| 研究生: |
左為鐸 Cheruiyot, Nicholas |
|---|---|
| 論文名稱: |
都市焚化爐及柴油引擎排放持久性有機污染物之偵測與控制 Monitoring and Control of Toxic Organic Pollutant Emissions from Municipal Solid Waste Incinerators and Heavy-Duty Diesel Engines |
| 指導教授: |
侯文哲
Hou, Wen-Che |
| 共同指導教授: |
李文智
Lee, Wen-Jhy |
| 學位類別: |
博士 Doctor |
| 系所名稱: |
工學院 - 環境工程學系 Department of Environmental Engineering |
| 論文出版年: | 2019 |
| 畢業學年度: | 108 |
| 語文別: | 英文 |
| 論文頁數: | 200 |
| 中文關鍵詞: | 有毒有機污染物 、持久性有機污染物 、冷起爐 、都市焚化爐 、重型柴油引擎 |
| 外文關鍵詞: | Toxic organic pollutants, POPs, Cold start-up, MSWIs, HDDE |
| 相關次數: | 點閱:101 下載:10 |
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我們研究了城市廢棄物焚化爐(MSWI)和重型柴油機(HDDE)對持久性有機污染物的排放監測和控制,包括持久性有機污染物(POP)和多環芳烴(PAH)。為解決各文獻中沒有研究到的部分。具體而言,這包括控制MSWI冷啟爐期間的POPs大量排放。此外,在HDDE方面,實驗由低至高的石油柴油-生物柴油混合物比率對PAHs和POPs排放的影響,以及POP排放對空氣污染防制設備用於處理傳統污染物的影響進行了全面研究。如本研究中所述,普通的MSWI啟動過程會產生極高濃度的氯化和溴化持久性有機污染物;例如:多氯聯苯對二噁英/二苯並呋喃(PCDD / Fs)為130 ng WHO-TEQ Nm-3,多氯聯苯(PCBs)為42.6 ng WHO-TEQ Nm-3,多溴聯苯為60.4 ng Nm-3 (PBBs)。因此,為期兩天的啟動過程會產生PCDD / Fs和PCBs排放量,大約是全年正常運行量的20倍。作為回應,這項研究提出了一些控制策略,包括完善的清理積聚在燃燒室爐床下方並沉積在過熱器和節能器壁上的爐灰,並縮短煙道氣在POPs形成窗口處的停留時間(250 – 450℃)在燃燒室中。同樣,在啟動過程中,延長活性炭和石灰的注入時間以減少POPs排放。研究結果顯示,該控制策略非常有效,所有其他POP排放量均減少了> 96%,PBDEs減少了61%。迄今為止,僅使用有限的燃料混合比研究了生物柴油對多溴聯苯醚多環芳烴和多氯二苯並對二噁英排放的影響。為了闡明使用更高比例的生物柴油對柴油發動機有毒有機污染物排放的影響,在這項研究中,以低至高廢食用油為燃料的EURO IV和EURO III HDDE的PM,PAHs和POPs排放(研究了基於WCO)的生物柴油-柴油混合物,包括D100(0%生物柴油),B20(20%),B40(40%),B60(60%),B80(80%)和B100(100%)。在EURO IV柴油機的結果顯示,與D100方案相比,直到B60方案,PM和持久性有機污染物的排放隨著混合比的增加而降低。這是因為生物柴油具有比石油柴油更高的氧含量和沒有或更低的芳香族含量。然而,在B80和B100情景中,由於生物柴油的高粘度特性,粒狀污染物和持久性有機污染物的排放增加,這對燃燒過程產生負面影響。由於其較低的燃燒效率,生物柴油對EURO III發動機排放的影響更為明顯,因此使用生物柴油改善燃燒可顯著降低PCDD/ Fs。由於其熱穩定性和較低的氧化SO2電位,HDDE中已採用銅沸石選擇性催化還原(CuZ-SCR)來還原NOx。然而,由於銅的存在以及工作溫度與形成POP的最佳溫度範圍相吻合,因此存在從HDDE中增加POP排放量的潛在風險。因此,本研究調查了在50%和75%的發動機負荷下,來自EURO I HDDE的CuZ SCR對PCDD / F、PCB、PBDD/F和PBB排放的影響。值得注意的是,PCDD / F和PCB的毒性排放分別增加了78.4%和201%。 PCDD / F的主要同源物是OCDD,OCDF,1,2,3,4,6,7,8-HpCDD和1,2,3,4,6,7,8-HpCDF和PCB-105,PCB- 118和PCB-77(用於PCB)。與PCDDs相比,形成了更多的PCDF,而較低的氯化同類物的增加量大於較高的氯化同類物。CuZ-SCR後,PBDD / F濃度也從不可檢測的水平(ND)增加到0.247 pg TEQ Nm-3(4.00 pg TEQ/L)。但是,只有1,2,3,4,6,7,8-HpBDF和OBDF有助於濃度。在SCR之後,PBBs是唯一減少的化合物。通過SCR之前和之後檢測到的唯一同系物是PBB15。該研究首次表明,在不對現有APCD進行任何修改的情況下,可以有效並可行性的減少與MSWI冷啟動的大量排放,且對現有APCD的運營成本影響不大。此外,該研究對石油柴油/生物柴油比率對高密度HDDEs排放的影響提出完整的了解。最後,我們表明在HDDE的中高發動機負荷下,CuZ SCR可能是POP的來源。為了進一步研究CuZ SCR中的POP形成現象,還需要進行進一步的詳細研究。
The monitoring and control of toxic organic pollutant emissions including persistent organic pollutants (POPs) and polyaromatic hydrocarbons (PAHs) from municipal solid waste incinerators (MSWIs) and heavy-duty diesel engines (HDDEs) were studied. The aim was to address the key research gaps in the literature. Specifically, this included controlling the extreme POP emissions observed during the cold start-up of MSWIs. Also, for HDDEs, having a comprehensive study on the effect of low to high petrodiesel-biodiesel blend on PAH and POP emissions and the effect of an air pollution control device (APCD) used to treat traditional pollutant on POP emissions. The common start-up process adopted in MSWIs can generate extremely high concentrations of chlorinated and brominated POPs; for instance, 130 ng WHO-TEQ Nm-3 for polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), 42.6 ng WHO-TEQ Nm-3 for polychlorinated biphenyls (PCBs), and 60.4 ng Nm-3 for polybrominated biphenyls (PBBs), as measured in this study. Accordingly, a two-day start-up process yields PCDD/F and PCB emission quantities around 20 times higher than those from an entire year’s normal operation. In response, this study proposed some control strategies, including extensively cleaning the ash accumulated beneath the furnace beds of the combustion chambers and deposited on the wall of the superheaters and economizers and shortening the residence time of the flue gas at the POP formation