臺灣博碩士論文加值系統

再生鋁產業中，以廢鋁熔煉比例較高，國內熔煉過程所產生的產出鋁集塵灰及鋁渣，每年產出超過十萬噸以上，鋁集塵灰主要成分為顆粒細小的金屬鋁、氧化鋁、氮化鋁及碳化鋁，若能有效回收或再利用鋁集塵灰，提昇鋁集塵灰中的鋁回收率，增加以氧化鋁作為資源化產品，將可減少廢棄物處理所需之掩埋場地及費用，且若有效提高氧化鋁產品純度，將可進一步提高資源化產品的附加價值。本研究以有效提取集塵灰中氧化鋁為目標並參考酸性法（Acid process），選用酸性較弱的磷酸配合適當溫度與時間之鍛燒，以產物中氧化鋁濃度與回收率為基準，研究目的包含分析：a)過濾步驟在以水溶出集塵灰中鋁之方法之影響；b)不同集塵灰與水之重量比在水溶出集塵灰中鋁之方法之影響；c)集塵灰與磷酸之不同重量比在氫氧化鈉溶出集塵灰中鋁之方法之影響；d)在氫氧化鈉溶出集塵灰中鋁之方法中，於不同集塵灰與磷酸之重量比條件下，添加不同質量之氫氧化鈉與磷酸之影響；e)攪拌方式之影響；以及f)總結所有數據，分析使用磷酸進行酸性法提取鋁集塵灰中氧化鋁之可行性。
研究過程中以添加與鋁集塵灰不同重量固液比之磷酸、反應後鹼添加量比較、煅燒與攪拌方法比較，配合適當溫度與時間進行酸性法。實驗結果顯示，氧化鋁多保留於與磷酸反應煅燒後固體殘渣中，鋁集塵灰與磷酸反應後，磷酸鋁不溶於水的特性，需以添加鹼方式溶出氧化鋁。取上澄液煅燒方式，與固體殘渣相互比較，可得知其氧化鋁皆保留於固體殘渣中，回收率約70%至接近90%。與磷酸反應煅燒後固體殘渣中五氧化二磷比例較低，以含量比較，氧化鋁含量明顯比上澄液中氧化鋁含量較高，且固體殘渣中氧化鋁含量皆比未固液分離氧化鋁含量高、另以回收率比較，可得知未固液分離仍保留氧化鋁全量。以攪拌方式，可得知高溫煅燒可使酸浸過程氧化鋁溶出效果較佳。以成品中氧化鋁含量最高為標準，最佳操作參數為取集塵灰2克，與磷酸重量固液比1:0.49，以275℃煅燒2.5小時，加入氫氧化鈉1.2克後再於85℃反應0.5小時，以滴管將其固液分離，僅取固體殘渣將其燒乾，此方法成品中氧化鋁含量59.6 %以及整體方法回收率為97.5 %。以成品中回收率最高為標準，最佳實驗操作參數為取集塵灰2克，與磷酸重量固液比1:0.49，以275℃煅燒2.5小時，加入氫氧化鈉0.8克後於85℃反應0.5小時，未固液分離，將其燒乾，以此方法可得到成品中氧化鋁含量36.7 %以及整體方法回收率為106.6 %。但氧化鋁及五氧化二磷以外雜質皆有明顯降低，五氧化二磷若能有效去除，以磷酸提取氧化鋁仍有發展技術的空間。

