臺灣博碩士論文加值系統

近來全球各地出現缺電與化石燃料飆漲的能源危機，促使各國迫切尋求替代的能源，再生能源成為各國重視的問題之一，其中最廣泛應用的為生質能。以務農為主的南台灣，每日皆會產生大量之體積大、含水率高、熱值低的農業廢棄物，其處置及再利用等問題是我們所關注的議題。對此，本研究選用臺南市特有及種植面積最廣、產量最大的作物所產生的農業廢棄物，以酪梨籽、龍眼廢棄物（籽與殼）、及柚子枝作為材料，搭配實驗設計進行微波加熱焙燒(torrefaction)，同時，混配臺灣各餐廳、速食店、及食品加工業大量產出且相對高熱值的廢食用油，以克服生質物對微波(microwave)吸收力弱及微波加熱不均等問題，期望可同時處理並資源化不同類型的廢棄物，以產製能源、環境、經濟有效益的替代能源。對此，本研究以田口方法進行實驗設計，實驗因子包含焙燒溫度（250-350 ℃)、持溫時間（5-15 min）、含油量（0-15%）、及含水率（3-12%），並評估微波焙燒後產物的物化特性與品質，以找出產製優良生物炭的最適化操作參數與組合。接著，評估焙燒前後的熱解機制、點燃及燃燼溫度，並將生物炭與標準規範進行比較，另外，討論產製生物炭的能源效益、環境衝擊減緩及成本效益。
研究結果發現，以三種生質廢棄物與廢食用油微波共焙燒，產製之生物炭的熱值（22-24 MJ/kg）及固定碳含量（27-34 wt%）大幅提升，且固體產率及能量產率皆可高於70%以上，而能量密度介於1.1-1.2。此外，三種原料以田口法進行實驗設計，並以「熱值」作為品質目標，發現各原料因子對實驗的影響，都是溫度、含油量影響最大；接續，發現實驗設計最適化的條件均在焙燒溫度為350 ℃、含油量為15%、最低含水率為3%，其中各材料最佳的持續時間不同（酪梨籽為5 min、龍眼廢棄物及柚子枝則為15 min）。
經元素分析結果，發現共焙燒後生物炭的碳化程度增加，且加劇脫氧程度。三種生質原料與廢食用油共焙燒後均發生H/C及O/C比下降的情況，且性質趨近於煤炭。由微觀結構（SEM）分析，發現共焙燒後生物炭的表面結構被破壞，且表面被廢食用油吸附包覆，呈現油脂狀結構。經熱重分析（TGA）結果，得知共焙燒後生物炭的熱穩定性明顯提高，而在一階的動力反應參數下，共焙燒後生物炭的活化能（Ea）提升，頻率因子（A）降低，加入廢食用油會使活化能升高，生物炭的活化能在脫揮發分及炭化階段較高，具高線性相關（R2＞0.9）。由燃燒特性結果，得知共焙燒後生物炭的燃料比（FR）雖略低於煙煤的FR（1.5-2.5），但將10%-20%生物炭混配煙煤進行混燒，將有利於其燃燒特性，使生物炭可燃性提高。生物炭的點燃及燃燼溫度均往高溫移動，表示產製的生物炭具有較佳的燃燒效率，且穩定性、安全性較高。與台電購煤標準相比，生物炭均可達到一般煙煤的標準，其中龍眼廢棄物與廢食用油共焙燒後生物炭可達高熱值煙煤的標準。
在能源效益方面，三種生質原料與廢食用油微波共焙燒後生物炭的能源投報率（EROI＝3－23）可大於社會可持續穩定發展的最低（EROI＝3）值。在環境衝擊方面，以實驗室規模模擬燃煤電廠混燒，將10%-20%生物炭混配煙煤進行混燒，可減少6%-16%的CO2排放。在成本效益方面，假設實廠處理1噸生質廢棄物，本技術處理所花費的成本可低於焚化處理方式，減少最多75%的成本，且將產製的生物炭作為生質燃料進行販售可淨賺2,820-2,888元。經上述驗證，本研究以「微波共焙燒廢棄生質物與廢食用油以產製生物炭」，是一種可行的處理技術，且可減緩環境衝擊同時資源化不同廢棄物，達成廢棄物回收再利用同時提高能源自主性。

