臺灣博碩士論文加值系統

摘 要
本論文主要探討不同種類與孔徑的分子篩吸附劑對於空氣中揮發性有機物的選擇性與吸附能力；吸附劑共包含了四種不同的商業化碳分子篩吸附劑與兩種自行合成的矽分子篩吸附劑，製備單一吸附劑吸附管或組合式吸附管，搭配本實驗室自行開發之前濃縮系統，針對揮發性有機物進行量測。利用一已知濃度且包含56個物種分別為C2-C12之混合氣體做為樣品來源，研究各吸附管之吸附能力與選擇性。由於無法找到一吸附劑對於C3-C12物種皆具有良好的捕捉能力，故組合數種吸附劑形成一多重床吸附管，多重床吸附管則對於C3-C12物種皆具有一致的捕捉效率。
此外本研究也測試了兩種自行合成之矽分子篩吸附劑與商業化吸附劑作為比較，所合成之矽分子篩吸附劑分別為MCM-41與MCM-48，其孔洞大小各自為2.5 nm與2.8 nm，而商業化吸附劑孔洞則小於1.5 nm。其結果正如同所預測的，大孔洞的分子篩對分子小於C8-C10範圍的VOCs捕捉能力較差。相對地大孔洞的矽分子篩吸附劑則對大分子的物種有較佳的捕捉能力，大致上對於C8以上的物種，具有優良的捕捉能力。由以上結果可推論分子篩的孔洞大小決定了其吸附能力與選擇性。
本論文的第二部份則是針對台灣中部地區VOCs垂直濃度分佈之結果作討論；過去中部地區常發生季節性高臭氧問題，而高臭氧的來源可能是來自於上風處都會區所排放的VOCs與NOx經過傳輸後在下風處產生高臭氧的問題。量測過程中每一個垂直剖面是由7個繫掛於滯空氣球的Tedlar採樣袋所組成，採樣高度最高可達到距離地面1公里的高空。我們利用長生命期物種與短生命期物種之比值，作為氣團老化的證據。由數個垂直探空的結果中可以發現，VOC的濃度呈現極度不均勻的結果。一般而言靠近地表的VOC呈現較高的濃度且為較新鮮的氣團。而高層的氣團，則呈現VOC經過光化學反應後氣團老化的結果，其老化的現象對應了高臭氧的結果，驗證了高臭氧的來源是來自於上風都會區排放，經過遠距傳輸在下風處產生高臭氧的結果。

Abstract
This study investigated the sorption selectivity of volatile organic compounds by various types of molecular sieve materials of different pores sizes, which consisted of 4 types of commercially available carbon based sorbents as well as two types of self synthesized silicon based mesoporous materials. These sorbents were packed either individually or in combination into a 9cm 1/8” O.D. s.s. tube to form enrichment traps used in a VOC analytical system. A standard gas mixture containing 56 C2-C12 species with known mixing ratios was analyzed by the traps for testing the enrichment efficiency and selectivity for these sorbents. While no single carbon sorbent can performed wide enough range of VOC sorption from C3-C12, the combination of several sorbents to form two multi-beds with one packed with carbosieve SIII, carboxen 1000 for the PLOT column, and the other packed with carbonxen 1000, 1003, and carbotrap, in this order, for the DB-1 column, however provided a uniform sorption efficiency across C3-C12.
We also tested the sorption characteristics of two types of self-synthesized silicon based molecular sieves, which fall into the categories of MCM-41 and MCM-48 with pore sizes of 2.5 nm and 2.8 nm, respectively, significantly larger than those of carbon sorbents with pore size smaller than 1.5 nm in general. As expected, when using silicon molecular sieves poor sorption efficiencies were observed for VOCs smaller than C8-C10 region. Conversely, for molecules larger than C8-C10 region excellent trapping efficiency can be obtained, suggesting sorption selectivity and efficiency is largely controlled by the pore size.

