應用US EPA Method 30B探討燃煤電廠之汞排放特性

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黃茂泓(Mao-Hung Huang) 查詢紙本館藏

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論文名稱

應用US EPA Method 30B探討燃煤電廠之汞排放特性
(Application of US EPA Method 30B for Characterization of Mercury Emission from a Coal-Fired Power Plant)

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摘要(中)

本研究基於美國EPA公告之汞採樣參考方法US EPA Method 30B建立汞採樣方法，內容包含採樣流程、採樣儀器設備操作、採樣紀錄表建立、採樣及分析之QA/QC等，並於國內某一燃煤電廠進行測試並調查其汞排放及分布，此外亦針對US EPA Method 30B與汞CEMS之採樣數據進行比較並評估US EPA Method 30B作為汞CEMS的RATA參考方法之可行性，研究結果顯示US EPA Method 30B之採樣與分析方法及其QA/QC已完整建立，實廠之汞排放及流布調查部分，三季煙囪煙道氣之汞排放濃度為0.04 ~ 0.346 µg/Nm3之間，皆遠低於電力設施空氣污染物排放標準中新設汽力機組規範的2 µg/Nm3，符合國家排放標準之規定，此外US EPA Method 30B與汞CEMS之數據絕對值差不超過1.0 µg/scm，結果為可接受，驗證US EPA Method 30B作為汞CEMS的RATA之參考方法為可行的，本研究亦針對空氣污染防制設備之固體與液體樣品進行分析，固體樣品部分，三季之燃煤汞濃度範圍為0.031 ~ 0.057 mg/kg；底灰除了第Ⅲ季2號機為0.01 mg/kg外，其餘皆低於方法偵測極限（ND）；飛灰之汞濃度介於0.075 ~ 0.712 mg/kg，相對富集因子則是飛灰遠高於底灰。液體樣品部分，各季之脫硫海水汞濃度範圍為0.057 ~ 1.190 µg/L，而第Ⅲ季之進流海水之汞濃度為0.029 µg/L，各季煙囪之排放係數為0.37 ~ 3.37 mg Hg/t coal並符合美國MATS燃煤電廠汞排放之規範，此外由於煙道氣中氯化氫(HCl)對汞氧化影響亦是重要關鍵，因此本研究亦針對商用SCR觸媒之汞氧化效率與HCl之影響進行實驗並探討，結果顯示於370℃且低汞濃度環境下(5.5 ~ 6.0 µg/Nm3)商用SCR觸媒之汞吸附現象仍然明顯，而加入20 ppm與30 ppm HCl則明顯提升汞之氧化效率(80% ~ 90%)。

摘要(英)

In this study, a mercury sampling method based on US EPA Method 30B, including the sampling process, the operation of sampling equipment and the QA/QC of sampling and analysis is developed. A survey of mercury emissions and distribution in the flue gas of stacks a coal-fired power plant in Taiwan is conducted in three seasons. In addition, the results obtained by US EPA Method 30B were compared with that obtained with the Continuous Emissions Monitoring Systems (CEMS). The results show that the sampling and analysis method of US EPA Method 30B and its QA/QC have been fully established and the difference between US EPA Method 30B and mercury CEMS data does not exceed 1.0 µg/scm. Mercury concentrations emitted from a large-scale coal fired power plant ranged from 0.04 to 0.346 µg/Nm3, which are lower than the emission standards enacted by Taiwan EPA (2 µg/Nm3). To verify that US EPA Method 30B is feasible as a reference method for Relative Accuracy Test Audits (RATA) of mercury CEMS, this research also analyzes the solid and liquid samples discharged by air pollution control devices. For solid samples, the mercury concentrations of coals in three seasons range from 0.031 to 0.057 mg/kg; the bottom ashes are below the method detection limit (MDL) except for the boiler No. 2 in season Ⅲ (0.01 mg/kg). The mercury concentrations of fly ashes are between 0.075 ~ 0.712 mg/kg. The relative enrichment factor of fly ash is much higher than that of bottom ash. For liquid samples, the mercury concentrations of desulfurized seawater in each season range from 0.057 to 1.190 µg/L, and the mercury concentration of influent seawater in season Ⅲ is 0.029 µg/L. The emission factors of the stacks in each season range from 0.37 to 3.37 mg Hg/t coal, which meets the mercury emission standards for coal-fired power plants in the US MATS. Moreover, the influence of hydrogen chloride (HCl) in the flue gas on the oxidation of mercury is also an important key. Thus, this research also conducts experiments and discusses the mercury oxidation efficiency of commercial SCR catalysts and the influence of HCl. The results show that at low concentrations (5.5 to 6.0 µg/Nm3), mercury is strongly adsorbed on commercial SCR catalyst even at 370oC. The addition of HCl, especially at 20 ppm and 30 ppm, can effectively increase mercury oxidation efficiency (80% to 90%).