Aluminum smelting is one critical process in the aluminum-regeneration industries. In Taiwan, the production of aluminum-containing dusts produced by smelting exceeds 100,000 tons/year. The principal constituents in aluminum-containing dusts include metal aluminum, aluminum oxide, aluminum nitride, and aluminum carbide. By effectively recycling and reusing aluminum-containing dusts, elevating the aluminum recovery of the processes, and increasing the feasibility of producing aluminum oxide-containing produces, the land area and cost needed for the aluminum-containing solid waste treatments can be critically reduced, simultaneously increasing the value of the end-point products. The objective of this study was to study the effectiveness and efficiency of extracting aluminum from the aluminum-containing dusts by using the acid process with phosphoric acid, with respect to the effects of temperature and time for calcination. The sub-topics are to test: a) the effect of filtration on the recovery and concentration of aluminum oxide in the products when water was used for aluminum dissolution; b) the effect of solid-to-water mass ratio on the recovery and concentration of aluminum oxide in the products when water was used for aluminum dissolution; c) the effect of solid-to-sodium hydroxide mass ratio on the recovery and concentration of aluminum oxide in the products when sodium hydroxide was used for aluminum dissolution; d) the effect of the solid-to-sodium hydroxide mass ratio and the amount of sodium hydroxide on the recovery and concentration of aluminum oxide in the products when sodium hydroxide was used for aluminum dissolution; e) the effect of different stirring approaches on the recovery and concentration of aluminum oxide in the products; and f) the feasibility of using phosphoric acid for extraction of aluminum oxide from aluminum-containing ashes.
In the results, aluminum oxide was mostly present in the solid residue after the reactions. Given the low solubility of aluminum, the addition of base is inevitable for dissolution of aluminum oxide. The recovery of aluminum oxide in the solid residue ranged from 70% to 90%, suggesting that most of the aluminum oxide was still present in the solid residue instead of the supernatant. The performance of this extraction process was better when high-temperature calcination was used for aluminum dissolution with phosphoric acid. To reach the highest aluminum oxide content in the products, the optimal parameters are as follows: 2 g of aluminum-containing ash was collected. The solid-to-phosphoric acid mass ratio was 1 to 0.49. The calcination temperature and time were 275℃ and 2.5 hr, respectively. 1.2 g of sodium hydroxide was added and the reaction was maintained at 85℃ for 0.5 hr. The solid and solution were separated, followed by drying the solid residue at a high temperature. The concentration and recovery of aluminum oxide in the product through this approach were 59.6% and 97.5%, respectively. To reach the highest aluminum oxide recovery, the optimal parameters are as follows: 2 g of aluminum-containing ash was collected. The solid-to-phosphoric acid mass ratio was 1 to 0.49. The calcination temperature and time were 275℃ and 2.5 hr, respectively. 0.8 g of sodium hydroxide was added and the reaction was maintained at 85℃ for 0.5 hr. The solid and solution were not separated, followed by drying the solid residue at high temperature. The concentration and recovery of aluminum oxide in the product through this approach were 36.7% and 106.6%, respectively. In the future study, the effective and efficient removal of the phosphor from the final product is the key to develop this extraction technology.

摘要 i
Abstract iii
目錄 vi
圖目錄 ix
表目錄 xi
第一章 緒論 1
1.1前言 1
1.2研究動機及目的 3
第二章 文獻回顧 5
2.1鋁 5
2.1.1鋁合金 7
2.1.2金屬鋁製品製造業及產品 8
2.1.3氧化鋁 9
2.2鋁冶煉方法 10
2.2.1拜耳法（Bayer process） 10
2.2.2霍爾－埃魯法（Hall–Héroult process） 12
2.2.3鋁回收再生技術 12
2.3煉鋁爐渣回收再生之經濟效益 13
2.3.1鋁渣之來源 14
2.3.2 鋁渣水解反應 15
2.3.3國內鋁集塵灰處理方式 16
2.3.4鋁渣對環境造成之影響 18
2.4鋁集塵灰之回收技術 19
2.4.1煅燒法（Sintering processes） 19
2.4.2 水化學法（Hydro-chemical process） 20
2.4.3酸性法（Acid process） 21
2.4.4其他特殊方法 22
2.5磷酸 23
2.5.1 五氧化二磷 24
第三章 研究方法 25
3.1實驗架構 25
3.2 實驗步驟與流程 26
3.2.1 第一階段實驗流程 26
3.2.2 第二階段實驗流程 27
3.2.3 第三階段實驗流程 28
3.2.4 第四階段實驗流程 29
3.2.5 第五階段實驗流程 30
3.3 實驗材料與藥劑 31
3.3.1 樣品來源 31
3.3.2 實驗試劑與器材 32
3.4 實驗分析儀器 33
3.4.1 X-光螢光分析儀(X-ray Fluorescence Spectrometer，XRF) 33
3.4.2 X-光繞射儀(X-ray Diffractor，XRD) 35
3.4.3 環境掃描式電子顯微鏡(Environmental scanning electron microscope，ESEM) 36
3.5品質保證與品質管理(QA/QC) 37
3.6 氧化鋁回收率計算 38
第四章 結果與討論 39
4.1 鋁集塵灰之成份 39
4.2 X-射線螢光光譜儀（XRF）分析結果 41
4.2.1過濾方式對氧化鋁回收及含量之影響 41
4.2.2以水溶出及以鹼溶出對氧化鋁回收及含量之影響 44
4.2.3 不同重量固液比對氧化鋁回收及含量之影響 47
4.2.4 氫氧化鈉添加量對氧化鋁回收及含量之影響 50
4.2.5 磷酸添加量對氧化鋁回收及含量之影響 62
4.2.6以攪拌方式對氧化鋁回收及含量之影響 70
4.3 X-光繞射儀（XRD）分析結果 73
4.4環境掃描式電子顯微鏡(ESEM)分析結果 76
4.5以磷酸提取氧化鋁可行性 79
第五章 結論與建議 80
5.1 結論 80
5.2 建議 84
參考文獻 85

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