphate. It has only a small cementation force, but it will react with calcium hydroxide at a humidity and normal temperature to produce a calcium citrate hydrate with a cementing force. This property is called the ash ash property. When Solan reacts, SiO2 and Al203 in fly ash react with calcium hydroxide in cement to produce crystalline calcium-aluminum salts (CAH) and calcium strontium colloid (CSH), which are used to increase the strength of small pores when filling concrete. Reduces the viscosity of the solidified body 201041669 and improves durability. Since the incinerator fly ash itself already contains metal oxides such as SiO 2 , Al 2 〇 3 and CaO, the composition is similar to that of cement, and the CaO content is extremely high due to the injection of a large amount of slaked lime in the semi-dry smog tower. Due to the release of Ca, the chemical reaction with Si〇2 and A1203 in the fly ash forms a hydrated knee, and the hydrated knee body is reduced, and gradually forms a crystalline state with time to remove the remaining heavy metals in the fly ash. The coating gj is placed on the crystallized towel to form a stable structure. In the Hydrati〇n cement, calcium citrate, calcium aluminate, calcium ferrite and the like are mainly composed in the process of adding water, and the hydration reaction forms a colloid of citric acid, yoghurt and iron hydrate. And gradually form a crystalline state with time to coat the remaining components of the fly ash in the crystal lattice to form a stable structure. ' 凊 Refer to the second figure for the cement ash ash reaction and hydration reaction mechanism; In addition, the residual amount of CaO in the fly ash after the ash reaction, and the hydration reaction during the cementation process Ca (〇H) 2, still provides a large amount of alkalinity, in addition to assisting the heavy metals contained in the fly ash to form insoluble metal hydroxides (except for lead: PbCl2 + Ca ( 〇H ) 2_> PbC 〇 3i + CaCl2), and it is necessary to maintain the fly ash solidified material in a high pH environment for the neutralization of the external acidic solution, and to break down the heavy metal in the crystal of the fly ash solidified material to dissolve again. However, since the fly ash towel still contains inorganic salts such as chloride salts and sulfates, it will lead to prolonged colloidal setting time and lower the durability of the cured product during the curing process. For example, when the content of the chlorine salt is high, the chlorination dance compound is formed. It is easy to promote the swelling and disintegration of the solid by the moisture absorption; if the cured product chemically changes with the sulfate to be contacted, it will cause partial expansion of the solidified material, and the gradual loss of strength and the decrease of weight due to expansion, resulting in The phenomenon that the quality of the cured product deteriorates, and there is still concern that the heavy metal is dissolved again after long-term burial. SUMMARY OF THE INVENTION The present invention is a kind of ash-stabilized financial method, which is a water-quenched slag powder produced by melting steel as a fly ash solidifying material, and adding 3 to 20 parts by weight of water per i (10) parts by weight of fly ash. The blast furnace powder is quenched, and the rest is moisture, and the method of curing the fly ash is up to 160 parts by weight. The invention is based on the same general-invention, design, application of water quenching blast furnace stone powder, water quenching blast furnace stone powder produced when smelting steel, for the purpose of solidification of fly ash' and adding 3 to the weight fraction of fly ash 2 parts by weight of water quenched blast furnace stone powder, and the rest is water for curing use of fly ash. Since the composition of the fly ash itself already contains Si金属2, Al2〇3, Ca〇 and other metal oxides, the composition is similar to that of cement. When the stabilization treatment, water-quenched blast furnace stone powder is used instead of cement to be added as a solidified fabric, and the effect and blast furnace cement _ It can obtain better processing quality and achieve the benefits of environmentally friendly waste reduction and cost saving. The hair machine of the present invention is mainly produced by the "blast furnace _" for the iron making process of the iron and steel plant! The silk is sprayed in the early stage by the disposal method, and the blast furnace is cooled