臺灣博碩士論文加值系統

稀有鎵金屬的含量在地球中僅有約0.0015%。鎵金屬化合物在高溫下，能與硫、硒、碲、磷、砷、銻反應，生成的化合物包括高頻率、高電子遷移率及低噪音等特性，故受電子科技業廣泛應用。經回收的稀有鎵金屬，可以出售進而獲取利潤。目前產生之研磨污泥皆以固化及掩埋方式處理。國內尚無適當的鎵金屬回收處理技術與機構，若處理不當，可能影響環境甚巨。因此，就經濟價值及環境影響而言，鎵金屬廢棄物急需進行回收處理。本研究主要針對電子業鎵金屬之廢棄物，進行烘乾與研磨、脫水烘乾、酸溶出、鋅置換、電解回收等流程，將稀有鎵金屬回收，以避免污染環境並達成廢棄物回收再利用之目標。並研究並探討電子業鎵金屬回收方法。根據本研究之成果顯示，酸溶解，分別選擇4N硝酸及4N硫酸作為最佳溶出濃度，可將使用量降至最低，且可達到最大的溶解效果。鋅置換實驗，硝酸溶解液在2.5安培時，添加鋅20克之電解效率與成品純度較佳；在5安培時，添加鋅20克之電解效率較佳。硫酸則無明顯差異。電解結果，硝酸溶解液在電解時控制溫度於20℃，比無控制溫度下電解效果較佳。不同安培電解，硝酸溶解液以5安培電解效率與成品純度皆較佳；硫酸溶解液以5安培電解效率較佳。電解後的氧化鎵生成物，並無砷金屬殘留。初步判定，電解後硝酸溶解液的電解成品為氧化鎵；硫酸溶解液的電解成品為硫酸鎵。本研究最佳研究條件，為硝酸溶解樣品，添加20克鋅與D2EPHA，以5安培電解後，取得成品氧化鎵效果(電解回收效率61.7%，純度98.2%)較佳。在最佳研究條件下，25克廢鎵樣品(55.6%)，由實驗過程鎵回收61.7%，獲得粗製氧化鎵8.8克，其純度為98.2%，其他成分為鉛(1.76%)與鋅(0.09%)。

There is approximatly 0.0015 % of gallium concentration in the earth. The Gallium metal chemical compound is can react with the Sulphur , Selenium , Tellurium , Phosphorus , Arsenic , and Antimony under high temperature; resulting chemical compound including high frequency , high electron person who move and characteristic such as being with low noise that produce, so receive the extensive application of electronic science and technology industry . Through the scarce Gallium metal retrieving , can sell then obtain profits. The ones that produce grind the mud all with solidification and bury the way to deal with at present. There is no proper Gallium metal that retrieve treatment technology and organization yet at home. If it is improper to be dealed with, may influence the environment to be very huge . So, as regards economic worth and environmental impact, the Gallium metal offal needs retrieving and dealing with badly. Bake the universe and procedure of grinding , dehydrating to bake the universe , acid to dissolve appearing , zinc replacement , retrieving electrolytically etc. to the offal of electron industry and Gallium metal mainly in this research, retrieve the scarce Gallium metal, retrieve the goal utilized again in order to avoid polluting the environment and reaching offals. And study and probe into the electron industry Gallium metal and retrieve the method . According to achievement of this research, the acid is dissolved, choosing 4N nitric acid and 4N sulphuric acid as dissolving out the thickness bestly separately, it is lowest that can drop the consumption to , and can reach the greatest result of dissolving . The Zinc replaces the experiment , when the nitric acid dissolves the liquid in 2.5 A, it is relatively good in purity to add 20 g of electrolytic efficiency of zinc and finished product; In 5 A, it is relatively good to add 20 g of electrolytic efficiency of Zinc. The sulphuric acid does not have obvious difference. Electrolytic result, the nitric acid dissolves the liquid and controls temperature in 20℃ when being electrolytic, the electrolytic result is better than to have no temperature of controlling. Different ampere is electrolytic, it is all relatively good in purity with electrolytic efficiency of 5A and finished product that the nitric acid dissolves the liquid ; It is relatively good that the sulphuric acid dissolves the liquid with electrolytic efficiency of 5A. Oxidizing gallium producting after being electrolytic, have arsenic metal to remain. Judge tentatively , the nitric acid dissolves the electrolytic finished product of the liquid in order to oxidizeGalliums after being electrolytic; The electrolytic finished product that the sulphuric acid dissolves the liquid is a sulphuric acid gallium. This best research condition of research, dissolve samples for the nitric acid , add 20 g of zinc and D2EPHA, after by 5A the electrolytic,whether make it last Gallium result finished product (the electrolytic to last 61.7% efficiencies, 98.2% of purity ) relatively good. Under the best research condition, 25 g abolish the Gallium sample (55.6% ) , is retrieved 61.7% by the experiment course gallium , get and make and oxidize 8.8 grams of Galliums thickly, its purity is 98.2%, other composition are Lead (1.76% ) and Zinc (0.09% ).

