臺灣博碩士論文加值系統

本研究以鋁箔包為材料，採用四種不同氧濃度 (5.37、10.40、14.82、20.95 %)及三種不同加熱速率 (5.25、10.36、15.06 K/min)，進行鋁箔包之部份氧化熱裂解實驗，以建立反應動力模式。在最大氧濃度 (20.95 %)、加熱速率為5.25 K/min時，收集鋁箔包部份氧化熱裂解後之固體殘餘物與產氣進行分析，並配合反應動力模式探討鋁箔包在不同氧濃度下部份氧化熱裂解之反應機制。
在熱裂解動力分析方面，鋁箔包在四種氧濃度下之部份氧化熱裂解反應可視為兩階段反應，第一階段與第二階段之重量消失比值約為0.6：0.4。第一階段反應之活化能、反應級數及頻率因子分別為E1=26.55 kcal / mol、n1=0.7964、m1= -0.4751、A1=7.03×106 sec-1。而第二階段反應則是E2=23.39 kcal / mol、n2=2.3143、m2=1.4658、A2=9.29×105 sec-1。將所得反應動力模式與實驗數據比較，其中氧濃度為5.37 % ~ 20.95 %時，反應溫度範圍為400 ~ 1000 K時，在三種不同加熱速率下其決斷係數為0.9469 ~ 0.9874，表示此模式在四種濃度下是可接受的。
在產物分析方面，最終固體殘餘物中所含之殘碳較純氮熱裂解所含之殘碳少，表示在有氧條件下反應較完全。將最終固體殘餘物中之鋁箔以X光粉末繞射儀鑑定，結果顯示所含之鋁箔並未被氧化成氧化鋁，仍為純鋁，增加了回收的價值。鋁箔包部份氧化熱裂解反應所得主要氣體產物包括CO2、CO、H2O和HCs，含量由小到大依序是CO2、CO、H2O、HCs，其中HCs以低碳數(C1~5)之烷類及烯類為主。

The tetra packs were pyrolyzed in four different oxygen concentrations (5.37, 10.40, 14.82, and 20.95 %) at the heating rates of 5.25, 10.36, and 15.06 K/min, and the reaction kinetic model of tetra packs was built up. For the product analysis, tetra packs were pyrolyzed in the oxygen concentration of 20.95 % at the heating rate of 5.25 K/min, and the solid residues and gaseous products were collected and analyzed .The mechanisms of tetra packs pyrolysis in different oxygen concentration . were investigated from the kinetic model and the product analysis.
For the reaction kinetics of tetra pack pyrolysis in four oxygen concentrations is described as two stage reaction.The mass loss ratio of the two reaction was 0.6 / 0.4. The reaction energy (E1), reaction order (n1,m1), and frequency factor (A1) of the first stage of the tetra packs pyrolysis are 26.55 kcal/mol, 0.7964, -0.4751, and 7.03×106 sec-1 respectively. The reaction energy (E2), reaction order (n2、m2), and frequency factor (A2) of the second stage of the tetra packs pyrolysis are 23.39 kcal/mol, 2.3143, 1.4658, and 9.29×105 sec-1 respectively. When the oxygen concentration is between 5.37 % and 20.95 %, the coefficients of determination (R2) of the mass residual curves deduced from the obtained reaction kinetic expressions at three different heating rates is between 0.9469 and 0.9874. Thus, the experimental data of tetra packs pyrolysis in four oxygen concentrations are fitted satisfactorily by the obtained reaction model.
For the product analysis, the char in the final residues was less than
that for the tetra packs pyrolysis in nitrogen. Thus, the reaction was more complete in oxygen condition. The aluminum foil in the final residues was analyzed by XRPD (X-ray powdered diffraction), and the results indicate that the aluminum foil in the final residues was pure aluminum. The results evaluate the recovery value of aluminum foil. The main gaseous products of tetra packs pyrolysis reaction were CO2、CO、H2O and HCs, by the turn is CO2、CO、H2O and HCs. The HCs consisted of low molecular paraffin and olefin (C1~5).

