臺灣博碩士論文加值系統

爐石為煉鋼廠一貫作業產出之副產物，其中，高爐鐵水脫硫後，冷卻之固體物稱為脫硫渣(desulfurization slag, DS)，因具高pH值特性，故至今仍無法有效資源再利用。本研究之目的針對經水洗及篩選程序處理後產生「脫硫渣細料」，進行資源化之可行性評估。基本特性分析結果顯示，脫硫渣細料之化學組成為CaO、SiO2、Fe2O3及Al2O3，主要組成晶相為SiO2、Ca(OH)2及CaCO3。表面微觀結構分析及比表面積分析結果顯示，脫硫渣細料表面孔隙含量較少，屬非多孔性材料。由pH值及鹼度釋出試驗顯示，脫硫渣細料可提升水中之鹼度，因此除將其做為土壤改良劑以改善酸性土壤外，亦可用於改善酸性水體。透過重金屬溶出試驗結果顯示，脫硫渣細料所含重金屬穩定性高，因此於環境中不易釋出。再利用試驗部分則評估其做為低價吸附材及藻類培養營養源之潛力。由吸附試驗結果顯示，當氨氮初始濃度為10 mg/L及30 mg/L時，飽和吸附量分別為0.036 mg/g及0.069 mg/g，且吸附行為較符合Langmuir等溫吸附曲線之描述；當磷酸鹽初始濃度為10 mg/L及30 mg/L時，飽和吸附量分別為26.4 mg/g及76.6 mg/g。另經熱力學(thermodynamics)參數計算結果顯示，脫硫渣細料對於氨氮之吸附反應為吸熱非自發程序；磷酸鹽部分為放熱自發程序，而由吸附熱(ΔH)判斷，脫硫渣細料吸附氨氮屬於物理吸附，而吸附磷酸鹽則為化學吸附。藻類培養試驗結果顯示，添加25 mg/L脫硫渣細料可使Chlorella sp.有較快之生長速率，故添加適量脫硫渣細料有助於Chlorella sp.生長。此外，本研究以脫硫渣細料為護岸材料之水產養殖池做為現地研究對象，結果顯示護岸前後對於地下水及養殖池水並無顯著影響，池水有機物特徵圖譜分析顯示，在Ex/Em： 330/400 nm與250/390 nm均有明顯波峰反應，分別為似腐植質(humus-like)及水溶性之類微生物代謝物質(soluble microbial product, SMP)。由藻類觀測得知，養殖池水中優勢藻類包括柵藻(Scenedesmus sp.)及小球藻(Chlorella sp.)，其存在表示養殖池之水質狀況良好。周遭環境介質重金屬分析結果顯示，其重金屬含量均可符合相關管制標準。綜合上述，本研究測試之材料並不影響水中之生態系統，對環境無明顯之影響，故脫硫渣細料為一種環境友善之資源化物質，具有極高之再利用潛勢。