目錄 頁次
中文摘要...........................................................................................................Ι
英文摘要...........................................................................................................Ⅲ
誌謝……...........................................................................................................Ⅴ
表目錄…...........................................................................................................Ⅵ
圖目錄.…..........................................................................................................Ⅶ
一、緒論.............................................................................................................1
1.1研究背景...............................................................................................1
1.2研究目標...............................................................................................1
二、文獻回顧.....................................................................................................2
2.1鎵元素之物化特性...............................................................................2
2.2砷化鎵之MSDS.......….........................................................................3
2.3電子產業界鎵金屬應用與回收的情況...............................................4
2.3.1電子產業界鎵金屬的應用與產品製程.......................................5
2.3.2電子產業界LED鎵金屬廢棄物來源........................................13
2.3.3電子產業界LED鎵金屬廢棄物回收的情況............................13
2.4國內外含鎵廢棄物相關回收之研究文獻.........................................14
2.4.1國外研究文獻.............................................................................14
2.4.2國內研究文獻.............................................................................18
三、實驗方法與實驗設備材料.........................................................................22
3.1研究流程.............................................................................................23
3.2 實驗藥品與設備................................................................................24
3.2.1實驗藥品.....................................................................................24
3.2.2實驗設備.....................................................................................24
3.3 實驗方法及步驟................................................................................25
3.3.1 樣品來源...................................................................................25
3.3.2 前處理與溶出方法...................................................................25
3.3.2定性及定量研究.........................................................................25
3.3.3鋅金屬置換鎵金屬與溶媒萃取法.............................................26
3.3.4電解回收法.................................................................................27
3.3.5 樣品純度分析...........................................................................27
3.3.6 高溫煅燒...................................................................................27
四、結果與討論.................................................................................................28
4.1 廢鎵樣品成分....................................................................................29
4.1.1 廢鎵固體含量...........................................................................29
4.1.2 樣品中金屬成分分析...............................................................30
4.2廢鎵之最佳酸溶解結果.....................................................................31
4.2.1廢鎵之硝酸溶解結果.................................................................31
4.2.2廢鎵之硫酸溶解結果.................................................................32
4.2.3硝酸與硫酸對廢鎵之溶解比較.................................................33
4.3廢鎵溶解液之最佳鋅置換.................................................................34
4.3.1硝酸系列.....................................................................................34
4.3.2.硫酸系列..............................…..................................................36
4.4最佳電解效率.....................................................................................38
4.4.1 控溫對鎵電解效率之影響.......................................................38
4.4.2 2.5安培電解效率....................................................................41
4.4.3 5安培電解效率.......................................................................43
4.4.4 總電解效率.............................................................................44
4.5 鎵成品純度與定性............................................................................46
五、結論與建議.................................................................................................50
5.1結論.....................................................................................................50
5.2建議.....................................................................................................50
參考文獻……...................................................................................................51
附錄一、有害事業廢棄物與一般有害事業廢棄物認定標準.........................54
附錄二、砷化鎵之MSDS..................................................................................58
附錄三、脫水實驗.............................................................................................62
附錄四、鎵金屬酸溶出實驗紀錄....................................................................64
附錄五、ICP電解實驗數據...............................................................................66
附錄六、火焰離子偵測器的鎵濃度分析之有效範圍....................................71
附錄七、八小時電解數據……………………………....................................72