關鍵字(中)

★ 汞及其化合物
★ 燃煤電廠
★ US EPA Method 30B
★ 汞CEMS
★ 商用SCR 觸媒

關鍵字(英)

★ Mercury (Hg)
★ Coal-fired power plants
★ US EPA Method 30B
★ Hg-CEMS
★ SCR catalyst

論文目次

摘要 I
Abstract II
目錄 IV
表目錄 VII
圖目錄 IX
第一章前言 1
1.1 研究緣起 1
1.2 研究目的及範疇 2
第二章文獻回顧 3
2.1 汞之基本特性 3
2.2 汞之排放來源 6
2.3 煤炭燃燒過程中汞之轉化 10
2.4 汞對環境與人體之影響及危害 11
2.5 汞之檢測方法 12
2.6 燃煤程序之汞控制技術 15
2.7 國內外燃煤電廠之汞相關法規 19
2.8 觸媒之基本介紹 22
2.8.1 觸媒催化之原理與機制 22
2.8.2 觸媒之成分 24
2.8.3 觸媒之形式 24
第三章研究方法 26
3.1 研究流程及架構 26
3.2 實廠採樣調查 28
3.2.1 採樣時間 28
3.2.2 空氣污染防制設備與採樣位置 28
3.2.3 樣品採樣程序 29
3.2.3.1 煙道氣中汞及其化合物之採樣程序 29
3.2.3.2 固體樣品之採樣程序 36
3.2.3.3 液體樣品之採樣程序 36
3.2.4 樣品分析 36
3.2.4.1 煙道氣樣品分析 37
3.2.4.2 固體樣品之分析 38
3.2.4.3 液體樣品之分析 38
3.2.5 汞CEMS數據之收集 39
3.3 商用SCR觸媒測試實驗 40
3.3.1 實驗設備 40
3.3.2 實驗藥品 42
3.3.3 實驗氣體 43
3.3.4 實驗設計方法 43
3.3.4.1 觸媒材料 43
3.3.4.2 觸媒材料之物化特性分析 44
3.3.4.3 實驗系統設置 46
3.4 公式計算 48
第四章結果與討論 51
4.1 US EPA Method 30B之建立與驗證 51
4.1.1 採樣前之場址現勘 52
4.1.2 燃煤電廠之預採樣 54
4.1.3 現場採樣紀錄表與採樣分析QA/QC準則表 55
4.2 燃煤電廠四季之調查結果 59
4.2.1 燃煤電廠之背景資料 59
4.2.2 煙道氣採樣結果 61
4.2.3 固體樣品採樣結果 64
4.2.4 液體樣品採樣結果 70
4.2.5 燃煤電廠中汞輸出/輸入量 72
4.2.6 燃煤電廠之汞質量平衡 74
4.2.7 燃煤電廠之汞排放係數 78
4.3 商用SCR觸媒轉化元素汞之效率探討 79
4.3.1 商用SCR觸媒之特性分析 79
4.3.1.1 BET (Brunauer–Emmett–Teller)比表面積分析結果 79
4.3.2 元素汞氧化效率與氯化氫影響之探討 81
第五章結論與建議 84
5.1 結論 84
5.2 建議 85
參考文獻 86
附錄一汞採樣紀錄表 94
附錄二預採樣之QA/QC 95
附錄三第Ⅰ季之QA/QC 97
附錄四第Ⅱ季之QA/QC 99
附錄五第Ⅲ季之QA/QC 101
附錄六各季當日之採樣操作參數 103

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行政院環保署水質保護處，放流水標準。
行政院環保署，電力設施空氣污染物排放標準。

指導教授

張木彬(Moo-Been Chang)

審核日期

2022-1-25

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