by the water raft, and the potential water is County Wei, Shi Najia concrete will increase the smear of the _ _ intensity of the long-term; the water quenched stone grinding into the 201041669 fine powder is the "water quenching blast furnace stone powder." The "water quenched blast furnace stone" referred to in the present invention or "water quenched blast furnace stone powder" has the same composition. In the present invention, the term "water-quenched blast furnace stone powder" is used as a term, and the actual meaning also includes "water-crushed blast furnace stone". More specifically, the principle, advantages and benefits of using water-quenched blast furnace stone instead of cement as the curing agent for fly ash stabilization treatment are as follows: 1. Portland reaction of water quenched blast furnace stone powder 水 "quenching blast" fUmace slag ): The molten whetstone is rapidly cooled by quenching to form a granular vitreous material containing little mineral crystals, and the quenching method can be formed by completely using water or mixing water and air. The cooling hearth contains the main gasification of the same chemical composition as * Portland cement, but the lime (Caly ' CaO) and the second gasified bismuth (Behind 2) have a higher proportion of components. This kind of water quenching furnace is ground to granulated blast ilimace slag 'GGBFS when it is less than 45μιη diameter. When water quenching blast furnace stone and active material such as hydroxide hydroxide ' Ca ( OH) 2) The hydrated CSH colloid which forms a cement clinker at the time of compounding has the same hydraulic and coagulation properties as Portland cement, so it can be used as a hydraulic dry knot material. Used to replace cement as a curing agent for fly ash stabilization. Second, water quenching blast furnace stone powder better treatment effect than cement with water quenching blast furnace stone powder instead of cement as fly ash stabilization treatment curing 201041669 agent, due to smaller particles, water quenching blast furnace stone powder for Portland material instead of cement The derivative will have a denser structure and a lower porosity. This effect has a direct positive effect on the strength and durability of the derivative, and the Portland material reacts to digest CH to produce CS-Η. The derivative is elongated over the time it takes for maturity and stability, so the derivative can be reacted in the long term, depending on its environment and internal humidity, pore P+', etc., so that the microstructure of the material can be more ambiguous. In the case of compactness, it is possible to obtain a better crystal lattice coating effect than cement and obtain better strength, so that the heavy metal dissolution of the derivative is further reduced after the fly ash is stabilized. III. Anti-gas salt, sulfate and other inorganic salt erosion As mentioned above, the scarf still contains (4), inorganic salts such as sulfates, which will prolong the condensation time of the intermediate frequency and reduce the durability of the derivatives. When the content of '10' is high, 'the formation of chlorine-lead compounds is easy to cause the solidified material to expand and disintegrate due to moisture absorption. It is very common to dissolve the heavy metal after long-term burial. The phenomenon 'sulfate intrusion (10) refers to the chemical change of the hard solid derivative and the sulfate, causing the volume expansion of the solidified part, and the gradual loss of strength and the decrease of the weight due to the expansion, resulting in deterioration of the quality of the cured product, in the water quenching blast furnace When the stone powder is substituted, the nitrogen oxide dance content in the cement hydrate can be reduced to only 2% to 3%, and when the general cement concrete is used, about 25% of the hydrated hydrate is oxidized, so even in the wave The cement contains a higher domain triad (or) or a more southerly active oxidation _ in the hearth, and can still be added with a high amount of hearthstone, 201041669 as a sulfur-resistant cement resistant to sulfate intrusion. In addition, due to the pores of the water quenching furnace powder in the fly ash derivative, the density of the derivative is increased, the durability of the derivative can be enhanced, and the quality of the fly ash stabilization treatment can be improved. It also has the advantages of reducing the hydration heat of the derivative, improving the late compressive strength and durability of the derivative, and also avoiding the environmental pollution problems caused by the blast furnace stone disposal. [Embodiment] Hereinafter, an embodiment of the present invention will be described by way of illustration, so that your reviewer has a better understanding of the case. 