201226578 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明主要係關於一種以二次鋁渣混製鋁質水泥之方法 ，尤指一種以工業所產生之二次鋁渣，混製成水泥之製 法。 【先前技術】 [0002] 國内鋁回收再生工業每年約產生1萬5千公噸之二次鋁 渣，二次鋁渣之組成非常繁雜且不均勻，其中主要成分 為氧化鋁，含量約為50〜80%，除了氧化鋁成分外，還包 Ο 含有殘留的金屬鋁，和易於與水反應的氮化鋁及碳化鋁 ，產生氨氮臭味問題。由於國内二次鋁渣再利用處理量 ，往往遠不及其產生量，傳統處理法皆以安定化固化掩 — 埋處理為主，對於土地狹隘的台灣，其廢棄物處理的合 法場地日益不易取得，常造成不法業者非法棄置，造成 環境公害。此外，將二次鋁渣混製成綠色鋁質水泥的附 加經濟價值及應用效能比先前專利技術間發成道路級配 ^ 砂、保水磚等，還要高出許多。 〇 [0003] 表一先前專利彙整 [0004] 專利名稱 作者 專利號 方法概述 將鋁渣灰資源 化利用之方法 蔡順元 455514 將二次鋁渣灰 先以酸（磷酸 、硫酸等）予 以穩定化處理 後再加水泥固 化，固化體之 099146788 表單編號A0101 第3頁/共14頁 0992080371-0 201226578 膨脹性隨添加 酸之種類及量 而變，以磷酸 為例，當磷酸 量添加量5 % ( 重量百分比） 可獲得強度 276kgf/cm2 ，而該無膨脹 性的固化體可 應用於隔間、 道路、防護牆 及其他工程之 利用，可有效 解決二次鋁渣 灰之公害。 利用二次鋁渣 製造保水磚之 方法 杳泰智 407068 將不同比例安 定化處理後之 二次鋁渣粉體 、高爐水泥、 玻璃質骨材， 粉碎後調成一 膠狀物，再壓 模成一粗胚， 接著先經加熱 乾燥硬化後再 表單編號A0101 第4頁/共14頁 0992080371-0 099146788 201226578 焙燒成一具微 細氣孔組織的 保水磚。合適 之焙燒溫度為 1 050。01200 X：。 ❹ ❹ 鋁渣安定化及 再利用之處理 方法 陳清齊等 1234587 使用氧化鈣物 質（脫硫渣等） 作為鋁渣廢棄 物安定劑，及 高壓混泥土磚 作為安定化鋁 渣最終再利用 產物。氧化1弓 經水溶解後產 生的強鹼性 (PH212)環 境，能促使鋁 潰中的氮化1呂 、碳化紹及金 屬鋁等有害物 質快速的水解 ，達成安定化 處理的目的； 而同樣具有高 鹼性效果的高 099146788 表單編號A0101 第5頁/共14頁 0992080371-0 201226578 壓混泥土磚製 程（pH 212) ，能使紹潰進 一步安定化並 以高壓磚作為 再利用產物。 以鋁渣灰製造 陶瓷濾料之方 法 蔡順元 1246938 將鋁渣灰經烺 燒處理形成『 α氧化銘』， 經研磨α氧化 銘後添加黏結 劑、成孔劑、 助溶劑及穩定 劑等配料再行 混煉，最後將 成型陶瓷濾料 胚型，經乾燥 、燒成、降溫 等步驟完成成 品，轉製成高 單價的陶瓷濾 料。 二次銘ί查灰資 源化之處理方 法 吳煜壑 1277463 先將鋁渣灰進 行比重分離作 業，使二次鋁 渣灰分離成較 表單編號A0101 第6頁/共14頁 0992080371-0 099146788 201226578 輕的碳化鋁、 碳化鈣及較重 的氮化鋁、氧 化鋁，然後再 分別將碳化铭 、碳化妈、氮 化鋁及氧化鋁 以rfj溫蒸氣作 業，使碳化鋁 、碳化鈣經高 溫蒸氣催化釋 出曱烷而安定 化，可作為填 土用材料，而 氮化銘及氧化 鋁經安定化後 ，可作為級配 砂、管路砂等 材料。 【發明内容】 [0005] 有鑑於先前問題，本發明人認為應有一套可以回收金屬 鋁之回收程序，以及對於二次鋁渣為安定化之技術，藉 以回收二次鋁渣中90%金屬鋁回製鋁錠，增加經濟效益 。此外將安定化二次鋁渣作為水泥原料，製成綠色鋁質 水泥，創新二次鋁渣再利用格局。希冀解決國内二次鋁 099146788 表單編號 A0101 第 7 頁/共 14 頁 0992080371-0 201226578 產問題，降低處理問題及成本，創造環境與產業經濟雙 贏之局面。按，二次鋁渣係指熔鋁業熔煉含鋁原料製成 相關金屬鋁製品過程中，以高溫熔煉、偏析熔煉、澆鑄 等程序後，經二次熔煉過程後所產生的尾渣。 [0006] [0007] 為達成前述目的，本發明人設計一種以二次鋁渣混製鋁 質水泥之方法，其步驟包括：先以粗篩、研磨、細筛及 分選等方法流程，將金屬鋁回收後熔煉鋁製品，再添加 女疋化藥劑於一次紹法中反應，使二次澄中之含氮量 降至0. 5%以下，達到去除氨臭之效果，最後測定安定化 二次鋁渣中氧化鋁含量，混拌特定比例之石灰石，計算 CaO與Al2〇3混合配比，兩者混合放入高溫電爐中，以高 溫燒結後倒入水中淬冷，乾燥淬冷後得到的玻璃質固體 ’再研磨至比表面積3〇〇〇~40〇〇cm2/g既成綠色紹質水 泥。 按，銘質水泥是一種銘酸鹤水'泥.，在水合::時不會釋放出 氫氧化鈣Ca(OH)2與流離性石灰使其具有優良的緻密性， 使用於特殊抗蝕環境下時，鋁貪水泥能抵抗許多腐蝕性 物質。鋁質水泥其高鋁質含量，以及水合物的特性，對 酸性以及細菌腐蝕有很好的抗蝕性。如海水、含硫酸鹽 之地下水、工業廢水、純水 '酸、糖液、油等，耐酸鹼 PH值4〜11，鋁質水泥混凝土之鹼性（pH118)輔以搗 實、保護層厚度足夠，可避免pH值之降低。銘質水泥也 是一種快凝水泥，在6小時内可以硬化，24小時之強度 相當於普通水泥28天之強度，在低溫也有良好耐磨耗性 貝八疋需有正確的混拌及施工設計。 099146788 表單編號《 A0101 0992080371-0 201226578 [0008] 鋁質水泥可以是為污水管管線而設計，由於它具有很高 的機械強度及低孔隙，特別適用於抗磨損的結構體如衛 生下水道管線。鋁質水泥製造時要將原料完全熔融，只 要化學成分劑量接近，即可製造出來，與一般固相反應 ，著重反應物的結晶相不同。 【實施方式】 [0009] 以下配合圖式之輔助，說明本發明之内容、特色與實施 例，俾使貴審查委員更進一步瞭解。 0 [0010] 本發明回收鋁渣中90%金屬鋁回製鋁錠，增加經濟效益 。此外將安定化鋁渣作為水泥原料，製成環保鋁質水泥 ，創新鋁渣再利用格局。希冀解決國内二次鋁渣問題， 降低處理問題及成本，創造環境與產業經濟雙贏之局面 [0011] 請參閱第一圖所示，本發明之以二次鋁渣混製鋁質水泥 之方法，其步驟包括： [0012] 1.二次鋁渣回收： [0013] 粗篩：利用篩分機之粗網篩出粒徑較大之粗金屬鋁塊破 碎：使用破碎機進行研磨破碎，較佳之粗篩粒徑係為標 準篩網#10號篩（2. 0mm)以上粒徑範圍。 [0014] 細篩：利用篩分機之細網篩出粒徑較小之細金屬鋁塊及 剩餘鋁渣粉，細篩粒徑係為標準筛網#80號篩（180画）以 下粒徑篩範圍。 分選：篩出著磁金屬後分選出金屬鋁塊，再回收產製金 屬銘產品分析回收技術前後金屬銘含量如表二所示，其 099146788 表單編號A0101 第9頁/共14頁 0 [0015] 201226578 金屬鋁回收率達90%以上，應用此技術於實廠上，實可 增加經濟效益。 [0016] 表二金屬鋁回收含量檢測 批次測試 1 2 3 4 原潰金屬 鋁含量％ 5. 21 4.32 3.81 4.18 回收流程 後鋁金屬 含量％ 0. 44 0.35 0. 36 0. 28 回收率％ 91. 6 91. 9 90.6 93. 4 2.二次鋁渣安定化程序： [0018] 安定化技術主要是降低二次鋁渣中氮含量，以減少鋁渣 遇水氣產出氨氮之臭味，其安定化流程： [0019] A.漿化鋁渣： [0020] 加入特定比例之水份，混拌鉬渣。該二次鋁渣安定化程 序，漿化鋁渣所使用之固液比範圍為1:0. 5〜1:3之間為 較佳之混合比。 [0021] B.安定化藥劑添加： [0022] 加入安定化藥劑與鋁渣中氨進行反應。該二次鋁渣安定 化程序，所使用之安定化藥劑為酸鹼值大於10之化學藥 劑為去除氨氮之較佳經驗PH。 [0023] C.加熱曝氣： [0024] 利用溫度及曝氣效應，加速安定化反應。該二次鋁渣安 099146788 表單編號A0101 第10頁/共14頁 0992080371-0 201226578 定化程序，所加熱溫度範圍為5 0〜9 0 °C ;加熱時間為1〜4 小時。乃是在有限之能源耗費下，所取得之較符合經濟 效益之溫度與時間。201226578 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention mainly relates to a method for mixing aluminum cement with secondary aluminum slag, especially a secondary aluminum slag produced by industry, mixed The method of making cement. [Prior Art] [0002] The domestic aluminum recycling industry produces about 15,000 metric tons of secondary aluminum slag per year. The composition of secondary aluminum slag is very complicated and uneven. The main component is alumina, and its content is about 50. ~80%, in addition to the alumina component, also contains residual aluminum metal, and aluminum nitride and aluminum carbide which are easily reacted with water to produce ammonia nitrogen odor problems. Due to the amount of re-use of secondary aluminum slag in China, it is often far from the amount of production. The traditional treatment methods are mainly based on stabilization and solidification. For Taiwan, where the land is narrow, the legal site for waste disposal is increasingly difficult to obtain. , often causing illegal dumping by illegal workers, causing environmental hazards. In addition, the additional economic value and application efficiency of mixing secondary aluminum slag into green aluminum cement is much higher than that of the prior patented technology. 〇[0003] Table 1 Previous Patent Collection [0004] Patent Name Author Patent No. Method Overview Method for Recycling Aluminum Slag Ash Cai Shunyuan 455514 After the secondary aluminum ash is stabilized with acid (phosphoric acid, sulfuric acid, etc.) Add cement to solidify, solidified body 099146788 Form No. A0101 Page 3 / Total 14 Page 0992080371-0 201226578 Expandability varies with the type and amount of acid added, taking phosphoric acid as an example, when the amount of phosphoric acid is 5% (% by weight) The strength of 276kgf/cm2 can be obtained, and the non-expanding solidified body can be applied to the utilization of compartments, roads, protective walls and other engineering, and can effectively solve the pollution of secondary aluminum ash. Method for manufacturing water-retaining bricks by using secondary aluminum slag 杳泰智 407068 The secondary aluminum slag powder, blast furnace cement and glassy aggregates which have been treated in different proportions are pulverized and then adjusted into a gel, and then pressed into a thick The embryo is then heat-dried and then hardened, and then the form number A0101, page 4 / 14 pages 0992080371-0 099146788 201226578 is fired into a water-retaining brick with fine pore structure. A suitable calcination temperature is 1 050. 