臺灣博碩士論文加值系統

摘要
放射性廢料焚化處理時，溫度愈高，放射性核種尤其是Cs核種，愈容易隨氣體逸出，所以把處理溫度降低，可降低放射性之污染擴散。本研究之主要目的，在降低廢離子交換樹脂熱處理溫度，避免放射性核種在焚化處理過程擴散。本研究係以添加硫酸銅、硫酸亞鐵或氧化銅於離子交換樹脂，並以熱重量分析儀，觀察樹脂在空氣中加熱氧化之行為，研究降低焚化溫度之可能性。
實驗結果顯示添加硫酸銅、硫酸亞鐵及氧化銅於陽離子交換樹脂中，可降低其氧化分解溫度，但硫酸亞鐵降溫幅度有限，硫酸銅及氧化銅之效果較佳。當添加20wt﹪之CuSO4.5H2O或8wt﹪之CuO於樹脂中，樹脂完全氧化溫度在590 ℃左右，比未添加時下降130℃；另將陽離子交換樹脂先以銅離子交換後，亦可達到相同的效果。添加硫酸銅或氧化銅的方法對陰離子交換樹脂及陰、陽混合離子交換樹脂，同樣具有降低溫度的效果。
本研究並依據離子交換樹脂TGA實驗結果，利用Arrhenius速率式模擬其在空氣中熱處理的動態行為，並以四階之Runge-Kutta數值演算法，求得Arrhenius速率式之參數，如反應級數、頻率因子與活化能等。

ABSTRACT
In the incineration of nuclear wastes, a higher incineration temperature would result in more nuclides, especially Cs-137 and Cs-134, to escape to the gas stream. This caused more dispersion of the radioactivity. This study aimed at lowering the incineration temperature of the radioactive spent ion exchange resins by incorporating resins with copper sulfate, ferro sulfate, copper oxide or silica in incineration, and their thermo-gravimetric phenomena were investigated.
Experimental results showed that the temperature for complete incineration of cationic exchange resins was significantly reduced by incorporating with the above mentioned inorganic compounds. It was shown that copper sulfate and copper oxide were more effective for this purpose. The cationic exchange resin incorporated with 20wt% CuSO4.5H2O or 8wt% CuO of the resin was completely incinerated at 590℃, which is 130 ℃ lower comparing to that in the absence of copper sulfate. Pre-loaded copper in the resins by cationic exchange also showed the same effect. The method is also effective for anionic exchange resins as well as mixed type ion exchange resins.
In this study,the dynamic behaviors of the heat treatment of the ion exchange resinswere also obsered. A dynamic behaviorwas developed in terms of the parameters of Arrhenius equation, and the parameters in Arrhenius equation for thereactions such as reaction order, pre-exponential factor and activation energy were determined by the 4th order Runge-Kutta algorithm.

摘要I
ABSTRACTII
誌謝III
目錄i
表目錄iv
圖目錄v
第一章 緒論1
1.1 前言1
1.2 研究動機2
1.3 文獻回顧2
1.3.1濕法2
1.3.2乾法3
1.4 研究目的4
1.5 研究方法及原理4
1.5.1觸媒作用原理5
1.5.2熱分解動態行為模式6
第二章 實驗方法10
2.1實驗藥品及儀器設備10
2.1.1實驗藥品10
2.1.2實驗儀器設備10
2.2 實驗步驟12
2.2.1樹脂熱處理實驗12
2.2.2樹脂加入添加物之熱處理實驗12
2.2.3樹脂熱處理動態反應模式實驗13
第三章 結果與討論14
3.1 離子交換樹脂在空氣中受熱之反應14
3.1.1陽離子交換樹脂14
3.1.2陰離子交換樹脂23
3.1.3混合離子交換樹脂32
3.2 觸媒對陽離子交換樹脂分解溫度之影響39
3.2.1不同觸媒對分解溫度之影響39
3.2.1-1添加Cu2+的影響39
3.2.1-2添加CuSO4.5H2O的影響40
3.2.1-3添加CuO的影響41
3.2.1-4添加Fe2+的影響51
3.2.1-5添加FeSO4.7H2O的影響51
3.2.2硫酸銅及氧化銅對陰離子交換樹脂分解溫度之影響57
3.2.2-1添加硫酸銅的影響57
3.2.2-2添加氧化銅的影響58
3.2.3氧化銅對混合樹脂分解溫度之影響60
3.3 亞銅及亞鐵觸化下離子交換樹脂之氧化反應62
3.3.1未添加觸媒之氧化反應62
3.3.2以氧化銅為觸媒之氧化反應63
3.3.3以銅離子及硫酸銅為觸媒之氧化反應63
3.4 樹脂熱分解之動態行為66
3.4.1陽離子交換樹脂分解反應66
3.4.2陽離子交換樹脂加入觸媒之分解反應73
3.4.3陰離子交換樹脂分解反應77
第四章 結論82
第五章 參考文獻84
自述88
附錄一89
附錄二92
附錄三95
附錄四98

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