臺灣博碩士論文加值系統

燒結場為鋼鐵工業重金屬排放汙染源之一，但燒結場重金屬排放資料大部分為實場重金屬排放資料，然有關燒結製程中其原料改變對重金屬排放特徵與分佈之影響仍有待探討。本研究利用小燒結鍋依實際燒結場之原料比例模擬燒結製程。本研究利用燒結原料（包含粉鐵礦、助熔劑及回收料）的改變，以探討原料、產物(燒結礦)及煙道廢氣內的重金屬成份含量。煙道重金屬採樣參考USEPA METHOD 29之等速煙道採樣方法，並同時收集燒結原料及燒結後之產物樣本。各樣本值利用感應耦合電漿原子發射光譜儀 (ICP-AES)以分析其內含之 As、Hg、Cd、Cr、Cu、Mn、Ni、Pb、Zn等九種金屬。最後藉重金屬排放量及分佈比例以找出粉鐵礦、助熔劑及回收料對重金屬排放之影響。結果發現，六種鐵礦(包括YAN、MAC、MTF、MBR、CVRD、CARA)重金屬含量以Mn所佔含量最高。比較六種鐵礦燒結過程之重金屬排放，亦以Mn元素為之。兩種測試之助熔劑試驗重金屬含量為：Reef (176mg/kg)＞Marble (120mg/kg)。探討兩種助熔劑的重金屬排放時可發現Reef因其CaO含量，致使Reef在燒結時有較低重金屬排放。添加回收料的試驗以添加5% EP dust取代5% YAN鐵礦，結果發現EP dust因其本身的高含量重金屬，導致重金屬排放量的增加。由本次試驗質量平衡結果發現重金屬含量除汞主要存在於煙道廢氣中之外，餘金屬均主要存在於燒結礦中(>70%)；煙道尾氣中，汞主要以煙道氣相存在，但砷（As）、鎘（Cd）、鉻（Cr）、銅（Cu）、錳（Mn）、鎳（Ni）、鉛（Pb）及鋅（Zn）等主要仍以粒狀物型態存在。而Cd、Pb、Zn、As等低熔點元素受到SiO2玻璃化的影響，主要都留在燒結礦中。探討各種燒結測試之原物料組成中不同重金屬之總量與其排放係數之預測模式如下，Cd：y = 0.234x - 3.673 (n=8, R² = 0.697)；Cr：y = 0.129x - 8.127 (n=8, R² = 0.582)；Cu：y = 0.210x - 3.082 (n=8, R² = 0.738)；Mn：y = 0.003 x + 0.460 (n=8, R² = 0.844)；Ni：y = 0.069x - 1.558 (n=8, R² = 0.702)；Pb：y = 1.096x - 49.622 (n=8, R² = 0.979)；Zn：y = 0.052x - 1.493 (n=8, R² = 0.875)；As：y = 0.029 x - 0.152 (n=8, R² = 0.612)；Hg：y = 0.203x + 0.113 (n=8, R² = 0.049)，且其回歸結果間之相關性除了Hg (R2=0.049)以外，其餘重金屬均具良好相關性(R2=0.582-0.979)，意即除了Hg以外，原物料內重金屬含量為主要影響鐵礦燒結後的重金屬排放的主要因素。預測模式推估某鋼鐵廠燒結製程(含四座燒結場)年排放率發現，Pb最高464 ton/year，所有重金屬汙染物之年總排放率可達到851 ton/year。模式推估之燒結製程(含四座燒結場)，經過污染防治設備(EP)校正後，燒結場重金屬排放率仍相當於6.84座燃煤火力發電廠；12.6座燃油火力發電廠。Pb的排放率更是燃煤發電廠的268倍；燃油發電廠的414倍。

