國 立 中 央 大 學 環 境工程研 究 所 博 士 論 文 以低溫熱裂解程序降解土壤中五氯酚之 研究 Investigation on Low-Temperature Pyrolysis of Pentachlorophenol-Contaminated Soil 研 究 生：Ngo Thi Thuan (歐婷芳) 指導教授：張木彬 教授 中 華 民 國 一百零一 年 七 月 國立中央大學圖書館 碩博士論文電子檔授權書 (100 年 月最新修正版) 本授權書授權本人撰寫之碩/博士學位論文全文電子檔(不包含紙本、詳備註 說明)，在 「國立中央大學圖書館博碩士論文系統」。(以下請擇一勾選) (●)同意 (立即開放) ( )同意 (一年後開放)，原因是： ( )同意 (二年後開放)，原因是： ( )同意 (三年後開放)，原因是： ( )不同意，原因是： 在國家圖書館「臺灣博碩士論文知識加值系統」 (●)同意 (立即開放) ( )同意 (請於西元 ( )不同意，原因是： 年 月 日開放) 以非專屬、無償授權國立中央大學圖書館與國家圖書館，基於推動「資源共享、互惠合 作」之理念，於回饋社會與學術研究之目的，得不限地域、時間與次數，以紙本、微縮、 光碟及其它各種方法將上列論文收錄、重製、公開陳列、與發行，或再授權他人以各種 方法重製與利用，並得將數位化之上列論文與論文電子檔以上載網路方式，提供讀者基 於個人非營利性質之線上檢索、閱覽、下載或列印。 研究生簽名: 歐 婷 芳 學號： 973406601 論文名稱: Investigation on Low-Temperature Pyrolysis of Pentachlorophenol-Contaminated Soil 指導教授姓名： 系所 ： 張木彬 博士 環境工程所 ▆博士班 碩士班 備註： 本授權書之授權範圍僅限電子檔，紙本論文部分依著作權法第 15 條第 款之規定，採推定原則即 預設同意圖書館得公開上架閱覽，如您有申請專利或投稿等考量，不同意紙本上架陳列，須另行加 填聲明書，詳細說明與紙本聲明書請至 http://thesis.lib.ncu.edu.tw/ 下載。 本授權書請填寫並親筆簽名後，裝訂於各紙本論文封面後之次頁（全文電子檔內之授權書簽名，可 用電腦打字代替） 。 請加印一份單張之授權書，填寫並親筆簽名後，於辦理離校時交圖書館（以統一代轉寄給國家圖書 館） 。 讀者基於個人非營利性質之線上檢索、閱覽、下載或列印上列論文，應遵守著作權法規定。 Abstract High energy cost and potential formation of dioxins during incineration/combustion of pentachlorophenol (PCP) have limited their application on simultaneous removal of highly contaminated soil of PCP, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) at AnShun in Taiwan In this dissertation, investigation of PCP pyrolysis in soil at a relatively low temperature range (150-400oC) and the behavior of PCDD/Fs formation, dechlorination and destruction during pyrolysis of PCP-contaminated soil have been examined in detail Most PCP (>90%) and PCP byproducts can be removed from soil at 350oC for 40 The PCP decay rates from soil increased exponentially from 0.20 to 1.96 min-1 as temperature was increased from 150oC to 400oC Very low levels of PCDD/Fs were found in soil (0.38-2.48 ng TEQ/kg) and gaseous phase (0.0015-0.0044 ng TEQ/Nm3) during pyrolysis of PCP-contaminated soil 70% of PCP removal from the soil was achieved, resulting in 1436230 ng/kg, the highest PCDD/F formation at 250oC; however, the highest toxic concentration was measured around 4.20  0.62 ng TEQ/kg at 300oC with 80% PCP removal from the soil Further analysis has revealed that OCDD is the most dominant congener supposed to form from the pyrolysis of PCP, while OCDF is the second prevailing congener, possibly due to 2,3,4,5-TeCP reaction which is a main byproduct of PCP pyrolysis Detection of less chlorinated dioxins and furans over 300 oC indicates the dechlorination of highly chlorinated dioxins and furans, especially OCDD at 350oC and 400oC Desorption from soil was supposed as a main mechanism for the distribution of PCDD/Fs in the gas phase, and not much difference in dioxins and furan levels was observed at 350oC and 400oC in the gas phase In order to test the nZVI reactivity with PCP, a thermally enhanced pump-and-treatment method coupled with nZVI was proposed to remove PCP from soil and to detoxify aqueous phase and soil The results indicated that total PCP removal in soil and aqueous phases increased with increasing nZVI dose The PCP distribution in aqueous phase was enhanced when PCP-contaminated soil was remediated