Furnace slag is the by-product from steel making process. Desulfurization slag (DS) was produced from the desulphurization process of molten irons in high temperature furnaces processes. DS is heterogeneous oxide materials which are compounded by some main oxides such as SiO2, FeO, CaO, SiO2, MnO, Al2O3, and MgO due to their mass percentage. Because DS has high pH characteristics (12.5), this limits its recycle and reuse. The objective of this study was to evaluate the potential of applying DS as the construction materials or amendments in the aquacultural industry to improve the aqualcultural water quality in the fish farm. The basic characteristic analyses show that the major chemical compositions of powder DS were CaO, SiO2, Fe2O3 and Al2O3. The major crystalline phase composed of SiO2, Ca(OH)2 and CaCO3. Results of DS release test show that when DS could increase pH and alkalinity value in water. Results of micro-structure analysis of powder DS surface showed there were many non-porous materials and heavy metals on DS. Results from the nutrient removal tests show that the ammonia nitrogen adsorption capacity were 0.036 mg/L and 0.069 mg/L when the initial concentration were 10 mg/L and 30 mg/L, respectively. Results form the adsorption model validation test indicate that the adsorption phenomena could fit in Langmuir model. The adsorption capacities of phosphate were 26.4 mg/L and 76.6 mg/L when the initial phosphate concentrations were 10 mg/L and 30 mg/L, respectively. The calculated values of thermodynamic parameters show that the adsorption reaction for ammonia nitrogen was endothermic non-spontaneous process, and the adsorption reaction for phosphate was exothermic spontaneous process. However, the enthalpy change (ΔH) showed that adsorption reaction of DS for ammonia nitrogen was physical adsorption, and the adsorption reaction for phosphate was chemical sorption. In the algae culture experiment, results show that when 25 mg/L of DS was supplied, the growth rate of Chlorella sp. could be enhanced. Thus, the powder DS could enhance the growth of Chlorella sp. A field study using a fish farm as the study site was conducted to evaluate the impact of DS on fish farm water quality when DS was applied as the filling and construction materials of the fish farm. Results show that addition of DS had no significant effect on groundwater and pond water quality. Results from the organic matter analysis of the pond water using EEFM show that humus-like and soluble microbial product (SMP) materials were detected. The dominant algae in the pond water included Scenedesmus sp. and Chlorella sp. indicating the pond water quality was in good conditions. Addition of DS would increase of water alkalinity preventing the acidification of pond water due to the fish feed and fish excreta. Results of heavy metal analysis of soil, groundwater, and pond water complied with the relevant environmental standards. Results of this study will aid in understanding the characteristics of DS and the results will be useful in designing a DS reuse system to achieve the zero waste and resource reuse goal.

誌謝 i
摘要 ii
Abstract iii
目錄 v
表目錄 viii
圖目錄 x
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 脫硫渣來源及基本特性 3
2.1.1 製程概述 3
2.1.2 物理及化學性質 4
2.2 重金屬溶出試驗與基質結合型態探討 9
2.3 吸附基本理論 18
2.3.1 物理及化學吸附 19
2.3.2 吸附模式評估 20
2.3.3 吸附熱力學 26
2.3.4 影響吸附速率之各項因子 27
2.4 螢光激發發射光譜圖 28
2.5 脫硫渣再利用 30
第三章 材料與方法 37
3.1 研究流程 37
3.2 實驗材料與設備 39
3.2.1 實驗藥品 39
3.2.2 實驗器材 39
3.3 研究方法 41
3.3.1 脫硫渣細料基本特性分析 41
3.3.2 重金屬溶出試驗 43
3.3.3 水中營養鹽吸附試驗 47
3.3.4 藻類培養試驗 49
3.3.5 現地研究概述 52
3.4 分析方法 55
第四章 結果與討論 59
4.1 脫硫渣細料基本特性分析 59
4.1.1 成分分析 59
4.1.2 晶相組成分析 61
4.1.3 表面微觀結構分析 62
4.1.4 比表面積分析 65
4.1.5 pH及鹼度釋出試驗 67
4.2 重金屬溶出試驗 68
4.2.1 毒性特性溶出試驗 68
4.2.2 無機成分可溶出量試驗 69
4.2.3 多重化學藥劑連續萃取法 70
4.3 營養鹽吸附試驗 73
4.3.1 動力吸附模式 75
4.3.2 等溫吸附模式 79
4.3.3 吸附熱力學之探討 85
4.4 藻類培養 86
4.4.1 pH值變化 86
4.4.2 藻濃度 87
4.4.3 微量元素 88
4.4.4 有機物參數分析 90
4.5 現地研究 98
4.5.1 水質分析結果 98
4.5.2 水中有機物特性分析結果 99
4.5.3 水中藻類觀測結果 100
4.5.4 周遭土壤重金屬含量分析結果 101
第五章 結論與建議 103
5.1 結論 103
5.2 建議 104
參考文獻 105

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