'Please refer to the first figure'. The present invention relates to a method for solidifying fly ash and the use of water-quenched blast furnace powder. The water-quenched blast furnace stone powder produced by melting steel is a fly ash solidification material. 3 to 20 parts by weight of water-quenched blast furnace stone powder is added per 100 parts by weight, and the balance is water, and 14 to 16 parts by weight is a method for curing the fly ash. In a preferred embodiment of the invention, the water-quenched blast furnace stone preferably has a weight fraction of 10-15. According to the fact that the 'hearthstone is a by-product produced by the smelting of steel,' it contains yttrium oxide (Si〇2), alumina (A12〇3) and iron oxide (Fe2〇3). The method can be divided into water quenching furnace stone and gas-cooled hearthstone. Although gas-cooled hearthstone can also be used, the present invention is more preferable to water quenching furnace stone, mainly blast furnace slag is rapidly water-cooled, and furnace stone is short-time. It is cracked into granules, and the crystal crushing activity is greatly increased and cemented, which can provide a cementation and solidification property for fly ash. Because 13 201041669 This is equivalent to the composition and properties of cement under the grinding, can make the fly ash. After the curing _ M to 丨 6 times the solidification of the lining up to the environmental protection of the ash. In addition to providing water quenched stone powder as a substitute cement in the fly ash solidification process, the present invention provides a new material for the method of solidification of fly ash, and also finds a new use for the whetstone, for saving economic cost. Help. Clearly, as shown in the second®, the average commercially available cement is about 2,500 yuan per metric ton, while the water quenched blast furnace stone powder averages about the new Taiwan illusion and the ston furnace powder is produced by smelting steel. The cement needs to be obtained after the mining and processing, and the influence of the other---the pollution of the vocational students is more meaningful for the environmental protection project, and it has the progress of the industry. The eight-water quenched blast furnace stone powder is a granular material with sharp angles and irregular shapes. It is about several mm in size and is ground to a particle size smaller than # and a fineness of about 50〇m2/kg Blaine. When it is a fine powder of 2 9 , it forms the "Under Quenching Blast Furnace Riding" (GGBFS), which is a problem; the chemical of the turning field is mainly composed of four components: gas cutting (SiQ2) and gas tilting (Al2 (6), etc. Among them, gas cutting (3) (8) belongs to k-based injury, and the remaining three are classified as components. Compared with Portland t-type cement, the composition is as follows:
化學成份 波特蘭I型水泥％ -...〜..¾棒爐石％ 氣化矽（Si〇2) 20^9 6.04 28^3? 8〜24 _國内％ ^^35 ...... 13.80 14 201041669 氧 4¾ (Fe203) ~· n 3.29 ~~042 _氧化鈣（CaO) 63.91 30 〜50 41.67 氧化鎂（MgO) 2.04 1〜18 7.45 氧化硫（S03) 1.81 — ------------··.····--------------------------------------------·····--------.一....... 1-2.5 0.878 燒失量（LOI) 1.06 - LT比重 3.15 _ ---- . 2.9-3 ASTM C989 規犯適用於爐石（讲0111^ iron blast-fUmace slag)，此規範為新規定，内容不特別指定爐石所需之化學或物 理條件’而由爐石活性指數（slag activity test，SAI)，將爐石 依其對爐石水泥強度之貝獻量而區分；依7天及28強度分為Chemical composition Portland I type cement % -...~..3⁄4 Bar furnace stone % gasification 矽 (Si〇2) 20^9 6.04 28^3? 8~24 _ domestic % ^^35 ... ... 13.80 14 201041669 Oxygen 43⁄4 (Fe203) ~· n 3.29 ~~042 _ Calcium Oxide (CaO) 63.91 30 ～50 41.67 Magnesium Oxide (MgO) 2.04 1~18 7.45 Sulfur Oxide (S03) 1.81 — ---- --------··.····----------------------------------- ---------·····--------. One....... 1-2.5 0.878 Loss on ignition (LOI) 1.06 - LT specific gravity 3.15 _ --- - 2.9-3 ASTM C989 is applicable to Hearthstone (0111^ iron blast-fUmace slag). This specification is new and does not specify the chemical or physical conditions required for hearth. (slag activity test, SAI), which distinguishes the hearthstone according to its contribution to the strength of the hearthstone cement; it is divided into 7 days and 28 strengths.
