以逆吹式氣相層析法分析氣體成份

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姓名

李明霞(Ming-xia Li) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以逆吹式氣相層析法分析氣體成份
(Construction of a back-flush GC system for gas analysis)

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摘要(中)

本研究為開發一套自動化定溫(isothermal)的氣相層析儀系統(Gas Chromatography, GC)，搭配逆吹(back flush)的設計，可達管柱自我調理的功能，而不需高溫烘烤，可大幅降低分析時間與電力耗損，並且兼具長期量測與穩定之特性。藉由分離管柱的組合搭配，可應用於三種不同的量測目標上：一、溫室效應氣體的監控；二、煙道中甲烷與非甲烷總碳氫的量測；三、生質氣體的組成成份分析。
實驗系統的主要架構為兩組二位十孔閥，藉由搭配適宜的管柱組合與偵測器，可達對不同的分析物種分離偵測的目的。管柱為自製的填充管柱，當填充不同的靜相材料，即可應用於不同分析目的之量測工作。
溫室氣體系統量測目標物種有二氧化碳(CO2)、甲烷(CH4)、氧化亞氮(N2O)，利用火焰離子偵測器(flame ionization detector, FID)偵測CH4與CO2、電子捕獲偵測器(electron capture detector, ECD)用於偵測N2O。由於CO2無法直接被FID所偵測，因此，CO2進入偵檢器之前，會先經過鎳觸媒(methanizer)轉化裝置使其還原成CH4再進入FID偵測，此系統可於10分鐘內完成一次大氣分析。甲烷與非甲烷總碳氫的部份，則使用單一十孔閥連接FID即可達成分析之目的，每筆實驗分析時間為5分鐘。生質氣體部份，使用GC-FID分析CH4與C2 ~ C4的主要成份；GC-TCD分析H2、O2、N2、CO、CO2等氣體，每筆實驗數據分析時間為5分鐘。
溫室氣體系統實際應用於採樣分析，於2012年02月14日在大台北都會區進行採樣，目的為觀察人為活動對溫室氣體排放之影響與干擾，並將分析結果與地圖繪整成濃度地形圖(contour mapping)，其結果顯示部份地區含有高度排放CH4與CO2，明顯為排放熱點(hotspot)；N2O的濃度則無明顯排放源，濃度分佈較為一致。而生質氣體系統實際應用於生質物炭化製程產氣組成成份分析，可對複雜成份的主要物種分離且偵測，並且因分析時間快速，可以即時反映製程狀況，藉由產物組成資訊以評估製程中之溫度、原料、效率等參數的影響，作為製程最佳化之依據，使生質能產品發揮最大經濟價值。

摘要(英)

In this study, an automated and isothermal gas chromatographic (GC) system was designed and constructed to analyze low-boiling non-methane hydrocarbons (NMHCs) and greenhouse gases (GHGs).
The GC system used two different column sets and detectors. The back-flush design was adopted for the system to permit column self-cleaning and conditioning under an isothermal condition. By doing so, continuous analysis of target gases without losing separation efficiency became possible. Each cycle of analysis took five to ten minutes with a sample aliquot of 2 mL.
To analyze greenhouse gases of CO2, CH4 and N2O, two types of detectors were used, one is the flame ionization detector (FID) for CH4 and CO2 detection, the other is the electron capture detector (ECD) for N2O detection. Because CO2 cannot be detected by FID directly, it must be reduced into CH4 by a Ni catalyst under a hydrogen flow. The system used two packed columns, i.e., Hayesep Q as the precolumn and Porapack Q as the analytical column kept at 70℃ inside the GC oven. The reproducibility (RSD) was better than 1% (N=7). The linearity was greater than 0.9999 for the range of 750 ~ 8200 ppbv for CH4, 150 ~ 1600 ppmv for CO2, and 160 ~ 1700 ppbv for N2O. The limits of detection (LOD) are 138.34 ppbv, 3.42 ppmv and 2.30 ppbv for CH4, CO2 and N2O, respectively. In later study, the system was applied to canister analysis. Contour plots were made to reveal “hotspot” of emission over the great Taipei metropolitan area. In the future, the system can be further expended to include more greenhouse gases, such as SF6.
In the application of determining methane and total non-methane hydrocarbons contents, the system used only one flame ionization detector (FID). Separation was made by a Unibeads 1S pre-column, and a Porapack Q analytical column kept at 70℃. Each cycle of analysis can be completed within 5 minutes.
In the biogas application, we use two different column sets and detectors to target H2, O2, N2, CO, CO2, CH4, and selected low-boiling NMHCs. For the category of permanent gases such as H2, O2, N2, CO, CO2, thermal conductivity detector (TCD) was employed for detection. Separation was made by a Hayesep D pre-column, and two analytical columns packed with Molecular sieve 5A and Hayesep Q, respectively, operated at 70℃. The CH4 and NMHC channel are detected by FID. For this purpose, two different lengths of Unibeads 2S columns were used as the pre-column and analytical column. NMHCs from C1 (CH4) to C4 (1-butene) can be analyzed within 5 minutes. Coupling of this GC system to a biogas reactor will be conducted to monitor on-line the composition of biogas in a continuous manner under various process conditions.

關鍵字(中)

★ 逆吹
★ 溫室氣體
★ 生質氣體
★ 非甲烷碳氫

關鍵字(英)

★ back flush
★ greenhouse gases
★ biogas
★ NMHCs

論文目次

摘要 I
英文摘要 III
謝誌 V
目錄 VII
圖目錄 X
表目錄 XVI
第一章前言 1
1-1 研究源起 1
1-2 溫室氣體相關量測方法 2
1-3 甲烷與非甲烷總碳氫化合物相關量測方法 7
1-4 生質氣體相關量測方法 13
1-5 方法統整 14
1-6 研究動機 17
第二章設備與材料 19
2-1 氣體與器材 19
2-1.1 實驗氣體 19
2-1.2 實驗器材 20
2-2系統設計 20
2-2.1逆吹系統 20
2-2.2進樣系統 – 大氣平衡 23
2-2.3 進樣系統 - 壓力控制 25
2-3工作標準品介紹 27
2-3.1 GHGs工作標準品 27
2-3.2 VOCs工作標準品 28
2-4 偵測器介紹 30
2-4.1 熱傳導偵測器 31
2-4.2 火焰離子偵測器 32
2-4.3 電子捕獲偵測器 32
2-5管柱的選擇 33
第三章溫室氣體之應用 46
3-1 溫室效應氣體介紹 46
3-2 GHGs系統 56
3-2.1 三孔二位電磁閥 - 甲烷分析 58
3-2.2 鎳觸媒甲烷化裝置 59
3-3 結果與討論 62
3-3.1 載流氣體之選擇 62
3-3.2 切除氧氣與不切氧氣系統之探討 63
3-3.3 GHGs層析條件 65
3-3.4 分析品質探討 68
3-4 大台北採樣實驗 71
第四章甲烷與非甲烷總碳氫之應用 82
4-1 甲烷與非甲烷總碳氫化合物系統 82
第五章生質氣體之應用 88
5-1 生質氣體介紹 90
5-1.1 生質能源種類 91
5-1.2 生質氣體的製程 92
5-1.3 生質氣體主要成份 95
5-2 生質氣體系統 96
5-2.1 升溫系統 99
5-2.2 分析條件的選定 105
5-2.3 恆溫系統 108
5-3 VOCs系統 119
第六章結論與未來展望 123
參考文獻 125

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指導教授

王家麟(Jia-Lin Wang)

審核日期

2012-7-19

推文