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研究生:陳清凉
研究生(外文):Ching-Liang Chen
論文名稱:空氣中VOC分析及其在石化廠的應用
論文名稱(外文):The Measurement of Airborne Volatile Organic Compounds (VOCs) and its Application in Petrochemical Plants
指導教授:方鴻源方鴻源引用關係徐啟銘徐啟銘引用關係
指導教授(外文):Hung-Yuan FangChi-Min Shu
學位類別:博士
校院名稱:國立雲林科技大學
系所名稱:工程科技研究所博士班
學門:工程學門
學類:綜合工程學類
論文種類:學術論文
畢業學年度:94
語文別:英文
論文頁數:198
中文關鍵詞:石化廠特性漏源揮發性有機物空氣調查測定等高線圖煉油廠
外文關鍵詞:Contour mapSurveyMeasurementCharacterizationEmission sourceVOCAirPetrochemical plantRefinery
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空氣中揮發性有機物(VOCs)主要來源為汽機車排氣、石化廠及化學工廠,其中汽機車排氣佔1/2至2/3,而石化廠及化學工廠次之。近年來,石化廠的VOCs排放漸漸受到環保單位及一般大眾的重視。過去有關煉油廠或石化廠的VOC排放相關研究,大部份在廠區外採樣,往往無法看出VOCs的全貌。本論文提出新的方法來找出煉油廠及石化廠的VOCs排放來源及定出VOCs的成份特性。
研究的對象包括一座位於高雄縣林園鄉大型的石化廠及另一座位於桃園縣的大型煉油廠。為了避免受馬路上汽機車排氣影響,採樣點設在廠區內。每個工廠佈置25個採樣點,位置離地面1.5公尺,每季採樣兩次,一年共八次。林園石化廠於2003年,桃園廠於2004年,進行調查,每廠各一年。採樣及分析均參考TO-14標準方法;以不鏽鋼採樣罐(Canister)採樣,再以GC-MS定性及定量出各VOCs成份。為了解析VOCs的特性,測得的資料全部以Excel整編成資料庫,再進行排序、條件查詢、交叉分析、統計處理及統計繪圖,以圖表的方式來展現出VOCs的特性。另外,透過Surfer軟體,將資料轉成等高線圖,並與工廠地圖合併,而變成VOCs分佈圖。利用各VOCs成份分佈圖即可成功地找出各類VOCs可能的排放源位置。
在林園石化廠調查方面,經由交叉分析,發現主要的VOCs為烷類 ( 57﹪)、烯類 ( 26﹪)及芳香烴 ( 17﹪),合計佔空氣中VOCs的99﹪。有六個排放源被找到,每個排放源的VOCs特性,均以統計值如平均值、標準偏差、90﹪信頼區間來表示。烷類及烯類主要由C3至C5的成份組成,而芳香烴主要成份為苯、甲苯及二甲苯。VOCs排放特性大致與各製程單元的特性一致。
在桃園煉油廠調查方面,發現主要的VOCs為烷類 ( 51﹪)、烯類 ( 27﹪)、芳香烴 ( 10﹪)及環烷類 ( 8﹪),合計佔空氣中VOCs的96﹪。有五個排放源被找到,其中以油槽區及廢水處理場最嚴重。五個排放源合併在一起,來解析其VOCs成份的變化。烷類以C3-C10為主,最主要的成份為丙烷、丁烷、正戊綄、異戊烷及已烷,合計佔71﹪。烯類以丁烯及戊烯最多,合計佔76﹪。芳香烴則以苯、甲苯及二甲苯為主,佔84﹪。烷環類則以甲基環戊烷及甲基環己烷為主。
過去很少有從煉油廠或石化廠內部進行VOCs採樣調查,對於大量VOCs的調查數據,往往不知如何進行解析。相信本研究,可提供相關研究者一個簡單可行的數據處理方法,也可讓大家了解煉油廠或石化廠的VOCs排放特性,並可協助環保人員正確地找出排放源,以便做有效整治。
本研究中採樣時間均為白天。若改為夜間採樣,其測得濃度值可能會比白天所測得值的1.4–2.9倍,主要原因係夜間的混合層高度較白天為低所致。
Surveys of VOCs have shown that vehicle exhausts were the greatest sources of emissions, especially in urban areas, accounting for one half to two–thirds of total emitted VOCs. The VOCs emitted from a refinery and a petrochemical plant was another environmental concern second to vehicle exhausts and its VOCs emissions have been drawing nearby inhabitants’ considerable attention over years. Among the researchers touching on characterization of VOCs from the petrochemical plants, most of them only paid attention to developing a VOC profile of the plant, whose samples were usually taken several kilometers downwind, rather than inside, of the plant. Sampling outside the plant usually made it impossible to gain insight into the VOCs. This thesis elucidated a novel approach to locating VOCs emission sources and characterizing their VOCs
The thesis surveyed a large-sized petrochemical plant at Linyan, Kaohsiung County and another large-sized refinery at Taoyan. To avoid interferences from vehicle exhaust, all sampling sites were positioned inside the plant. In order to characterize VOCs and locating possible emission sources, we sampled the ground-level air with pre-evacuated canisters at 25 selected locations inside this plant, and identified and quantified all possible VOCs by GC–MS. The survey period extended from January, 2003 to December, 2004 and sampled twice per quarter, with 400 samples in total. The survey of each plant covered one whole year. To keep track of surveyed data and to report them in an easy-to-read, easy-to-retrieve form, all data were consolidated into database on Microsoft Excel. The database could provide some inherent functions, such as retrieving, sorting, arranging, statistical calculation and plotting, which served to characterize the VOCs emitted. On the other hand, the geographic distribution of VOCs inside this plant was presented by the help of the software Surfer in the form of contour map, which served to locate possible emission sources.
