隨著全球對生質能與廢棄物再利用之重視日益提升，如何有效整合高含氧的生質物與高熱值的廢塑膠回收料，進而轉化為具商業潛力的再生燃料，已成為當前能源技術研究的重要課題。本研究以造紙製程中產生之黑液經過乾燥程序後變為乾燥黑液與廢聚乙烯為混摻原料，探討其於共熱裂解反應下的動力學特性、油品產率與組成變化，並評估碳酸鈣作為催化熱裂解之催化劑的潛在助益。本研究對於BLS與PE進行熱值、近似與元素分析，再使用熱重分析儀探討BLS與PE在N2環境下的熱裂解與共熱裂解特性，同時分析協同效應與活化能的變化，瞭解原料特性。協同效應顯示混摻過後在500°C 前具有明顯促進BLS失重的效應，提升裂解效率。此外，使用Starink方法計算活化能，發現摻入PE助於降低混摻比的平均活化能，使裂解反應更容易啟動。後續於管狀高溫爐進行催化共熱裂解實驗，並與田口實驗法做搭配。實驗後的油品以氣相層析質譜儀進行分析，以便於探討整體化合物成份趨勢變化。本研究找出三種最佳化標的，分別最大裂解油產油率實驗參數為:溫度550°C、混摻比BLS∶PE為40∶60、碳酸鈣添加5 %、N2流率為600 mL/min，最大裂解油產油率為41.25 %；最佳類HVO產油率實驗參數為:溫度550°C、混摻比BLS∶PE為55∶45、碳酸鈣添加5 %、N2流率為600 mL/min，最佳類HVO產油率為23.30 %，最大可用能實驗參數為:溫度550°C、混摻比BLS∶PE為85∶15、碳酸鈣添加10 %、N2流率為800 mL/min，最大可用能為78.95 %。

With the growing global emphasis on biomass energy and waste valorization, the effective integration of oxygen-rich biomass with high-calorific-value waste plastics for the production of value-added renewable fuels has become a critical research focus in energy technology. This study systematically investigates the co-pyrolysis behavior of dried black liquor solids (BLS), a papermaking by-product, and waste polyethylene (PE), with a focus on their reaction kinetics, pyrolysis oil yield, and product composition. The potential catalytic effect of calcium carbonate (CaCO₃) as a co-pyrolysis catalyst was also evaluated. The properties of BLS and PE were characterized through proximate analysis, elemental analysis, and calorific value determination. Thermogravimetric analysis was conducted under nitrogen atmosphere to study their individual and co-pyrolysis behaviors while evaluating synergistic effects and changes in activation energy to understand feedstock characteristics. The synergistic interactions clearly enhanced BLS overall weight loss upon blending before 500°C, thereby improving pyrolysis efficiency. Activation energies calculated via the Starink method showed that adding PE lowers the average of activation energy,facilitating the initiation of the pyrolysis reaction.Subsequent catalytic co-pyrolysis experiments were carried out in a tubular furnace, applying the Taguchi method for experimental design. The pyrolysis oils were analyzed by gas chromatography–mass spectrometry (GC/MS) to assess the compound distribution trends. Three optimal operating conditions were identified. The highest overall oil yield(41.25%) was achieved at 550°C with a BLS/PE blend ratio of 40:60, 5 wt% CaCO₃ catalyst loading, and a nitrogen flow rate of 600 mL/min. The maximum hydrotreated vegetable oil-like fraction yield(23.30%) occurred at 550 °C with a BLS/PE ratio of 55:45 under the same catalyst loading and nitrogen flow conditions. The highest exergy efficiency(78.95%) was obtained at 550°C with a BLS/PE ratio of 85:15, 10 wt% CaCO₃ addition, and a nitrogen flow rate of 800 mL/min.

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