with nZVI In addition, decrease in pH resulted in decreasing PCP distribution in aqueous phase but increasing PCP dechlorination Dechlorination rate was enhanced from 2.26 to 6.84 h-1 as the temperature was increased from 25oC to 85oC Dechlorination and PCP residual in soil were increased to 42% and decreased to 6%, respectively, at 85oC and pH1 The dechlorination of PCP preferred to occur at ortho> meta> para positions in the respect of OH group Based on the results of nZVI reactivity with thermal enhancement, the combination of pyrolysis and nZVI was proposed to investigate the PCP removal from soil Consequently, the decay rate constant (k) of pyrolysis combined with nZVI increased exponentially from 0.59 to 3.67 min-1 which were times higher than that without nZVI in the temperature range of 150°C -300°C The activation energies of PCP removal from soil with and without nZVI are 23.80 and 36.98 kJ/mol, respectively PCP degradation increases linearly with increasing nZVI dose The rate decay constant increased from 0.21 min-1 to 1.56 min-1 as nZVI dose was increased from 0% to 10% at 200oC The order of PCP dechlorination during pyrolysis coupled with nZVI is the same as that in the absence of nZVI but dechlorination process during pyrolysis with nZVI occurred more completely into the final product as phenol Increasing temperature to 300oC resulted in the predominant TeCP ((0.4  0.1) %) in soil and none byproducts was detected in soil as either temperature or time was increased above 300 oC and 30 min, respectively Especially, both PCP and byproducts were not detected in gaseous phase This study provides relevant information for risk assessment for PCP contaminated soils when low thermal pyrolysis is applied for remediation of PCP contaminated soil Key words: Pentachlorophenol, low thermal, nano scale zero valent iron, soil, byproducts, dioxin formation 中文摘要 焚化與燃燒之高能量消耗與戴奧辛之生成限制了台灣安順廠同時處理含高濃度 PCP 和 PCDD/Fs 汙染之土壤之能力。本研究探討低溫下(150-400°C)土壤中的 PCP 裂解和多 氯聯苯和呋喃之生成特性。受 PCP 汙染土壤裂解時之脫氯與裂解在本研究中有詳細的探 討。大部分的 PCP (>90%)和 PCP 之副產物可在 350°C 經 40 分鐘處理被去除。PCP 之衰 減率在溫度從 150°C 升到 400°C 時明顯上升(0.20-1.96 min-1)。裂解過程中發現 PCDD/F 濃度很低，土壤中為 0.38-2.48 ng TEQ/kg，氣相中為 0.0015-0.0044 ng TEQ/Nm3。土 壤中 PCP 去除率達到 70%時，最高的 PCDD/F 生成在 250°C，為 1436±230 ng/kg。然而， 最高的毒性濃度(4.20±0.62 ng TEQ/kg)是在 PCP 去除效率為 80%且操作溫度在 300°C 時。本研究進一步指出 OCDD 是裂解 PCP 之主要生成物種，OCDF 則是第二顯著物種，可 能原因是因為 PCP 裂解的主要副產物 2,3,4,5-TeCP 反應所造成。溫度大於 300°C 時， 少量的戴奧辛與呋喃會被偵測到是由於高氯數之戴奧辛與呋喃脫氯所造成，尤其是 OCDD 在 350°C 和 450°C 時。土壤脫附是 PCDD/F 在氣相中分布的主要機制，350°C 和 400°C 的戴奧辛與呋喃濃度並無明顯的差別。 為 測 試 nZVI 對 於 PCP 的 活 性 ， 熱 促 進 處 理 方 法 (thermally enhanced pump-and-treatment method)與 nZVI 被用來移除土壤中的 PCP 和去除土壤中和液相之 毒性。結果顯示土壤中與液相之 PCP 去除效果隨 nZVI 劑量增加而上升。利用 nZVI 復育 土壤時 PCP 在水中的分布會增加。而 pH 降低會導致 PCP 在液相中分布減少但 PCP 脫氯 增加。當溫度從 25°C 提升至 85°C 時，脫氯速率從 2.26 h-1 提高至 6.84h-1。在 85°C 與 pH = 的條件下，脫氯提升了 42%，PCP 殘餘量則降低了 6%。此系統中脫氯位置發生傾 向於 ortho>meta>para。基於此結果，本研究利用裂解結合 nZVI 去除土壤中之 PCP。在 150-300°C 時，裂解結合 nZVI 之裂解速率為 0.591-3.699 min-1，為未結合 nZVI 之四倍。 活化能部分有 nZVI 為 23.80 kJ/mol，無 nZVI 為 36.98 kJ/mol。當 nZVI 劑量增加時， PCP 之降解速率呈線性上升。衰減速率在 200°C 時 nZVI 劑量從 0%到 10%為 0.21 min-1 到 1.56 min-1。PCP 之脫氯在有無 nZVI 之情況下皆相同，但若有 nZVI 則裂解會更完全 使最終產物變為 phenol。