Global warming and conventional fossil-fuel depletion have augmented the value of renewable energy. Agricultural wastes, known as biomass materials, have an important potential to produce sustainable energy from renewable fuels. Morever, ablout 6×104–7×104 metric tons of waste cooking oil (WCO) in Taiwan produced per year. This increase may leads to environmental pollution if disposed of untreated. To overcome this problems, microwave torrefaction was examined via taguchi approach for its technical, energy, environmental, and economic feasibility in co-torrefaction of agricultural and fruit waste biomass (such as Persea americana seeds (PAs), Dimocarpus longan seeds and shells (DLw), and Citrus maxima branches (CMb)) and WCO simultaneously to product biochar. Key operating parameters, including different temperatre (250–350 ℃), reaction time (5–15 min), oil content (0–15%), and moisture content (3–12%).
The results exhited that the the effects of influencing factors based on higher heating value (HHV) decreasing order as follows: temperatre> oil content> moisture content> reaction time (for PAs and DLw) and temperature> oil content> reaction time> moisture content (for CMb). The blending of three different biomasses with WCO increased HHV (22–24 MJ/kg), fixed carbon content (27–34 wt%), energy density (1.1–1.2) with more than 70% emergy yield. The optimal HHV were achieved by the biochar of blending biomass and WCO after co-torrefaction at 350 ℃ for 5 min (for PAs) or 15 min (for DLw and CMb) with oil content of 15%, and low moisture content. The H/C and O/C atomic ratios of the biochar from blending of biomass with WCO was close to that of lignite. The deoxygenation, dehydration, and decarboxylation of the torrefied or co-torrefied samples resulted in the the weak intensities and chemical bond breakage in terms of fourier transform infrared (FTIR) spectroscopy, and displated relatively rough with a grease-like structure in terms of scanning electron microscopy (SEM). The biochar obtained through three different biomasses blending with WCO can upgrade the thermal stability, activation energy (Ea) and ignition and combustion temperatures. In terms of combustion characteristic, the biochar had a high fuel ratio (FR> 1.5),when 10%–20% biochar was co-fired with 80%–90% bituminous coal.
The HHV of optimal biochar can achive the specification of the general bituminous coal in Taiwan Power Company, which means the biochar was an excellent coal substitute for power generation. The energy return on investment (EROI) of the biochar reached 3-23, which was higher than the minimum EROI (approximately 3) proposed for biomass-based biofuels. Co-firing 10%–20% biochar with bituminous coal is favorable for reducing GHG emissions by 6%-16%, and 75% less cost than the traditional biomass waste disposal method (such as inineration). Therefore, microwave-assisted co-torrefaction is a potential technology for sloving biomass waste and WCO disposal problems, and biofuel production, and enhanced energy efficiency as well as environmental and economical friendliness. It is expected that this study can provide reference for the development and application of localized biofuels in Taiwan.

摘要
Abstract
誌謝
目錄
表目錄
圖目錄
第一章 前言
1.1 研究源起
1.2 研究目的
第二章 文獻回顧
2.1 生質能源發展與現況
2.2 廢棄物種類特性及處理現況
2.2.1 生質物種類及特性
2.2.2 生質物轉換能源技術
2.2.3 廢食用油來源及特性
2.2.4 廢食用油處理現況
2.3 焙燒技術簡介
2.3.1 焙燒原理及應用
2.3.2 焙燒反應動力機制
2.4 微波加熱原理及應用
2.4.1 微波原理
2.4.2 微波之應用
2.5 生質燃料品質特性
2.5.1 燃料標準
2.5.2 燃燒特性
2.6 田口法實驗設計
第三章 研究材料與方法
3.1 研究架構
3.2 實驗材料與設備
3.2.1 材料來源及特性
3.2.2 實驗設備及藥品
3.3 實驗設計及方法
3.3.1 生質物與廢食用油共焙燒含油量試驗
3.3.2 田口法實驗設計
3.3.3 實驗步驟
3.4 分析方法
3.4.1 產物特性分析
3.4.2 產物能源、環境效益評估
第四章 結果與討論
4.1 微波焙燒生質物與廢食用油前後特性評估
4.1.1 熱值分析
4.1.2 近似分析
4.1.3 固體產率、能量產率及能量密度分析
4.1.4 小結
4.2 產製優良生物炭的實驗設計結果
4.2.1 實驗因子影響
4.2.2 變異數分析(ANOVA)
4.2.3 最適化條件確認
4.2.4 小結
4.3 生物炭物化特性分析
4.3.1 元素分析
4.3.2 表面化學結構組成分析
4.3.3 表面形貌分析(SEM)
4.3.4 熱穩定性分析
4.3.5 小結
4.4 生物炭燃燒特性及反應動力學
4.4.1 燃燒特性
4.4.2 燃燒動力反應機制
4.4.3 小結
4.5 生物炭再利用成效評估
4.5.1 製成生物炭品質規範
4.5.2 能源效益
4.5.3 環境衝擊減緩評估
4.5.4 產製生物炭之成本效益評估
4.5.5 小結
第五章 結論與建議
5.1 結論
5.2 建議
參考文獻
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