01200 X:. ❹ 处理 Treatment of aluminum slag stabilization and reuse method Chen Qingqi et al. 1234587 Use calcium oxide substance (desulfurization slag, etc.) as an aluminum slag waste stabilizer, and high pressure concrete brick as the final reuse product of stabilized aluminum slag. The strong alkaline (PH212) environment produced by the oxidation of the oxidized 1 bow can promote the rapid hydrolysis of harmful substances such as nitriding, carbonization and metal aluminum in the aluminum collapse, and achieve the purpose of stabilization treatment; The high alkaline effect is high. 099146788 Form No. A0101 Page 5 of 14 0992080371-0 201226578 The pressed concrete brick process (pH 212) can further stabilize the slag and use high pressure brick as a reuse product. Method for manufacturing ceramic filter material from aluminum ash ash Cai Shunyuan 1246938 The aluminum ash ash is sintered to form "α 氧化 铭", after adding α-oxidation, adding binder, porogen, cosolvent and stabilizer, etc. Mixing, finally forming the ceramic filter embryo type, drying, firing, cooling and other steps to complete the finished product, converted into high-priced ceramic filter material. The treatment method of the secondary Ming ί ash resource utilization Wu Hao 1277443 First, the aluminum ash ash is separated into specific gravity, so that the secondary aluminum ash ash is separated into the form number A0101 Page 6 / 14 pages 0992080371-0 099146788 201226578 Light Aluminum carbide, calcium carbide and heavier aluminum nitride, alumina, and then carbonization Ming, carbonized mother, aluminum nitride and alumina are operated by rfj warm steam, so that the aluminum carbide and calcium carbide are catalyzed by high temperature steam. The decane is stabilized and can be used as a material for filling, and after nitriding and alumina are stabilized, it can be used as a graded sand or pipeline sand. SUMMARY OF THE INVENTION [0005] In view of the previous problems, the inventors believe that there should be a recycling process for recovering metal aluminum, and a technology for the stabilization of secondary aluminum slag, thereby recovering 90% of the metal aluminum in the secondary aluminum slag. Remanufactured aluminum ingots to increase economic efficiency. In addition, the stabilized secondary aluminum slag is used as a cement raw material to produce green aluminum cement, and the secondary secondary aluminum slag reuse pattern is innovated. Hope to solve the domestic secondary aluminum 099146788 Form No. A0101 Page 7 of 14 0992080371-0 201226578 Production problems, reduce processing problems and costs, create a win-win situation between the environment and the industrial economy. According to the secondary aluminum slag, it refers to the tailings produced after the secondary smelting process in the process of melting the aluminum-containing raw material into a related metal aluminum product by high-temperature