溫度增加至 300°C 時土壤中主要為 TeCP (0.4±0.1%)並且無其 他副產物之生成，當溫度上升至 300°C 以上且時間在 30 分鐘以上情況亦同。特別的是 在氣相中皆未偵測到 PCP 以及任何副產物。此研究提供了利用低溫熱裂解處理 PCP 汙染 土壤之相關風險評估資訊。 Key words: Pentachlorophenol, low thermal, nano scale zero valen iron, soil, byproducts, dioxin formation Acknowledgements First of all, I would like to express my great appreciation to my advisor, Professor Moo Been Chang, for his guidance, patience and encouragement during the past years This dissertation could not be finished without his continuous support I also wish to thank Mrs Chang for her kindness Special thanks to Assistant Professor Kai Hsien Chi for his help, good advice and experiences on doing research and writing paper The author is greatly appreciated to Mr Pao Chen Hung, Mr Shu Hao Chang and Nguyen Thanh Dien for their assistance in dioxin analysis and nZVI synthesis I gratefully acknowledge all faculty members of Graduate Institute of Environmental Engineering who have provided the basic knowledge, support and encouragement during my studies at NCU I would like to thank all Taiwanese students of Graduate Institute of Environmental Engineering, especially my labmates in Professor Chang group for the friendship and willingness to help me during the experiment I would also like to thank my Vietnamese friends at NCU for their funny stories and daily encouraging conversations I would like to thank the financial support from National Science Council (NSC 98-2221E-008-019-M Y3), National Central University and Vietnam National University, Hochiminh City Finally but perhaps most importantly, I would like to delicate this dissertation to my parents and my husband who are always by my side to help me getting balance my life and show me the value of love, hard work and perseverance NCU, 16/07/2012 Ngo Thi Thuan Table of Contents Abstract Chapter1 Introduction 1.1 Background and motivation ………………………………………………………… 1.2 Objectives and Scope………………………………………………………………… Chapter Literature Review 2.1 History of production and use of PCP ………………………………… 2.2 History of An Shun site ………………………………………………………………… 2.3 Chemical and physical properties of PCP …………………………………… .7 2.4 Chemical and properties of PCDD/Fs …………………………………… 2.5 Technologies for PCP remediation from soil ………………………………………… 2.6 Thermal remediation technologies …………………………………………… 10 2.6.1 Incineration/ combustion …………………………………………………… 10 2.6.2 Potential PCDD/Fs formation from chlorophenols during thermal…… .11 2.6.3 Mechanism of PCDD/F formation from chlorophenols …………………… 13 2.7 Low-thermal technologies ………………………………………………… 15 2.7.1 Thermal desorption …………………………………………………… 15 2.7.2 Low-temperature pyrolysis ………………………………………………… 16 2.8 Removal of chlorinated phenols by nZVI ………………………… .19 2.8.1 nZVI characteristics ………………………………………………………… 19 I 2.8.2 nZVI synthesis …………………………………………………… 19 2.8.3 General mechanisms of pollutant remediation by nZVI ………… .21 2.8.4 Literature review on remediation of chlorinated compounds with nZVI… 21 Chapter Materials and Experimental Methods 3.1 Materials ………………………………… 55 3.2 Soil preparation ……………………………………………………………………… 55 3.3 Experimental systems ……………………………………………………………… 56 3.3.1 Thermal system ……………………………………………………………… 56 3.3.2 nZVI system for testing nZVI reactivity with PCP contaminated soil 57 3.3.2.1 nZVI synthesis …………………………………………………………57 3.3.2.2 Experimental setup for PCP degradation with nZVI ………………57 3.4 Analytical methods ………………………………………………… .58 3.4.1 Analytical methods for PCP determination in soil ………………………… 58 3.4.2 Analytical methods for PCDD/F ……………….