The second part of the thesis discusses the results from a field campaign in an attempt to obtain vertical distributions of VOC concentrations in central Taiwan where seasonal high ozone regularly plagues this area. It was postulated that the transport of VOCs and NOx from urban areas to the downwind rural areas causes maximum ozone formation. As a result, vertical profiles of VOCs mixing ratios were performed in a mountainous downwind area in an attempt to shed light to the transport theory. Each vertical profile was obtained from 7 air samples in Tedlar bags fastened along the string of a balloon elevated up to 1km. We used ratios of VOC pairs of longer lifetime species to short lifetime species to suggest the age of air masses. Based on several vertical measurements it was found that the VOC mixing ratios were highly inhomogeneous vertically and exhibited dramatic layer structure. While the layer near the surface usually showed higher VOC mixing ratios in general, the age of air masses in this elevation was significantly younger than those in the upper layer where aged air mass correlating with elevated O3 suggested long-range transport from upwind VOC source areas.

目 錄
目次 頁次
中文摘要 Ⅰ
英文摘要Ⅲ
目錄Ⅴ
圖目錄Ⅸ
表目錄XIII
第一章 前言
1-1研究緣起1
1-2文獻回顧4
1-2.1揮發性有機物性質與排放源4
1-2.2大氣條件影響揮發性有機物之濃度變化6
1-2.3揮發性有機物之危害性8
1-2.4揮發性有機物對於近地表臭氧生成之重要性8
1-2.5大氣中揮發性有機物監測10
1-2.6揮發性有機物之採樣與分析12
1-3研究目的17
第二章 多重床吸附管與中孔洞分子篩之吸附特性
2-1研究背景18
2-1.1活性碳吸附劑19
2-1.2碳分子篩吸附劑20
2-1.3石墨炭黑吸附劑21
2-1.4多孔聚合物吸附劑22
2-1.5中孔洞分子篩MCM-41之介紹23
2-2研究方法25
2-3實驗方法與儀器裝置26
2-3.1多重床吸附管之製備26
2-3.2中孔洞分子篩吸附管之製備28
2-3.3大氣中揮發性有機物量測流程28
2-3.4前濃縮系統29
2-3.5氣相層析儀31
2-3.6電腦程序控制系統33
2-3.7樣品濕化裝置35
2-4結果與討論36
2-4.1多重床碳分子篩吸附管37
2-4.2中孔洞矽分子篩吸附管41
2-4.3結論與建議47
第三章大氣中揮發性有機化合物垂直探空量測
3-1研究背景49
3-2研究目的51
3-3分析儀器裝置52
3-3.1十六聯裝自動進樣系統53
3-3.2前濃縮儀53
3-3.3氣相層析儀56
3.3.4系統控制用電腦57
3-3.5探空氣球57
3-3.6採樣袋58
3-3.7自動採樣裝置58
3-4分析條件QA/QC60
3-4.1空白實驗60
3-4.2工作標準品60
3-4.3定性分析60
3-4.4定量分析61
3-4.5分析方法之再現性62
3-4.6採樣污染之來源62