In the survey of the Linyan petrochemical plant, it followed from the cross analysis of the database that the abundant VOCs were alkanes (57%), alkenes/dienes (26%), and aromatics (17%), all of which accounted for 99 % of total VOCs. By contour mapping, the emission sources for alkanes, aromatics, alkenes/dienes were successfully located. With statistical analysis, the database could provide the range, 90 % confidence interval of each species from each emission source. Both alkanes and alkene/dienes came from tank farm and naphtha cracking units, and were mainly composed of C3–C5 members. Regarding aromatics, benzene, toluene and xylenes were the primary species; they were emitted from tank farm, aromatic units and xylene units. Of VOCs, alkanes were most abundant, taking up about 50% and mainly consisted of C3-C10 members. The five more plentiful species were propane, butane, 2-methylbutane, pentane, hexane, the sum of which was responsible for 71 % of alkanes. As for aromatics, they were mostly composed of, benzene, toluene, xylenes, accounting for 84 %. The alkenes mainly comprised of butene and pentene, representing 76 %. As regards cyclic HCs, they were mostly made up of methylcyclopentane and methylcyclohexane.
In the survey of the Taoyan refinery, the dominant VOCs were found to be alkanes (51%), alkenes(27%), aromatics(27%) and cyclic HCs(10%). By mapping these four types of VOCs, we located six main emission sources including Filling Station, No.1, No.2 Topping Units, No.2 Alkylation Unit, Tank Farm and Wastewater Treatment Unit, of which Wastewater treatment unit and Tank farm much heavier than others. The surveyed data of these six emission sources were merged to characterize their VOCs by means of mean concentration, standard deviation, minimum concentration and maximum concentration. Alkanes were mainly composed of C3-C10 members, of which propane, butane, pentane, isopentane, and hexane were the most plentiful species, the sum of them accounting for 71%. As for alkenes, they were mainly consisted of butane and pentene, taking up 76% and as for aromatics, benzene, toluene and xylenes were the richest, approaching 84%. Of Cyclic HCs, methylcyclopentane and methylcyclohexane were the most plentiful species.
In a survey of VOCs from petrochemical plants or urban areas, difficulty was often encountered in handling a large number of data. By consolidated into a database, data become much more easily manageable and can be readily converted into meaningful information. This study featured the use of ordinary application software like Excel and Surfer, instead of expensive one like GIS, to deal with this problem This approach helped the environmental engineers not only to characterize VOCs emitted, but also successfully to locate the VOCs emission sources inside the plant.
The concentration of each VOCs, if sampled at nighttime, might be 1.4–2.9 times as high as that surveyed in this study, which was due to the lower mixing layer height at nighttime.
CATALOG PAGE
Abstract in Chinese ……………………………………………….. i
Abstract in English ………………………………………………… iii
Acknowledgements ………………………………………………… vi
Table Captions ……………………………………………………… xi
Figure Captions …………………………………………………….. xiii
1. Introduction ……………………………………………………... 1
2. Literature survey ………………………………………………… 5
3. Goal of Study ……………………………………………..……. 18
4. Materials and Methods …………………………………….…... 19
4.1 Sampling …………………………………………………………… 19
4.2 Analytical Method …………………………………………………. 20
4.3 Database …………………………………………………………… 22
4.4 Estimation of Unknown Values ……………………………………. 23
4.5 Contour Map ………………………………………………………. 25
5. Results and Discussions ………………………………………. 25
5.1 Source Location and Characterization of Volatile Organic Compound Emissions inside the Linyan Petrochemical Plant …… 25
5.1.1 Abundant VOCs ……………………………………………………. 26
5.1.2 Locating Emission Sources ………………………………………… 26
5.1.3 Characterization of VOCs Emitted from Sources …………………….. 29
5.2 Source Location and Characterization of Volatile Organic Compound Emissions inside the Taoyan Refinery. ………………… 31
5.2.1 Abundant VOCs ……………………………………………………….. 31
5.2.2 Locating Emission Sources ……………………………………………. 32
5.2.3 Overall Comparison of Emission Sources …………………………….. 34
5.2.4 Characterization of VOCs Emitted from Sources ………………………35
5.3 Estimation of the Concentration of Airborne VOCs if sampled at Night ………………………………………………………………….. 37

6. Conclusions ……………………………………………………..... 38
7. References ………………………………………………………….39
8. Tables ……………………………………………………………… 46
9. Figures …………………………………………………………….. 64
10. Autobiography ………………………………………………………96
11. Appendix A The paper published in Journal of the Air & Waste Management Association………………………………………….97
12. Appendix B The Manuscript accepted by Environmental Monitoring & Assessment …………………………………………………..108
13. Appendix C The Manuscript accepted by Environmental Forensics. ……………………………………………………….120
14. Appendix D The Manuscript accepted by Journal of the Air & Waste Management Association ………………………………………. 147
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