…………………………… 59 3.4.3 Analytical methods for chloride determination …………………………… 60 3.4.4 Instruments for analysis of nZVI reactivity ………………………………….60 Chapter Results and Discussion 4.1 Analytical methods for PCP analysis …………………………………………… .66 4.2 Degradation of PCP contaminated soil with low thermal pyrolysis (200-400o) …… 66 4.2.1 Kinetics of PCP removal from soil ……………………………………………66 II 4.2.2 Analysis of the temperature impact on the fate of PCP during pyrolysis ….69 4.2.3 Analysis of the temperature impact on byproduct releases………………….70 4.2.4 Analysis of time impact on byproduct releases ………………………………71 4.2.5 Formation and degradation of PCDD/Fs in soil…………………………… 71 4.2.6 Formations and degradation of PCDD/F congeners in soil………………….73 4.2.7 Formation and degradation of PCDD/Fs in gaseous phase …………………75 4.2.8 Proposed pathways leading to PCDD/F formation and removal ………… 76 4.2.9 Possible overall pathways of PCP removal from soil ……………………… 77 4.3 PCP degradation in slurry soil with nZVI………………………………… 79 4.3.1 Characteristics and reactivity of nZVI ……………………………………….79 4.3.1.1 Effect of synthesis environment …………………………………… 79 4.3.1.2 Effect of acid washing after reaction ……………………………… 81 4.3.2 Effect of nZVI dose …………………………………………………………….81 4.3.3 Effect of initial pH on PCP removal from slurry soil………………… 81 4.3.4 Effect of temperature ………………………………………………………… 83 4.3.5 Effect of time ………………………………………………………… .84 4.3.6 Identification of byproducts ………………………………………………… 84 4.4 PCP degradation in soil with nZVI coupled with thermal…………………………….85 4.4.1 Temperature effect on PCP removal from soil ………………………………85 4.4.2 Effect of nZVI dose …………………………………………………… 88 4.4.3 Analysis of PCP byproducts ………………………………………………… 89 4.4.3.1 Temperature effect on byproduct releases ………………………… 89 4.4.3.2 Time effect on byproduct releases ……………………………………90 III Bandara, J., Mielczarski, J.A., Kiwi, J., 2001 Adsorption mechanism of chlorophenols on iron oxides, titanium oxides and aluminum oxide as detected by infrared 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from pyrolysis of PCP -contaminated soil …………………………………………………………………………………95 Figure 4-8b Effect of temperature on PCDD/F release into gas phase during pyrolysis of PCPcontaminated soil ……………………………………………………………… 95 Figure 4-9 Effect of temperature on congener formation in pyrolysis of. .. chromatogram of temperature effect on product release from pyrolysis with 5% nZVI of PCP contaminated soil into soil …………………………… 111 Figure 4-31b GC/MS chromatogram of temperature effect on product release from pyrolysis with 5% nZVI of PCP contaminated soil into gaseous phase………………… 112 Figure 4-32 Pathways of PCP removal from contaminated- sandy soil during pyrolysis in the temperature range of 150-400oC………………………………………………... Time effect on PCP recovery from extraction…………………………………… 92 Figure 4-3 Residual PCP concentrations