3-4.7數據之統計與篩選63
3-5結果與討論65
3-5.1光化探討64
3-5.3結論68
參考文獻69
圖 目 錄
目次 頁次
圖(一) MCM-41合成反應途徑示意圖76
圖(二) M41家族76
圖(三) 吸附管製備過程示意圖77
圖(四) C2-C6吸附管中吸附劑組合示意圖78
圖(五) C6-C12吸附管中吸附劑組合示意圖78
圖(六) MCM-41 XRD圖79
圖(七) MCM-48 XRD圖79
圖(八) 大氣中揮發性有機物量測之基本流程圖80
圖(九) 前濃縮儀管路閥門組合示意圖81
圖(十) 升溫裝置示意圖82
圖(十一) 自動控制軟體GenieDAQ之三個主要作業視窗84
圖(十二) GenieDAQ軟體與界面卡結合閥門等硬體示意圖85
圖(十三) 系統管路狀態圖-Standby狀態86
圖(十四) 系統管路狀態圖-Trapping狀態87
圖(十五) 系統管路狀態圖-Dry Purge狀態88
圖(十六) 系統管路狀態圖-Injection狀態89
圖(十七) 系統管路狀態圖-By pass狀態90
圖(十八) 自動化前濃縮系統與氣相層析儀分析時序示意圖91
圖(十九) 濕化罐實體圖92
圖(二十) 多重床吸附管之空白實驗層析圖93
圖(二十一) PLOT column中個別吸附管之感應因子94
圖(二十二) DB-1 column中個別吸附管之個別感應因子95
圖(二十三) Carbotrap吸附管捕捉工作標準品之層析圖譜96
圖(二十四) MCM-41與多重床吸附管捕捉工作標準品之層析圖譜比較97
圖(二十五) MCM-41在不同溫度脫附所得之結果與多重床吸附管之比較98
圖(二十六) MCM-48與多重床吸附管捕捉工作標準品之層析圖譜比較99
圖(二十七) MCM-48混合玻璃珠與多重床吸附管捕捉工作標準品之層析圖譜比較100
圖(二十八) MCM-48吸附管與MCM-48混合玻璃珠吸附管與多重床吸附管之RF值比較101
圖(二十九) MCM-41吸附管之檢量線103
圖(三十) 混合玻璃珠之MCM-48吸附管之檢量線105
圖(三十一) 惠蓀林場地理位置圖106
圖(三十二) 十六聯裝自動進樣系統107
圖(三十三)皮爾特效應示意圖與降溫晶片的工作原理示意圖108
圖(三十四) 機械手臂與降溫裝置109
圖(三十五) 滯空氣球與氣象感知器全貌110
圖(三十六) 採樣裝置與採樣袋全貌111
圖(三十七) 實驗前系統之空白實驗層析圖112
圖(三十八) 工作標準品之分析圖譜113
圖(三十九) 系統之檢量線114
圖(四十) 探空氣球採集之樣品分析圖譜115
圖(四十一) 分析開始前與開始後之室內空氣層析圖譜116
圖(四十二) 採樣袋內分別為零級空氣與真實樣品之PLOT column層析圖譜117
圖(四十三) 採樣袋內分別為零級空氣與真實樣品之DB-1 column層析圖譜118
圖(四十四) 10月28日下午3點垂直分佈圖119
圖(四十五) 10月24日凌晨2點垂直分佈圖120
圖(四十六) 10月26日中午12點垂直分佈圖121
圖(四十七) 10月29日下午3點垂直分佈圖122
圖(四十八) 10月20日下午4點垂直分佈圖123
圖(四十九) 10月31日下午3點垂直分佈圖124
圖(五十) 10月30日下午3點垂直分佈圖125
圖(五十一) 10月29日中午12點垂直分佈圖126
表 目 錄
目次 頁次
表(一) 美國EPA標準方法(TO)與我國EPA標準方法(NIEA)比較127
表(二) 美國PAMS所制定之具臭氧前驅物生成潛勢之目標物種128
表(三) 本研究中所使用之商業化吸附劑規格表129
表(四) 本研究中氣相層析儀之各項分析條件130
表(五) 購自Spectra gases公司之工作標準品所含之物種131
表(六) C3-C6多重床吸附管吸附工作標準品之再現性132
表(七) C6-C12多重床吸附管吸附工作標準品之再現性133
表(八) 本實驗室自製多重床吸附管與商業化系統感應因子比較134
表(九) C6-C12多重床吸附管之再現性與檢量線之趨勢線的R2 值135
表(十) MCM-41吸附管之再現性與檢量線之趨勢線的R2值136
表(十一) 探空實驗中氣相層析儀之各項分析條件137
表(十二) 系統再現性之結果138

表(十三) 本實驗室自製前濃縮系統對工作標準品檢量線所得之R2值139
表(十四) 所挑選之VOCs物種在25℃下對OH自由基之反應數率常數140

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