melting, segregation melting, casting and the like. [0007] In order to achieve the foregoing object, the inventors have devised a method for mixing aluminum cement with secondary aluminum slag, the steps of which include: first, coarse screening, grinding, fine screening and sorting, etc. After the metal aluminum is recovered, the aluminum product is smelted, and the female bismuth chemical is added to the reaction in a single method, so that the nitrogen content of the second smelting medium is reduced to 0.5% or less, and the effect of removing ammonia odor is achieved, and finally the stability is determined. The content of alumina in the secondary aluminum slag is mixed with a certain proportion of limestone, and the mixing ratio of CaO and Al2〇3 is calculated. The two are mixed and placed in a high-temperature electric furnace, sintered at a high temperature, poured into water and quenched, and obtained after drying and quenching. The vitreous solid is 'grinded to a specific surface area of 3 〇〇〇 40 〇〇 cm 2 / g to form a green cement. According to the name, cement is a kind of acid sluice water 'mud. When hydration:: does not release calcium hydroxide Ca(OH)2 and fluidized lime to make it have excellent compactness, used in special anti-corrosion environment. When it comes down, aluminum cement can resist many corrosive substances. The high aluminum content of aluminum cement, as well as the characteristics of hydrates, is very resistant to acid and bacterial corrosion. Such as sea water, sulphate-containing groundwater, industrial wastewater, pure water 'acid, sugar liquid, oil, etc., acid and alkali pH value 4~11, aluminum cement concrete alkali (pH118) supplemented with tamping and protective layer thickness Sufficient to avoid a drop in pH. Ming Cement is also a kind of quick-setting cement, which can be hardened in 6 hours. The strength of 24 hours is equivalent to the strength of ordinary cement for 28 days, and it also has good wear resistance at low temperature. Baqiu needs proper mixing and construction design. 099146788 Form No. A0101 0992080371-0 201226578 [0008] Aluminium cement can be designed for sewer pipes. Due to its high mechanical strength and low porosity, it is particularly suitable for wear-resistant structures such as sanitary sewer lines. When aluminum cement is manufactured, the raw materials are completely melted. As long as the chemical components are close to each other, they can be produced. The reaction with the general solid phase is focused on the crystal phase of the reactants. [Embodiment] [0009] The contents, features, and embodiments of the present invention will be described with reference to the accompanying drawings, and the reviewing committee will be further understood. 