表目錄
表2-1鎵的物化性質.........................................................................................2
表2-2 鎵金屬電子元件應用於各產業類別與項目.........................................4
表2-3矽(Si)、鎵金屬化合物(Ga)所製成之元件特性比較................................5
表2-4日本同和礦業公司金屬原料的佔有率與市場經濟規模.......................6
表2-5. 化合物之性質、製造方式與危險性......................................................7
表2-6 國內電子產業各種鎵金屬化合物的功能與研究的半導體製造廠商.8
表2-7 2005年國內鎵金屬產業廠商........................................…....................11
表2-8 金屬鎵廢棄物表...................................................................................12
表3-1鎵的相關反應式.....................................................................................20
表3-1鎵的相關反應式.....................................................................................23
表4-1硝酸系列各實驗變因代號表.................................................................28
表4-2硫酸系列各實驗變因代號表.................................................................28
表4-3. 經ICP分析之樣品金屬成分...............................................................30
表4-4 鎵Ga成品物化性質試驗......................................................................45
表4-5. 廢鎵樣品中金屬成份分析.............…….............................................47

圖目錄
圖2-1鎵金屬在常溫下以固體的形式存在.......................................................3
圖2-2 LED鎵產品的製程.............................................................................10
圖2-3 鋅廢液中鎵金屬的回收程序實驗流程...............................................13
圖2-4 鎵廢棄物液/液萃取鎵金屬回收法實驗流程......................................14
圖2-5 利用溶媒PC-88A進行溶媒萃取析出三價鎵實驗流程.....................15
圖2-6 針對砷化鎵中鎵的浸漬之研究實驗流程...........................................16
圖2-7 砷化鎵晶片回收成形成含鎵之鹽類實驗流程...................................16
圖2-8砷化鎵廢屑濕式與乾式回收法之簡易回收流程比較.........................17
圖2-9 砷化鎵廢棄物資源回收之研究...........................................................19
圖3-1. 實驗流程..............................................................................................22
圖4-1 鎵廢棄物...............................................................................................29
圖4-2. 水分與乾燥後重量比例......................................................................30
圖4-3. 原始樣品中金屬成分比例..................................................................31
圖4-4. 廢鎵樣品在不同硝酸濃度之溶解量..................................................32
圖4-5. 廢鎵樣品在不同硫酸濃度之溶解量..................................................33
圖4-6. 以硝酸與硫酸對廢鎵之溶解試驗比較..............................................34
圖4-7. 2.5安培下，以硝酸電解之鋅置換之效率與純度..........................35
圖4-8. 5安培下，以硝酸電解之鋅置換之效率與純度.......……………......36
圖4-9. 2.5安培下，以硫酸電解之鋅置換之效率與純度................................37
圖4-10. 5安培下，以硫酸電解之鋅置換之效率與純度....…………….......38
圖4-11電解時間與鎵濃度、溫度之變化.........................................................39
圖4-12. 於控溫下，硝酸溶解液之鎵濃度變化圖..........................................39
圖4-13. 硝酸在控溫對鎵濃度之電解效率比較............................................40
圖4-14. 於控溫下，硫酸溶解液之鎵濃度變化圖..........................................40
圖4-15. 在控溫下，硫酸對Ga濃度之電解效率比較圖.............……............41
圖4-16. 在2.5A下，以4N 硝酸、硫酸電解之鎵濃度變化圖........................41
圖4-18. 2.5安培對不同酸液與鋅置換之鎵電解效率....................................42
圖4-17. 在2.5A下，以4N 硝酸、硫酸電解之回收效率圖............................42
圖4-18. 2.5安培對不同酸液與鋅置換之鎵電解效率....................................42
圖4-19. 在5A對不同酸液與鋅置換之鎵電解效率.......................................43
圖4-20. 廢棄鎵電解回收效率總曲線............................................................44
圖4-21. 鎵金屬電解回收效率比較................................................................44
圖4-22 氧化鎵成品.........................................................................................46
圖4-23 硫酸鎵成品.........................................................................................46
圖4-24. Ga2O3成品純度之金屬比例.............................................................47
圖4-25. 純度與電解效率比較........................................................................48

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