window (250 ℃ – 450 ℃) in the combustion chambers. Also, advancing the injection time of activated carbon and lime to reduce POP emissions during the start-up processes. Findings show that the control strategies were highly effective and reduced all the other POP emission quantities by > 96 % and PBDEs by 61 %. The POP reductions were mostly attributed to strategies that reduced the potential for POP formation, which were, extensively cleaning the ash accumulated beneath the furnace beds of the combustion chambers and deposited on the wall of the superheaters and economizers and reducing the residence time of the flue gases in the combustion chamber within the POP formation temperature range. Yet, the effect of biodiesels on the emissions of PAHs and PCDD/Fs from HDDEs has only been studied using limited fuel blend ratios. To clarify the influence of using higher fractions of biodiesel on the emissions of toxic organic pollutants from diesel engines, in this research, the emissions of PM, PAHs, and POPs from EURO IV and EURO III HDDEs fueled by low to high waste cooking oil (WCO)-based biodiesel-petrodiesel fuel blends were studied, including D100 (0% biodiesel), B20 (20%), B40 (40%), B60 (60%), B80 (80%), and B100 (100%). The results for the EURO IV diesel engine showed that the PM and toxic organic pollutant emissions were reduced with increases in the blending ratio up until the B60 scenario when compared to the D100 scenario. This is because biodiesel has higher oxygen content and no or lower aromatic content than petrodiesel. Nevertheless, during the B80 and B100 scenarios, the PM and toxic organic pollutant emissions increased due to the high viscosity property of biodiesel, which negatively affected the combustion process. The biodiesel effect on the emissions from EURO III engine was more pronounced because of its lower combustion efficiency, and therefore the improvement in combustion using biodiesel resulted in greater PCDD/F reductions. Due to its thermal stability and lower potential of oxidizing SO2, Copper-zeolite selective catalytic reduction (CuZ-SCR) has been adopted in HDDEs to reduce NOx. However, because of the presence of Cu and the operating temperature coinciding with the temperature range optimal for POP formation, there is a potential risk for increased emissions of POPs from HDDEs. Therefore, this study investigated the effect of CuZ-SCR on PCDD/F, PCB, PBDD/F, and PBB emissions from a EURO I HDDE at 50% and 75% engine load. Notably, PCDD/F and PCB toxicity emissions increased by 78.4% and 201%, respectively. The dominant PCDD/F congeners were OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF and PCB-105, PCB-118 and PCB-77 for PCBs. More PCDFs were formed compared to PCDDs and lower chlorinated congeners increased more than the higher chlorinated ones. There was also an increase of PBDD/F concentrations from undetectable levels (ND) to 0.247 pg TEQ Nm–3 (4.00 pg TEQ L–1) after the CuZ-SCR. However, only 1,2,3,4,6,7,8-HpBDF and OBDF contributed to the concentrations. PBBs was the only compound measured that reduced after the CuZ-SCR. The only congener detected before and after the CuZ-SCR was PBB 15. The study is the first to show that the extreme emissions associated with the cold start-up of MSWIs can be reduced effectively and feasibly with no modifications to existing APCDs while having little influence on operational cost. In addition, the research presents a comprehensive understanding on the effect of petrodiesel-biodiesel ratio on emissions from HDDEs. Finally, we showed that CuZ-SCR could be a source of POPs under mid and high engine loads of a HDDE. Further detailed research is needed to conclusively study the POP formation phenomenon in CuZ-SCR.
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