0 [0010] The invention recovers 90% metal aluminum recycled aluminum ingot in aluminum slag, thereby increasing economic benefits. In addition, the stabilized aluminum slag is used as a raw material for cement to make environmentally-friendly aluminum cement, and the innovative aluminum slag reuse pattern. Hope to solve the problem of secondary aluminum slag in China, reduce processing problems and costs, and create a win-win situation for the environment and industrial economy [0011] Please refer to the first figure, the method for mixing aluminum cement with secondary aluminum slag according to the present invention The steps include: [0012] 1. Secondary aluminum slag recovery: [0013] coarse screening: using a coarse mesh of a sieving machine to sieve a coarse metal agglomerate having a larger particle size to be crushed: using a crusher for grinding and crushing, preferably The coarse sieve particle size is in the range of the above sieve size of the standard sieve #10 sieve (2.0 mm). [0014] Fine sieve: using a fine mesh of a sieving machine to sieve a fine metal aluminum block with a small particle size and a residual aluminum slag powder, and the fine sieve particle size is a standard sieve #80 sieve (180 paintings) below the sieve size range. Sorting: After sieving out the magnetic metal, the metal aluminum block is sorted out, and the metal ingot product is recovered and analyzed. The metal content of the product is shown in Table 2, which is 099146788 Form No. A0101 Page 9 / Total 14 Page 0 [0015 201226578 Metal aluminum recycling rate of more than 90%, the application of this technology in the actual plant, can increase economic benefits. [0016] Table 2 metal aluminum recovery content test batch test 1 2 3 4 original metallurgical aluminum content% 5. 21 4.32 3.81 4.18 aluminum metal content after recovery process% 0. 44 0.35 0. 36 0. 28 recovery rate 91 6 91. 9 90.6 93. 4 2. Secondary aluminum slag stabilization procedure: [0018] The stabilization technology is mainly to reduce the nitrogen content in the secondary aluminum slag to reduce the odor of ammonia slag in the production of ammonia nitrogen. The stabilization process: [0019] A. Slurry aluminum slag: [0020] A specific proportion of water is added, and the molybdenum slag is mixed. The secondary aluminum slag stabilization process, the solid-liquid ratio of the slurry of the aluminum slag is in the range of 1:0. 5~1:3 is the preferred mixing ratio. [0021] B. Stabilizing agent addition: [0022] Adding a stabilizer to react with ammonia in the aluminum slag. The secondary aluminum slag stabilization procedure uses a chemical agent having a pH greater than 10 as the preferred experience for removing ammonia nitrogen. [0023] C. Heating aeration: [0024] The stabilization reaction is accelerated by the temperature and aeration effects. The secondary aluminum slag 099146788 Form No. A0101 Page 10 of 14 0992080371-0 201226578 The characterization procedure, the heating temperature range is 5 0~9 0 °C; the heating time is 1~4 hours. It is the temperature and time that are more economically viable under the limited energy consumption.