as a function of time at various temperatures………93 VIII Figure 4-4 Temperature effect on fate of neat PCP and PCP -contaminated sandy soil during pyrolysis at  = 30 min…………………………………………………………… 93 Figure 4-5a Effect of temperature on byproduct yield in soil from pyrolysis of PCP contaminated sandy soil at... of PCP -contaminated soil ……………………………………………………………………………….96 Figure 4-10 Effect of temperature on congener release into gas phase during pyrolysis of PCPcontaminated soil ……………………………………………………………… 96 IX Figure 4-11 Mechanisms leading to OCDD and OCDF formation in pyrolysis of PCPcontaminated soil ……………………………………………………………… 97 Figure 4-12 Pathways of PCP removal from contaminated- sandy soil during pyrolysis. .. Figure 4-5b Effect of temperature on byproduct release to gas from pyrolysis of PCP contaminated sandy soil at  = 30 min…………………………………………… 94 Figure 4-6a Effect of time on byproduct yield in the soil from pyrolysis of PCP contaminated sandy soil at 350oC…………………………………………………………………94 Figure 4-6b Effect of time on byproduct release to the gas from the pyrolysis of PCP contaminated sandy soil at 350oC………………………………………………….94... Dechlorination process with nZVI during pyrolysis of PCP contaminated soil in the temperature range of 150-250oC……………………………………………108 Figure 4-29 Variations with time in the byproduct yield during pyrolysis of PCP contaminated soil in the presence of 5% nZVI at (a) 200oC and (b) 250oC………………… 109 Figure 4-30 GC/MS chromatogram of product release from pyrolysis of PCP contaminated soil into (a) soil and... 200-400oC conditions Therefore, the first part of the dissertation is to investigate: - Effect of temperature, time and flow rate on PCP removal - Kinetics of PCP removal in the temperature range of 200-400oC - Analysis of byproducts of PCP remediation in the soil and the gaseous phase during pyrolysis - Elucidation of removal pathways 2 The second part involves the feasibility of nZVI application in PCP... physical-chemical properties of soils collected…………………………… 65 V Table 4-1 Temperature effect on byproduct releases in gaseous phase and soil during pyrolysis of PCP -contaminated soil …………………………………………………… 98 Table 4-2 The measurement of rate constant (k) and activation energy (Ea) of PCP contaminated soil during pyrolysis with and without nZVI…………………… 114 Table 4-3 The pseudo-first-order constants of PCP by nZVI... degradation during pyrolysis coupled with nZVI in the temperature range of 150-300oC……………………………………………… 106 Figure 4-25 Effect of nZVI dose on PCP degradation during pyrolysis at 200oC………… 106 Figure 4-26 Effect of nZVI dose on PCP degradation during pyrolysis ………………….107 Figure 4-27 Temperature effect on byproduct releases during pyrolysis of PCP -contaminated soil in the presence of 5% nZVI………………………………………………... 4-22 Temperature effect on PCP removal from soil with nZVI and pyrolysis …… 105 Figure 4-23 Residual PCP concentrations during pyrolysis with nZVI as a function of time at various temperatures…………………………………………………………… 105 Figure 4-24a Activation energy of PCP degradation during pyrolysis in the temperature range of 200-350oC……………………………………………………………………106 X Figure 4-24b Activation energy of PCP degradation