煉鋼爐石為煉鋼製程伴隨產生的副產品，因具有豐富的游離石灰適合作 為碳酸化材料，利用游離石灰結合二氧化碳，可使其轉變成穩定的碳酸鹽類， 解決體積膨脹、高鹼度等不安定性的問題。本研究應用超臨界二氧化碳反應 系統進行碳酸化試驗，以田口式實驗設計法探討溫度、壓力、時間、液固比 等參數對碳酸化效率之影響，後續以斷層掃描觀察碳酸化產物密度分布，並 測量比重及吸水率，評估碳酸化反應後煉鋼爐石之工程穩定性。本研究歸納 之超臨界碳酸化最適條件為: 煉鋼爐石粒料（4.76~9.50mm）於 50°C、88.5 atm、液固比 0.5 L/kg、反應時間 30 分鐘，游離石灰反應率達 59%；煉鋼爐 石細粉料（0.42~2.00 mm）於 80°C、74.5 atm、液固比 0.5 L/kg、反應時間 30 分鐘，游離石灰反應率可達 76%。結果顯示，超臨界碳酸化反應為濕式反 應途徑，液固比為主要影響因子之一，過量的水分會影響質傳，導致碳酸化 效率下降；碳酸化反應率會隨著時間延長而增加，然而碳酸化產物會堆積在 煉鋼爐石表面，導致反應率的提升有逐漸趨緩的情況。觀察反應後煉鋼爐石 之密度分布結果，除了表層有碳酸化產物堆積外，煉鋼爐石內部也有碳酸化 反應的發生，證實超臨界流體因具有較高的擴散率，易於滲入煉鋼爐石之微 孔中進行反應，反應後煉鋼爐石粒料之工程特性顯示，吸水率略下降且比重 微增加，顯示超臨界碳酸化反應有助於提升煉鋼爐石之工程穩定性。

Steelmaking slag is a by-product from the steel industry, which is characterized by abundant free CaO and thus has high potential for carbonation. The combination of free CaO and CO2 to form stable carbonates is beneficial for solving issues related to volume expansion and high alkalinity. The aim of this study is to study the carbonation of steelmaking slags using supercritical system. The influence of parameters of supercritical CO2 (including temperature, pressure, time, and liquid-solid ratio) on carbonation efficiency was examined through Taguchi method. The density distribution, specific weight, and water absorbency of carbonated steelmaking slags were then analyzed to assess the engineering stability. Results showed that approximately 59% reaction rate of free CaO was obtained for steelmaking slag (4.76~9.50 mm) at 50°C, 88.5 atm, 0.5 L/kg of water-to-solid ratio, and 30 mins, and that for steelmaking slag powder (0.42~2.00 mm) was 76% at 80°C, 74.5 atm, 0.5 L/kg of water-to-solid ratio, and 30 mins. It was shown that the liquid-solid ratio is one of the main factors in the wet carbonation reaction. Excessive water may affect the mass transfer, leading to a decrease in carbonation efficiency. The carbonation reaction rate was found to be increased with increasing reaction time. However, carbonated products were then accumulate on the surface of the steelmaking slags, inhibiting the reaction and slowing down the reaction rate. Furthermore, results of the density distribution revealed that the accumulation of carbonated products were observed not only on the surface but also inside the steelmaking slags, which confirmed the supercritical fluid is easy to penetrate into the micropores of the steelmaking slags for carbonation due to its high diffusivity. In addition, the lower water absorbency and higher specific weight of steelmaking slags after carbonation, III indicating that the engineering stability of the steelmaking slags can be improved by using supercritical carbonation.

摘要 I
Abstract II
誌謝 IV
目錄 V
圖目錄 VIII
表目錄 X
第一章 前言 1
1.1 研究背景 1
1.2 研究目的 1
第二章 文獻回顧 3
2.1 煉鋼爐石基本特性 3
2.1.1 來源 3
2.1.2 物化特性 5
2.1.3 安定化處理 9
2.1.4 再利用 12
2.2 碳酸化技術 21
2.2.1 二氧化碳封存 21
2.2.2 碳酸化反應機制 23
2.2.3 碳酸化反應影響參數 26
2.3 超臨界流體 31
2.3.1 超臨界流體簡介 31
2.3.2 超臨界流體之應用 34
2.3.3 超臨界碳酸化之應用 36
第三章 研究材料、設備與方法 39
3.1 研究架構 39
3.2 研究材料與設備 41
3.2.1 實驗試藥 41
3.2.2 實驗設備 41
3.2.3 超臨界反應系統 43
3.3 研究與分析方法 45
3.3.1 田口式實驗設計 45
3.3.2 田口式實驗數據分析 48
3.3.3 分析方法 50
第四章 結果與討論 56
4.1 煉鋼爐石之特性分析 56
4.1.1 基本特性 56
4.1.2 元素組成 59
4.1.3 官能基及晶相組成 60
4.1.4 熱重分析 62
4.2 田口式實驗設計於超臨界碳酸化反應參數之探討 64
4.2.1 S-SS碳酸化結果分析 64
4.2.2 P-SS碳酸化結果分析 68
4.2.3 碳酸化產物之熱重分析 71
4.3 超臨界碳酸化最適條件探討 76
4.3.1 時間對碳酸化效率之影響 76
4.3.2 液固比對碳酸化效率之影響 83
4.3.3 碳酸化產物官能基及晶相組成 91
4.3.4 碳酸化產物顯微結構 98
4.3.5 碳酸化產物之密度分布 101
4.3.6 小結 07
4.4 碳酸化產物工程特性及效益評估 109
4.4.1 工程特性分析 109
4.4.2 碳酸化效益評估 112
第五章 結論與建議 114
5.1 結論 114
5.2 建議 115
第六章 參考文獻 116

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