Grade80、100、120等三級，如表所示： 尊級 ---------··.·._‘····.. 爐石活性指數(SAI) _ 7天最小數 爐石活性指數(SAll~° 28天最小數 5個連續試體 平均試驗值 任何個別 試體試驗值 5個連續試體 平均試驗值 任何個別+ 試體試驗值 80級 -75 75 70 100級 — 95 70 95 90 120級 90 115 110 ~~ λ ^ ―•… "·—·—.····-..····- 註：爐石活性指數（slag activity index ’ SAI)定義為以50%爐石和 50%波特蘭水泥混合後，製成比例為1 : 2·75及流度ιι〇±5% 之標準水泥砂漿試體，在不同齡期下試驗所得的抗壓強度，與 以純波特蘭水泥所製成的標準水泥砂漿試體抗壓強度之比值： ------—_______________ 我國國家標準規範「CNS 1223水淬高爐爐碴粉」（1988 年公佈）及「CNS 12549混凝土水泥墁料用水淬高爐爐碴粉」 (1989年公佈）為相關的水淬高爐石規範，將水淬高爐石等 級依細度（cm2/g)及爐石活性指數（SAI)為指標，依細度分 為4000、6000及8000等三級，依爐石活性指數分為8〇、1〇〇 15 201041669 國内麟細轉鎌聽賴為侧級， 及120等三級，目 SAI约80〜1〇〇級 =所述，本發明確實符合產業利用性，且 於刊物或公賊用，縣為公眾所 麵=見 性，符合可專利之要件，爰依法提出專卿顯而易知 惟上述所陳’為本發業上1佳實關，舉凡 明申請專利範圍所作之均等變化 本發 白屬本案訴求標的之範疇。 201041669 【圖式簡單說明】 第一圖係本發明之方法流程圖 第.一圖係水泥價格曲線圖 第三圖係水泥固化之矽灰反應及水合反應反應機制示意圖 【主要元件符號說明】 無 ΟGrade 80, 100, 120 and other three levels, as shown in the table: 尊级---------····._'····.. Hearthstone Activity Index (SAI) _ 7 days minimum Hearthstone activity index (SAll~° 28 days minimum 5 consecutive test average test values Any individual test value 5 consecutive test average test values Any individual + Test value 80 grade -75 75 70 100 grade - 95 70 95 90 120 90 111 110 ~~ λ ^ ―•... "················· Note: The slag activity index (SAI) is defined as After mixing with 50% hearthstone and 50% Portland cement, the standard cement mortar samples with a ratio of 1: 2·75 and fluidity 〇 5% ± 5% are used to test the compressive strength at different ages. The ratio of the compressive strength of the standard cement mortar to the pure Portland cement: ------________________ China National Standard Specification "CNS 1223 Water Quenching Blast Furnace Powder" (announced in 1988) and " CNS 12549 concrete cement concrete water quenching blast furnace furnace powder" (promulgated in 1989) is the relevant water quenching blast furnace stone specification, the water quenching blast furnace stone grade according to the fineness (cm2 / g) and Hearthstone activity index (SAI) is an index, divided into three levels according to the fineness of 4000, 6000 and 8000. According to the activity index of the hearthstone, it is divided into 8〇, 1〇〇15 201041669. , and 120, etc., the SAI is about 80~1〇〇======================================================================================爰 提出 提出 提出 提出 提出 提出 提出 提出 爰 爰 2010 2010 2010 2010 2010 2010 2010 2010 2010 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专 专The first picture is the flow chart of the method of the present invention. The first picture is the cement price curve. The third picture is the schematic diagram of the ash reaction and the hydration reaction mechanism of the cement solidification [the main component symbol description]
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