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系統識別號 U0026-0808201615220700
論文名稱(中文) 煤鐵礦複合球團在碳熱還原反應中之熔融性質研究
論文名稱(英文) Study on Melting Properties of Iron Ore/Coal Composite Pellets during Carbothermic Reduction
校院名稱 成功大學
系所名稱(中) 材料科學及工程學系
系所名稱(英) Department of Materials Science and Engineering
學年度 104
學期 2
出版年 105
研究生(中文) 賴柏廷
研究生(英文) Po-Ting Lai
學號 N56031051
學位類別 碩士
語文別 中文
論文頁數 122頁
口試委員 指導教授-陳引幹
口試委員-劉世賢
口試委員-連雙喜
口試委員-黃文星
中文關鍵字 高料層煉鐵製程  碳熱還原反應  直接還原鐵  熔融性質  添加劑  渣相配比 
英文關鍵字 carbothermic reduction  iron ore/coal composite pellets  melting properties  additive 
學科別分類
中文摘要 溫室效應為最近極受矚目的環保議題,各界皆致力於減少溫室氣體的排放。而鋼鐵工業的溫室氣體排放量佔總量的3%,故各家鋼鐵工業皆致力於發展節能減碳技術。

其中高料層碳熱還原煉鐵製程將煤礦與鐵礦混合造粒後堆料7~8層,並使用熱空氣由上方加熱球團進行碳熱還原(Carbothermic Reduction)反應,在還原過程中藉由球團的產氣保護球團免於再氧化,最後可得到高金屬化率之直接還原鐵(Direct Reduced Iron, DRI)。在高料層碳熱還原煉鐵製程中,若球團產生熔融崩塌,則整個料層亦會受到影響並坍塌,影響製程的產率以及金屬化率。

為探討煤鐵礦複合球團在碳熱還原過程中的熔融性質,本研究使用不同原料配比的球團進行碳熱還原實驗,利用還原過程影像紀錄、SEM微觀結構分析、XRD相分析、熱分析、化學分析等討論球團熔融崩塌的成因。並且挑選在碳熱還原實驗中產生熔融的球團,藉由添加劑調整球團中的渣相配比,觀察渣相配比對於球團熔融性質的影響。

實驗結果顯示,球團因低熔點的渣相熔化會在球團表面產生液泡,並且球團中心會因金屬鐵滲碳作用而使金屬鐵液化而流失,在特定配比下的球團會呈現中空的金屬鐵殼。而調整渣相配比亦使球團呈現不同形貌,添加氧化鋁可以使球團生成熔點1310 oC之FeAl2O4,減少低熔點1205 oC的Fe2SiO4的生成量,故可使球團表面觀察到液泡的時間點延後,並且還原後球團可維持完整形貌;添加氧化鈣的球團會使球團產生FeO-CaO的造渣反應,使球團的熔融現象加劇,並且球團會產生軟熔崩塌的現象;添加氧化鎂的球團可提高二元渣相熔點,但因金屬鐵滲碳造成的液相流失現象,故還原後球團僅餘中空的金屬鐵殼。而圓柱狀樣品在碳熱還原實驗下除添加氧化鈣及二氧化矽會使圓柱軟熔崩塌及形成不規則的形貌外,皆無表現出軟熔性質。
英文摘要 In order to reduce the CO2 emissions of the blast furnace process, inromaking industry are working on a low CO2 emission process. Tall-bed carbothermic reduction uses iron ore/coal composite pellets packed in several layers. It uses the gas generated by the carbothermic reduction to protect the pellets from re-oxidation, and finally we can get high-metallization-degree direct reduced iron(DRI). In tall-bed carbothermic reduction process, if the pellets melt or collapse, the layer will also collapse and re-oxidize.
In this study, we focus on the melting properties of the pellets during reduction. We use optical imaging, SEM and XRD, to analyze the mechanism for pellet melting. Next we use an additive to adjust the ratio of the slag system (FeO, Al2O3, CaO, MgO, and SiO2), and then we observe the property changes caused by the additive. The result shows that both low-melting-point slag melting and iron carburization are part of the reason for pellet melting. When these two mechanisms work together, the pellets will melt, and maybe even collapse. By adding the Al2O3, it will make the pellets form FeAl2O4, which has a melting point of 1310 oC, and the amount of Fe2SiO4, which has a lower melting point of 1205 oC, will become lower, so the temperature when the pellets form liquid bubbles will be delayed. Adding CaO will make the pellets severely melt and collapse, which is caused by FeO-CaO binary slag, as it has a melting point of only 1125 oC. MgO will form a 1400 oC melting point in FeO-MgO binary slag, but iron carburization still works, and the center of the pellet will be lost, with only the iron shell remaining. Adding SiO2 will promote the formation of Fe2SiO4, so the pellets will melt more severely.
論文目次 摘要 I
圖目錄 XI
表目錄 XIX
第一章 緒論 1
1.1 研究背景與動機 1
1.2 研究目的與內容 3
第二章 文獻回顧 5
2.1 碳熱還原反應機構與動力學因素 5
2.2 RHF及PSH煉鐵製程介紹 7
2.3渣相組成對於鐵碳複合球團的熔融性質影響 9
2.4 渣相組成對於球團還原性質影響 11
第三章 實驗方法及步驟 20
3.1 原料 20
3.1.1 鐵礦 20
3.1.2 煤礦 21
3.1.3 黏結劑 21
3.1.4 添加劑 22
3.2 實驗設備 25
3.2.1 配料成形設備 25
3.2.2 高溫爐、氣氛供給、冷卻供應及移動式進料設備 25
3.2.3 樣品保存設備 26
3.2.4 樣品後處理設備 26
3.3 實驗分析方法 27
3.3.1 差示掃描量熱儀(Differential Scanning Calorimetry, DSC) 27
3.3.2 高溫二維X光繞射分析儀(2D-XRD) 27
3.3.3 掃描式電子顯微鏡(Scanning Electronic Microscopy, SEM) 28
3.3.4 電子散佈光譜儀(Electron Dispersive Spectroscopy, EDS) 28
3.3.5 全鐵定量法 29
3.3.6 X光螢光分析法(X-ray Fluorescence Spectrometer, XRF) 29
3.3.7 碳硫分析 30
3.4 實驗步驟 31
3.4.1 配料與球團成形 31
3.4.2 高溫碳熱還原實驗 31
3.4.3 鑲埋處理 32
3.4.4 熱分析 33
3.4.5 坩鍋酸洗 33
3.4.6 圓柱熔融反應測試 34
第四章 實驗結果與討論 38
4.1 煤鐵礦複合球團於還原過程還原及熔融崩塌現象 38
4.1.1 球團還原現象觀察 38
4.1.2 影響球團熔融崩塌之因素討論 39
4.1.3 液化渣相流動方向探討 43
4.2 煤鐵礦複合球團搭配不同渣相配比在碳熱還原實驗對熔融現象之影響 58
4.2.1 球團搭配不同渣相配比還原過程熔融現象及外觀觀察 58
4.2.2 球團搭配不同渣相配比液化成份之XRD分析 62
4.2.3 球團搭配不同渣相配比液化過程之微觀結構分析 64
4.2.4 球團搭配不同渣相配比還原之熱特性分析 67
4.3 圓柱狀樣品之還原過程外觀形貌變化 108
第五章 結論 116
引用文獻 118
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