| dc.description.abstract | 行政院環保署於民國106年預告「固定污染源有害空氣污染物排放標準」草案，將分三階段進程管制72項重要有害空氣污染物，並訂定製程排放標準。然對於部分污染物仍欠缺合宜的分析技術，以致無法對其排放源推動管制作業，本研究即是針對此類物種開發管道中標準分析技術，亦即1,3-丁二烯 (1,3-Butadiene)、醋酸乙烯酯 (Vinyl acetate)、甲基丙烯酸甲酯 (Methyl methacrylate)、苯甲氯 (Benzyl chloride)、溴甲烷 (Bromomethane)、氯甲烷 (Chloromethane)、1,2-二溴乙烷 (1,2-Dibromoethane)、1,1-二氯乙烯 (1,1-Dichloroethylene)、1,1,2-三氯乙烷 (1,1,2-Trichloroethane)、氯丙烯 (Allyl chloride) 及1,4-二氯苯 (1,4- Dichlorobenzene) 等11種化學品即為首要關注之化學物質。1,3-丁二烯 (1,3-Butadiene) 等11項有害空氣污染物，目前多為針對周界、作業環境或固態廢棄物的檢測方法，為克服排放管道內高溫、容易受水氣干擾、採樣不易等問題，參考環檢所公告方法NIEA A722.75B，使用採樣袋方式採樣，搭配氣相層析火焰離子偵測器 (GC-FID) 及氣相層析電子捕捉偵測器 (GC-ECD) 進行分析。
本研究針開發完成1,3-丁二烯、醋酸乙烯酯及甲基丙烯酸甲酯等3項空氣污染物以採樣袋採樣經由GC-FID分析技術；氯甲烷、溴甲烷、1,1-二氯乙烯、氯丙烯、1,1,2-三氯乙烷、1,2-二溴乙烷、苯甲氯及1,4-二氯苯等8項空氣污染物以採樣袋採樣經由GC-ECD分析技術。11種空氣污染物的檢測技術建立，包括分析技術之品保規範，檢量線、偵測極限、樣品保存、精密度、準確度等，並完成真實樣品採樣分析。
針對11項目標物分別建立高、低濃度兩組檢量線，低濃度檢量線區間為0.67~10 ppm，線性結果，R2 =0.993~0.999；高濃度檢量線區間為3~50 ppm，線性結果，R2 =0.997~0.999，經預估確認後得11項目標物之偵測極限介於0.0128~0.527 ppm。樣品保存方面，利用採樣袋採樣之11項目標物中，除1,4-二氯苯保存期限僅2小時外，其餘10項目標物保存期限介於12小時至2天，精密度與準確度結果，11項目標物RSD值介於1.5~4.9 %，回收率介於96.2~104.3 %。
樣品保存上，1,1-二氯乙烯、1,2-二溴乙烷、苯甲氯、醋酸乙烯酯及甲基丙烯酸甲酯於採樣袋中樣品保存時間為12小時，1,4-二氯苯於採樣袋中樣品保存僅2小時，針對上述6種保存效率較差之物種，嘗試以採樣管採樣方法，改善採樣袋對高沸點物種保存不佳之情況。採樣管保存測試結果顯示，樣品保存於採樣管中，Tenax TA材質對樣品之保存期限最短皆可以達到1天，相較於採樣袋有更好的保存能力。
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| dc.description.abstract | In 2017, Environmental Protection Administration (R.O.C.) announced the draft “Stationary Pollution Source Hazardous Air Pollutants Emissions Standards” to control 72 critical hazardous air pollutants (HAPs) in a three-stage process and set emission standards for these HAPs. However, until now some of the listed HAPs still lack suitable analytical techniques, which may inevitably prolong the implementation of the emission control policy of HAPs. The main objective of this study is to develop sampling and analytical methods for selected HAPs in flue gas from stacks, i.e., 1,3-butadiene, vinyl acetate, methyl methacrylate, benzyl chloride, bromomethane, chloromethane, 1,2-dibromoethane, 1,1-dichloroethylene, 1,1,2-trichloroethane, allyl chloride and 1,4-dichlorobenzene. These 11 target HAPs are the primary species of concern and most of which have already been addressed by existing methods for ambient gas, working environment, or solid wastes. Meanwhile, taking samples of flue gas from stacks always has to deal with high temperature and humidity conditions. For the sampling part, we mainly exploited the existing method of NIEA A722.75B - the use of sampling bags combined with gas chromatography - flame ionization detection (GC-FID) and GC-electron capture detection (GC-ECD) to expand the target compounds to include these 11 HAPs.
The study divided the target compounds into two separate groups, with tailored methods for each. The first group of 3 HAPs (1,3-butadiene, vinyl acetate and methyl methacrylate) were analyzed by GC-FID, whereas the second group of 8 HAPs (benzyl chloride, bromomethane, chloromethane, 1,2-dibromoethane, 1,1-dichloroethylene, 1,1,2-trichloroethane, allyl chloride and 1,4-dichlorobenzene) were analyzed by GC-ECD. The criteria of quality assurance for the 11 target HAPs, including calibration, detection limits, sample preservation, precision, accuracy, were performed in the laboratory. Moreover, real flue gas samples were also collected and analyzed using the established methods of GC-FID and GC-ECD.
To test for linearity and construct calibration curves, we further divided the 11 target compounds into two concentration ranges of low and high. For the low range from 0.67 ~ 10 ppm, the R2 = 0.993~0.999, whereas for the high range from 3~50 ppm, the R2 = 0.997~0.999, both ranges showing very high linearity. The detection limits of the 11 target analytes are in the range 0.0128~0.527 ppm. The sample preservation test for the 11 HAPs in sampling bags showed that, except for 1,4-dichlorobenzene, which has a very short preservation time of no longer than 2 hours, the other 10 analytes showed much longer preservation time of 12 hours to 2 days. The precision for the 11 target analytes are in the range1.5~4.9%. The recoveries are in the range 96.6~104.3%, demonstrating high accuracy.
Of the 11 HAPs, 1,1-dichloroethylene, 1,2-dibromoethane, benzyl chloride, vinyl acetate and methyl methacrylate showed preservation times only stable within 12 hours, and 1,4-dichlorobenzene only stable within 2 hours in sampling bags. In order to increase the overall preservation period for the aforementioned 6 analytes, sorbent tubes instead of sampling bags were attempted. Our findings indicate that, for the above 6 HAPs, using sorbent tubes with Tenax TA adsorbent showed a much longer preservation time of more than 1 day, which may provide a better alternative than sampling bags to collect and preserve flue gas for the 6 HAPs.
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