隨著全球人口的增加和生活水平的提高，過去幾十年來全球範圍內的能源需求大量增加。在眾多正在開發的可再生能源和替代燃料中，生質能源是最有前途的可再生能源之一，並且可以滿足替代化石燃料及減少溫室氣體排放的需求。氣化、液化、裂解和發酵等方式都是常見可將生質物轉化為氣體或液體燃料的前處理過程。生質物中的成分包含了纖維素（一種聚合物葡聚醣），半纖維素（也稱為多醣），木質素（一種複雜的酚醛聚合物），有機萃取物和無機礦物質（也稱為灰分）。 其中纖維素，半纖維素和木質素為生質物的主要組成成分，含量佔了其重量百分比超過90%。本研究也透過粒子群優化法輔助動力學模型計算出等溫焙燒和裂解反應下之活化能和前置因子，並有助於反應器之設計和有效地產生生物燃料和生質能。
第一部分主旨是為了透過使用等溫焙燒的兩步法模型與粒子群優化法相結合併使用傅里葉轉換紅外光譜儀（Fourier-transform infrared spectroscopy, FTIR）來鑑定焙乾過程中釋放出的氣體，研究纖維素，半纖維素和木質素的焙燒動力學。在250 °C等溫焙燒前半纖維擁有最嚴重的重量損失，而在300 °C等溫焙燒中，纖維素成為重量損失最大的成分，其次是半纖維素，最後則是木質素。此外，使用TG-FTIR收集並分析了等溫焙燒過程中木質纖維素的三種主要成分所釋放的揮發性氣體。在等溫焙燒下，纖維和半纖維收集的氣體中CO和CO2占主要成分，而木質素測得擁有CH4的產生。纖維素，半纖維素和木質素的焙燒動力學分別在166-260、48-55和59-70 kJ mol-1的範圍內。根據等溫焙燒動力學計算，在300 °C的焙燒下，纖維素具有最大的揮發性產物，其次是最終產物C。在半纖維素的等溫焙燒下，最終產物C的產率約為60.04-74.05 ％，第二多普遍的產物是中間固體B，其含量為3.34-8.20 ％。木質素在300 °C之前的等溫焙燒下產生的中間固體B最多，佔86.41-97.50 ％。最後，在等溫焙燒兩步法中，反應二擁有相較於反應一來的大的的活化能。
在本研究的第二部分中，為了更深入的了解木質纖維素生質物的複雜熱裂解過程，本篇研究使用了熱重分析儀(Thermogravimetric analyzer, TGA)對纖維素，半纖維素和木質素進行熱裂解反應。此外，本研究成功使用了粒子群優化（PSO）法結合了獨立平行反應（IPR）進行動力學模型計算。纖維素，半纖維素和木質素的IPR動力學模型可分別使用1個偽反應，4個偽反應和5個偽反應進行建模，並且可以獲得高於95 ％的良好擬合質量（少數情況適用於木質素）。本研究也探討了分別採用1、5、20和40 °C·min-1四種不同的加熱速率在對熱解過程的影響。由於樣品與加熱環境之間發生熱滯效應，因此造成導數熱重分析曲線（derivative thermogravimetric, DTG）峰移至更高的溫度範圍。總體而言，纖維素，半纖維素和木質素的熱降解溫度範圍分別在269-394、170-776和127-791 °C之內。木質纖維素熱解的動力學有利於反應器設計，以有效地產生生物燃料和生物能。

With an increasing global population and increasing living standards, there has been a massive increase in energy demand worldwide over the last few decades. Among the renewable energy and alternative fuels under development, biomass energy or bioenergy is one of the promising resources to match the requirements of substituted fossil fuels for reducing greenhouse gas emissions. Torrefaction, pyrolysis, combustion, and gasification are the common thermochemical conversion processes to convert lignocellulosic and non-lignocellulosic biomass into biofuels. Cellulose, hemicelluloses, and lignin are the three main components of lignocellulosic biomass. Torrefaction is a thermochemical process that produces solid energy carriers with improved fuel characteristics. This process involves heating of biomass at a temperature range of 200–300 °C and in an inert or oxygen-reduced environment within a desired time interval.
The first part aims to investigate the thermal degradation kinetics of cellulose, hemicelluloses, and lignin by using a two-step model of isothermal torrefaction combined with an optimized algorithm and using the Fourier Transform Infrared Spectroscopy to identify the gas released during the torrefaction process. The most severe weight loss in isothermal torrefaction before 250 °C is hemicelluloses, while using 300 °C isothermal torrefaction, cellulose became the component with the largest weight loss, followed by hemicelluloses, and finally lignin. In addition, using the TG-FTIR collected and analyzed the volatile gas released by the cellulose, hemicelluloses, and lignin during isothermal torrefaction. Under isothermal torrefaction, CO and CO2 dominate in the gas collected by cellulose and hemicellulose while CH4 production has been measured by lignin. The torrefaction kinetics of cellulose, hemicelluloses, and lignin are in the range of 166-260, 48-55, and 59-70 kJ/mol, respectively. From the calculation by the torrefaction kinetics, at 300 °C torrefaction, cellulose has the most volatile products, followed by the final residual C. Under the isothermal torrefaction of hemicelluloses, the final residual C yield is approximately 60.04-74.05 % and the second most prevalent product is the intermediate solid B with 3.34-8.20 %. Lignin produced the most intermediate solid B under isothermal torrefaction before 300 °C, accounting for 86.41-97.50 %. Finally, the activation energy of reaction number two appears to be greater than that of the isothermal torrefaction reaction number one under two stages.
For the second part, to understand the complex pyrolysis process of lignocellulosic biomass, three model components of cellulose, hemicelluloses (xylan), and lignin were pyrolyzed using a thermogravimetric analyzer. An independent parallel reaction (IPR) kinetic model was optimized using a particle swarm optimization (PSO) algorithm. The IPR kinetic models of cellulose, hemicelluloses, and lignin could be modeled with 1 pseudo-reaction, 4 pseudo-reactions, and 5 pseudo-reactions, respectively, and good fit qualities higher than 95% can be achieved (except a few cases for lignin). Four different heating rates of 1, 5, 20, and 40 °C·min-1 were applied to examine the effect of heating rate on the pyrolysis process. When increasing the heating rate, the derivative thermogravimetric (DTG) peaks shifted to a higher temperature range, stemming from the thermal lag between the samples and heating environment. Overall, the temperature ranges of the thermal decomposition for cellulose, hemicelluloses, and lignin were within 269-394, 170-776, and 127-791 °C, respectively. The kinetics of lignocellulosic pyrolysis is beneficial for reactor design to efficiently produce biofuel and bioenergy.

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