臺灣博碩士論文加值系統

本研究針對生質物於快速裂解(fast pyrolysis)及慢速裂解(slow pyrolysis)所產製之生質油，探討快速裂解生質油混合丁醇及慢速裂解生質油混合丁醇液滴燃燒特性其生質油混摻丁醇比例為0 vol.%(純生質油)、50 vol.%、70 vol.%、90 vol.%及100 vol.%(純丁醇)，以懸掛單顆液滴之方式，在相同溫度723K引燃液滴，透過高速攝影同步紋影技術及化學螢光法分析生質油混摻不同丁醇比例之液滴燃燒行為，透過紅外顯熱像儀量測液滴表面溫度及利用熱重分析(TGA)串聯傅立葉紅外線光譜(FTIR)和氣相層析質譜法(GC-MS)分析燃油之特性。生質油的組成特性受到生質物中纖維素、半纖維素和木質素的裂解特性影響，因此生質油中富含多種化合物而當中含較多的脂肪族化合物，則會導致燃燒時產出芳香族化合物，而生質油混合丁醇明顯可以降低生成微粒前驅物的多環芳香烴及油品黏度和提高熱值。熱重分析中顯示生質油不同的重量變化。快速裂解生質油中包含較多的輕質組份(C2-C8)及水分，在低沸點(<434K)組份較容易揮發；然而，慢速裂解油中則包含較多的重質組份(C16-C21)其化合物沸點也相對較高(>573K)，由於生質油屬於高濃度含氧有機物，容易發生聚合反應形成殘留物，在高溫中持續加熱導致殘留物燃燒，產生放熱反應；在受熱蒸發過程中主要的官能基可以分為兩個部分，第一部分為輕質化合物在低溫的裂解，其吸熱反應的產物主要含有O-H、C-H、C=C、C-O官能基；第二部分為重質化合物在高溫下的聚合和燃燒，其放熱反應時主要產物為CO2及CO。在高比例混合丁醇(10 % bio-oil/90 % butanol,PF10B90)的熱分解動力學，303K~412K活化能為60.61KJ/mol，在723K~756K活化能則為8.83 KJ/mol，表示可以改善揮發性物質的釋放組份，混合燃油中揮發階段的活化能逐漸增加和燃燒階段的活化能逐漸降低，有助於明顯改善生質油的燃燒性能。快速裂解和慢速裂解生質油且皆有較劇烈的氣泡膨脹或微爆。由於慢速裂解生質油揮發性較低的影響，造成蒸發時間較長，且高黏度會抑制揮發性組分擴散到表面，此現象是因為表面張力的增加，抑制了液滴表面液相到氣相的質量擴散；當混合了高比例的丁醇，使液體密度降低，而密度低的燃料從高濃度區向火焰區域擴散的速度增加，使燃燒時間變短，此外，表面溫度上升時間逐漸減少，由於液體密度改變了氣體擴散係數，而導致影響液滴表面的升溫時間。生質油液滴燃燒的C2*化學螢光亮度幾乎包含著液滴的火焰下游區域，表示大部分燃料在此反應，C2*化學螢光的輻射強度增加，特別為火焰尾流區域，此反應可能為中間產物與碳微粒在尾端燃燒。當生質油混合丁醇時，C2*化學螢光逐漸減弱，這表示減少微粒的形成。另一方面，生質油混合丁醇的Grashof number (Gr數)明顯地增加，由於丁醇揮發性增強了史蒂芬通量，本研究在較高混合丁醇比例下和產生較高的Gr數，皆有助於減少微粒煙尾的生成。