[0025] 安定化技術反應後之鋁渣氮含量如表三所示，其中鋁絕 大部分是以氧化鋁形式存在，且超過含量30%，且可去 除超過90%的氯，以利氧化鋁產物的後續再利用。此技術 確實已能達到預期之使用目的及功效，特別用於處理經 過回收之金屬鋁後剩餘的二次熔鋁渣粉，且提供產業利 用上具實質經濟效益。 [0026] 表三安定化鋁渣元素含量檢測 元素 (%) A1 Si N Cl Mg Ca 原始鋁 渣 37. 1 2. 58 1.52 0. 85 1. 45 2. 01 安定化 鋁渣 35. 7 2. 23 0. 48 0. 04 0. 68 2.25 [0028] 3.以石灰石添加混拌，並經高溫燒結以及淬冷、研磨產 生鋁質水泥。主要係將去除氨臭之安定化鋁渣製成水泥 應用之方法，其方法流程： [0029] A.混拌石灰石： [0030] 加入特定比例之石灰石，混拌鋁渣； 099146788 表單編號A0101 第11頁/共14頁 0992080371-0 201226578 [0031] 其中該鋁質水泥之配比，較佳為鋁渣氧化鋁與石灰石氧 化鈣掺拌比例為0. 8 5 :卜1. 4 : 1。 [0032] B.高溫燒結： [0033] 利用高溫促使鋁渣中之氧化鋁與石灰石反應形成鋁質水 泥基本成份鋁酸鈣CA。其中該鋁質水泥之燒結溫度範圍 為1 000〜1 800°C ;燒結時間為2~6小時為較佳之經驗值。 [0034] C.淬冷： [0035] 利用水冷或氣冷方式，加速冷卻安定。 [0036] D.研磨： [0037] 利用研磨設備，研磨至比表面積3000〜4000cm2/g既成 綠色鋁質水泥。 [0038] 綜上所述，本發明誠已符合發明專利申請要件，爰依法 提出發明專利之申請，懇請惠予審查，並早日賜准專利 ，實感德澤。 【圖式簡單說明】 [0039] 第一圖係本發明之流程圖 【主要元件符號說明】 [0040] 099146788 表單編號A0101 第12頁/共14頁 0992080371-0[0025] The aluminum slag nitrogen content after the stabilization technology reaction is shown in Table 3, wherein most of the aluminum is in the form of alumina, and the content exceeds 30%, and more than 90% of the chlorine can be removed to facilitate the alumina. Subsequent reuse of the product. This technology has indeed achieved the intended use and efficacy, especially for the treatment of secondary molten aluminum slag powder remaining after the recovered metal aluminum, and provides substantial economic benefits for industrial use. [0026] Table 3 Anodized aluminum slag element content detection element (%) A1 Si N Cl Mg Ca original aluminum slag 37. 1 2. 58 1.52 0. 85 1. 45 2. 01 stabilized aluminum slag 35. 7 2. 23 0. 48 0. 04 0. 68 2.25 [0028] 3. Adding mixed limestone, and sintering at high temperature, quenching and grinding to produce aluminum cement. Mainly the method for removing ammonia odor stabilized aluminum slag into cement application, the method flow thereof: [0029] A. mixing limestone: [0030] adding a certain proportion of limestone, mixing aluminum slag; 099146788 Form No. A0101 8 5:卜1. 4 : 1。 The ratio of the aluminum slag alumina and limestone calcium oxide blending ratio is 0. 8 5 : Bu 1. 4: 1. [0032] B. High Temperature Sintering: [0033] The use of high temperature promotes the reaction of alumina in the aluminum slag with limestone to form calcium aluminate CA, the basic component of the aluminum cement. The sintering temperature of the aluminum cement ranges from 1 000 to 1 800 ° C; the sintering time is from 2 to 6 hours, which is a preferred empirical value. [0034] C. Quenching: [0035] The cooling and stabilization is accelerated by water cooling or air cooling. [0036] D. Grinding: [0037] Grinding to a specific surface area of 3000 to 4000 cm 2 /g by a grinding apparatus to form a green aluminum cement. [0038] In summary, the invention has met the requirements of the invention patent application, and the application for the invention patent is filed according to law, and the application for review is granted, and the patent is granted as soon as possible. BRIEF DESCRIPTION OF THE DRAWINGS [0039] The first diagram is a flow chart of the present invention [Description of main component symbols] [0040] 099146788 Form No. A0101 Page 12 of 14 0992080371-0