Sinter plant is one of the heavy metal pollution sources from the iron and steel industry. Currently the heavy metals emission data of the sinter plant are almost obtained from the real plant emissions, but the relationship between changing raw materials and its effects on heavy metals emission characteristic and their fates are needed to further investigate. In this study, mini sinter pot was applied to simulate the iron ore sintering process. The raw materials (iron ores, fluxes and west returns) blending ratios were specified based on a real plant and was used as a basic to evaluate the heavy metal emissions. An iso-kinetic sampling method of EPA Method 29 for heavy metal from stack flue gases has been used to collect samples. In addition, bulk samples of raw materials and sinters were collected during flue gases samplings. All collected samples were analyzed for their As, Hg, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn contents by ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer). Finally the metal emissions and distribution proportions were determined and were used to find the effects on heavy metal emission caused by iron ores, fluxes and west returns. Results showed that highest heavy metal content in six iron ores(including YAN, MAC, MTF, MBR, CVRD and CARA) is Mn; all the second highest is Pb. Comparing heavy metal emissions of six different iron ores, the highest one is Pb among all heavy metals might because its lower melting point . Heavy metal contents of two tested fluxes shows Reef (176mg/kg)＞Marble (120mg/kg). The results of heavy metal emissions of the two tested fluxes show Reef had a lower heavy metal emission than Marble. This might because the CaO content containing in the Reef. When waste returns of EP dust was used to replace 5% YAN iron ore, we found that a higher heavy metal emission. That might because high heavy metal content originally containing in the EP dust. Because on our mass balance results, we found that with an exception of Hg exists in the flue gases, all other metals mostly remain in the sinters (>70%). In the flue gases, with the exception of Hg exist in the gas phase, all other metals are mainly preserved in the particle phase. Among them Cd, Pb, Zn and As are the heavy metals with low melting point, their major existence in the sinters may be influenced by SiO2. The predicted model of heavy metals contents containing in raw materials and their corresponding emission factors are as follows, Cd: y = 0.234x - 3.673 (n=8, R² = 0.697); Cr: y = 0.129x - 8.127 (n=8, R² = 0.582); Cu: y = 0.210x - 3.082 (n=8, R² = 0.738); Mn: y = 0.003 x + 0.460 (n=8, R² = 0.844); Ni: y = 0.069x - 1.558 (n=8, R² = 0.702); Pb: y = 1.096x - 49.622 (n=8, R² = 0.979); Zn: y = 0.052x - 1.493 (n=8, R² = 0.875); As: y = 0.029 x - 0.152 (n=8, R² = 0.612); Hg: y = 0.203x + 0.113 (n=8, R² = 0.049)。High correlation (R2=0.582-0.979) were found between eight heavy metals contents containing in raw materials and their corresponding emission factors, with an exception found in Hg (R2=0.049), Above data means heavy metal contents containing in raw materials plays the most important role on heavy metal emissions with an exception of Hg. Precdicting the heavy metals annual emission rate from sinering process(including four sinter plants) found the highest one is Pb 464 ton/year among all heavy metals and total heavy metal annual emission rate is 851 ton/year。Total heavy metal emission from sinering process (including four sinter plants) is 6.84 times higher than coal fired power plant and 12.6 times higher than oil fired power plant. Pb emission from sinering process (including four sinter plants) is 268 times higher than coal fired power plant and 414 times higher than oil fired power plant.

第一章 前言 1
1-1 研究背景 1
1-2 研究目的 2
表1-1 一貫鋼鐵作業廠各製程金屬排放係數 3
表1 2 不同作業下原物料和金屬排放的關係 4
第二章 文獻回顧 5
2-1 金屬元素的性質 5
2-1-1 金屬元素的物化特性 5
2-1-2 金屬元素的毒性 7
2-1-3 金屬元素的排放源 9
2-1-4經由燃燒後重金屬的排放 10
2-2 鐵礦之燒結製程 11
2-2-1 燒結機簡介 11
2-2-2 燒結機制及原理 12
2-2-3 燒結原料在燒結機制中扮演角色 13
第三章 研究方法及設備 16
3-1 研究架構 16
3-2 小燒結鍋設備 17
3-2-1 小燒結鍋之各設備介紹 18
3-3 採樣方法 19
3-3-1測試之燒結條件 19
3-3-2重金屬採樣方法及設備 20
3-4 樣品回收 26
3-5 樣本分析 27
3-5-1 樣本前處理 27
3-6 礦石之採樣分析 29
3-7 感應耦合原子發射光譜(ICP-AES)分析重金屬 30
第四章 品質控制與品質保證 31
4-1 製作檢量線 31
4-1-1 製備檢量線 31
4-1-2 檢量線確認 32
4-2 樣品分析 35
第五章 結果與討論 41
5-1 測試物質之重金屬含量分析 41
5-1-1 六種鐵礦比較 41
5-1-2 兩種助熔劑比較 46
5-1-3其他燒結原料之重金屬成分分析 49
5-1-4 EP dust重金屬成分分析 52
5-2 不同鐵礦燒結時尾氣中重金屬排放特徵 54
5-2-1燒結全程之尾氣中重金屬排放量比較 54
5-2-2燒結全程之尾氣中重金屬排放量係數比較 54
5-2-3重金屬排放特徵質量平衡氣固相及燒結礦分布 57
5-3 不同助熔劑燒結時尾氣中重金屬排放特徵 64
5-3-1燒結時燒結全程之尾氣中重金屬排放量比較 64
5-3-2燒結時燒結全程之尾氣中重金屬排放係數比較 65
5-3-3重金屬排放特徵質量平衡氣固相及燒結礦分布 68
5-4 添加5% EP DUST燒結時尾氣中重金屬排放特徵 71
5-4-1燒結時燒結全程之尾氣中重金屬排放量比較 71
5-4-2 燒結時燒結全程尾氣中重金屬排放係數比較 71
5-4-3重金屬排放特徵質量平衡氣固相及燒結礦分布 74
5-5 燒結製程之重金屬排放預測模式與應用 77
5-5-1原物料重金屬量對重金屬排放之預測模式 77
5-5-2 推估燒結製程(含四座燒結場)年排放量與日排放量 80
5-5-3 模式推估值燒結場每日排放率與其他行業比較 83
第六章、結論與建議 87
6-1 結論 87
6-2 建議 89
參考文獻 90
附錄 94

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