In this study, the bio-oils produced by fast pyrolysis and slow pyrolysis were used to investigate the combustion characteristics of droplets of bio-oil blended with butanol fuels The proportion of the bio-oil blended with butanol was 0 vol.% (pure bio-oil), 50 vol.%, 70 vol.%, 90 vol.% and 100 vol.% (pure butanol), respectively. Using a suspended droplet heating device at the same temperature 723K.When the droplets were burned, the droplet combustion behaviors of the bio-oil blended with different butanol ratios were analyzed by high-speed photography synchronous schlieren and chemiluminescence. The surface temperature of the droplets were measured by the infrared thermal imaging camera. The characteristics of fuels were analyzed by using thermo-gravimetric analyzer (TGA) coupled with a fourier-transform infrared spectrometers (FTIR) and the gas chromatography mass spectrometry (GC-MS). The composition of the bio-oil was affected by the pyrolysis characteristics of cellulose, hemicellulose and lignin in the biomass. Therefore, the bio-oil contained more aliphatic compounds, leading to produce aromatic compounds when bio-oil burned. When bio-oil blended with butanol, the polycyclic aromatic hydrocarbons of the soot precursors decreased, the viscosity of mixed bio-oils decreased, and the heat value of mixed bio-oils increased. The weight change of the pure bio-oil in the TGA was observed. The fast pyrolysis bio-oil contained more water and light components (C2-C8) evaporating in low boiling point (<434K). However, the slow pyrolysis bio-oil contained more heavy components (C16-C21) which had relatively high boiling points (>573K). Since the bio-oil belonged to a high concentration of oxygen-containing organic matter, the residues of bio-oil was produced by a polymerization reaction. The residues were continuously heated at a high temperature to generate exothermic reaction. The main functional groups in the thermal evaporation process could be divided into two parts. The first part was O-H, C-H, C=C, and C-O functional groups of the substances produced during the endothermic reaction when the light compounds pyrolysised at low temperature; the second part was the products, CO2 and CO, produced during the exothermic reaction when heavy compounds polymerized and combustion at high temperature. In the thermal decomposition kinetics, high-mixed butanol (10 % bio-oil/90 % butanol, PF10B90) had activation energy (60.61 KJ/mol) from 303K to 412K and activation energy (8.83 KJ/mol) from 723K to 756K, indicating that the release of volatile substances could be improved. The activation energy of the volatile stage in the Bio-oil Blended with Butanol Fuels gradually increased and the activation energy in the combustion stage gradually decreased, which significantly improved the combustion performance of the mixed bio-oils. Fast pyrolysis bio-oil and slow pyrolysis bio-oil both had bubble growth or micro-expansion. Because the slow pyrolysis bio-oil was low volatile, it caused the longer evaporation time of the droplets. The high viscosity inhibits the diffusion of the volatile components to the surface because the surface tension was increased and the mass diffusion of the liquid phase to the gas phase on the surface of the droplet was suppressed. When a high proportion of butanol was mixed, the density of the liquid was lowered. The diffusion rate of the low-density fuel from the high concentration zone to the flame zone was increased, so that the burning time was decreased. In addition, the surface temperature rise time was gradually decreased due to the change of liquid density and the gas diffusion coefficient, which affected the heating time of the droplet surface. The C2* chemiluminescence of the combusted bio-oil droplets surrounded in the flame downstream zone of the droplet, indicated that most of the fuel was reacted here. The radiation intensity of the C2* chemiluminescence was increased, especially in the flame wake zone. This reaction may be the intermediate product and the soot burned. When the butanol blended in bio-oil, the radiation intensity of the C2* chemiluminescence gradually decreased, which indicated that the soot formation was reduced. On the other hand, The Gr number of the bio-oil with butanol increased significantly, because the butanol volatility enhanced the Stefan flux. In this study, higher mixed butanol ratios and producing higher Gr numbers both helped to reduce the formation of the soot tail.

摘要...............................i
Abstract..........................ii
誌謝..............................iv
目錄..............................v
表目錄............................viii
圖目錄............................ix
符號說明..........................xi
第一章 前言...................................1
1.1 為何使用生質燃料?.........................1
1.2生質物裂解產油技術.........................2
1.2.1 生質物快速裂解..........................3
1.2.2 生質物慢速裂解..........................3
1.3 為何研究生質液滴燃燒?......................3
1.4 研究重點..................................4
1.5 論文架構..................................5
第二章 生質液態燃料特性及應用問題...............6
2.1 生質液態燃料特性...........................6
2.1.1 生質物性質..............................6
2.1.2 裂解製程性質............................18
2.2生質液態燃料動力機械測試....................24
2.3生質液態燃料噴霧燃燒........................27
第三章 液滴燃燒................................33
3.1液滴蒸發與燃燒基礎理論.......................36
3.2多組份液滴燃................................42
3.3生質油/醇類液滴燃燒..........................46
3.4小結........................................48
第四章 實驗設備與方法............................49
4.1單顆液滴燃燒實驗設備..........................49
4.1.1 背光法量測................................50
4.1.2 火焰影像量測..............................51
4.1.3 顯微影像量測..............................52
4.1.4 紅外線熱像儀量測...........................52
4.1.5 自然螢光法量測.............................54
4.1.6 紋影流場可視化技術.........................57
4.2 燃油備製....................................60
4.2.1 快速裂解系統...............................60
4.2.2 慢速裂解系統...............................61
4.2.3 混合燃油備製...............................62
4.2.4燃油特性分析及方法...........................63
4.3 TG-FTIR量測系統..............................65
4.3.1動力學計算..................................67
第五章 結果與討論.................................69
5.1 燃油特性分析..................................69
5.1.1 生質油氣相層析質譜分析.......................69
5.1.2 熱重分析....................................71
5.1.3 傅立葉轉換紅外光譜分析.......................76
5.2 生質油混合丁醇液滴燃燒特性.....................78
5.2.1 液滴燃燒直接影像............................78
5.2.2 液滴燃燒直徑變化............................80
5.2.3 液滴表面溫度................................82
5.2.4 液滴燃燒火焰影像.............................83
5.2.5 液滴燃燒內部影像觀測.........................86
5.2.6 液滴燃燒化學螢光分析.........................89
5.2.7 生質油混合不同比例丁醇Grashof number之變化....92
第六章 結論及未來工作..............................94
6.1 結論..........................................94
6.2 未來工作......................................97
參考文獻..........................................99
Extended Abstract................................115

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