目錄
中文摘要……………………………………………………………...Ⅰ
英文摘要……………………………………………………………...Ⅱ
目 錄………………………………………………………………Ⅳ
圖 目 錄………………………….…………………………………..Ⅶ
表 目 錄………………………………………...……………..……ⅩⅧ
符號說明…………………………………………………………….ⅩⅩ
第一章 緒論………………….…………………………………….….1
1-1研究緣起…………….…………………………………….…..1
1-2研究目的…………….………………………………………...3
1-3研究內容………………………………………………………3
第二章 文獻回顧與基本理論…………………………………..….5
2-1惰性氣流下之熱裂解研究……………………………………5
2-1-1鋁箔包的熱裂解………………………………………….5
2-1-2紙類和纖維素的熱裂解………………………………….6
2-1-3聚乙烯(PE)的熱裂解……………………………………11
2-2有氧條件下之熱分解………………………………………..13
2-2-1鋁箔包在有氧條件下之熱分解………………………...13
2-2-2纖維在有氧條件下之熱分解…………………………...13
2-2-3橡膠在有氧條件下之熱分解…………………………...16
2-3反應動力分析基本理論……………………………………..22
第三章 實驗設備與方法……………………………………..29
3-1實驗設備與材料……………………………………………..29
3-2研究流程……………………………………………………..33
3-3鋁箔包樣品成份分析………………………………………..34
3-3-1樣品來源………………………………………………...34
3-3-2三成份分析……………………………………………...34
3-3-3熱值分析………………………………………………...34
3-3-4重金屬分析…………………………………………...…34
3-3-5元素分析………………………………………………...34
3-3-6金屬鋁之純度分析……………………………………...35
3-4實驗步驟……………………………………………………..35
3-4-1實驗操作條件…………………………………………...35
3-4-2部份氧化熱裂解動力學方面之實驗步驟……………...36
3-4-3部份氧化熱裂解產物分析方面之實驗步驟…………...36
3-5產物分析方法與設備………………………………………..39
3-5-1氣相層析儀-熱傳導偵測器(GC-TCD)……………….39
3-5-2氣相層析儀-火焰離子偵測器(GC-FID)……………...40
3-5-3溫濕度計………………………………………………...42
3-6標準品………………………………………………………..43
3-6-1氣體標準品……………………………………………...43
3-6-2液體標準品……………………………………………...43
3-6-3檢量線之製作…………………………………………...43
第四章 結果與討論…………………………………………..46
4-1樣品成份分析………………………………………………..46
4-2鋁箔包在不同含氧率下之部份氧化熱裂解動力學………..46
4-2-1重量殘餘率曲線………………………………………...46
4-2-2瞬時速率曲線…………………………………………...51
4-2-3反應動力學參數………………………………………...56
4-2-4反應模式與實驗值之比較……………………………...70
4-3鋁箔包部份氧化熱裂解產物分析…………………………..79
4-3-1固體殘餘物分析………………………………………...79
4-3-2氣體產物分析…………………………………………...85
第五章 結論與建議…………………………………………105
5-1結論…………………………………………………………105
5-2建議…………………………………………………………106
參考文獻……………………………………………………..107
附錄A 樣品成份分析方法………………………………….111
A-1三成份分析方法….…….…………………………………111
A-2熱值分析方法……..…..…………………………………..112
A-3重金屬分析方法……..……………………………………113
附錄B 水氣含量計算方法………………………………….114
附錄C 樣品成份分析結果……………………..…………….115
C-1三成份分析及熱值……….………………………………..115
C-2元素分析………………….………………………………...115
C-3重金屬分析……………….………………………………..116
附錄D 實驗系統特性……………………………………….117
D-1加熱速率評估……….……….…………………………….117
D-2反應管溫度梯度….………………………………………..117
D-3天平穩定性試驗與熱重量天平空白試驗….……………..117
D-4系統再現性評估……….…………………………………..117
附錄E 純鋁熱裂解試驗…………………………………….122
附錄F 動力學補充………………………………………….124
F-1.反應動力學參數…………………………………………..124
F-2反應模式與實驗值之比較………………………………..125
附錄G GC-FID圖譜…………………………………………140

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