應用催化裂解技術評估熱塑型塑膠轉換能源之可行性研究;Evaluation on the feasibility of converting thermoplastics into energy by catalytic pyrolysis

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Title:	應用催化裂解技術評估熱塑型塑膠轉換能源之可行性研究;Evaluation on the feasibility of converting thermoplastics into energy by catalytic pyrolysis
Authors:	蔡明志;Tsai, Min-Chih
Contributors:	環境工程研究所
Keywords:	丙烯腈-丁二烯-苯乙烯共聚物;聚甲基丙烯酸甲酯;熱裂解;催化劑;催化熱裂解;Acrylonitrile Butadiene Styrene (ABS);Poly methyl methacrylate (PMMA);pyrolysis;catalyst;catalytic pyrolysis
Date:	2022-09-27
Issue Date:	2022-10-04 12:26:44 (UTC+8)
Publisher:	國立中央大學
Abstract:	本研究利用直立式固定床反應爐，探討丙烯腈-丁二烯-苯乙烯共聚物(Acrylonitrile Butadiene Styrene, ABS)及聚甲基丙烯酸甲酯(Poly methyl methacrylate, PMMA)兩種熱塑型塑膠，催化熱裂解轉換為能源之可行性，其中試驗條件包括熱裂解溫度650°C、1:1摻混比例及添加5–15 wt.%之自製鐵鎳基催化劑等條件。研究結果顯示，ABS熱裂解產物以氣體為主，產量為55 wt.%，其次為38 wt.%之裂解油，此外，添加10 wt.%催化劑之條件下，裂解反應有最大之氣體產物產生。PMMA因其化合物特性，導致裂解產物主要以氣體為主，產量為85 wt.%，然當添加10 wt.%催化劑之條件時，裂解油之產量約增加至13 wt.%。摻混1:1之ABS與PMMA條件時，裂解油產量由未添加催化劑之17.14 wt.%，增加至添加15 wt.%催化劑之24.0 wt.%。裂解油產物主要分為輕質油及重質油，主要均以碳、氫、氧及氮元素所組成，其中ABS裂解油之熱值，則介於3,354 kcal/kg至4,548 kcal/kg之間，且裂解油所含之水分含量約介於0.11%至4.98%。另根據裂解油之黏滯度分析結果顯示，輕質油之黏滯度約為4.52 cP至12.90 cP，均較重質油之16.47 cP–124.97 cP為低，主要原因係與裂解油之化合物種有關。至於1:1摻混之條件下，裂解油之熱值介於3,354 kcal/kg至4,382 kcal/kg之間，與ABS及PMMA個別裂解反應產生裂解油之熱值，極為相似。根據ABS衍生輕質油之化合物物種分析結果顯示，化合物含碳數目主要集中在C7-C9，且以芳香族化合物為主，並且隨著催化劑的添加，其含碳數目化合物之分布，呈現上升趨勢。此外，ABS衍生重質油之化合物物種，則以C10-C16為主，且均以芳香族化合物種類居多。至於 PMMA 衍生之裂解油，主要以PMMA單體（甲基丙烯酸甲酯，MMA）之含氧化合物，大約占90%，後續若能進一步提煉分離，將可做為再合成聚合物之單體化合物。整體而言，本研究已成功驗證ABS及PMMA共同催化裂解之可行性，同時依據相關衍生裂解油之物種鑑定分析結果，相關成果應有助後續相關裂解技術之選擇，以及工程應用之參考依據。 ;This research investigated the feasibility of converting two types of thermoplastics, including Acrylonitrile Butadiene Styrene (ABS) and Polymethyl methacrylate (PMMA), into energy using a vertical fixed bed reactor. The pyrolysis conditions included the pyrolysis temperature of 650°C, blending ratio (1:1), and 5-15 wt.% self-made iron-nickel-based catalyst addition. The experimental results show that the pyrolytic gaseous products are dominant and yield is approximately 55 wt.%. The pyrolytic oil yield is approximately 38 wt.%. In the case of adding 10 wt.% catalysts, the pyrolytic gaseous product presents the maximum gas product yield. However, due to the PMMA characteristics, the pyrolytic product derived from PMMA is mainly gas corresponding to 85 wt.% yields. On the other hand, the pyrolytic oil yields 13 wt.% with the catalyst addition increasing to 10 wt.%. In the case of 1:1 ABS:PMMA blending, the pyrolytic oil yield increased from 17.14 wt.% to 24.0 wt.% with the catalyst addition increasing from 0% to 15 wt.%. The pyrolytic oils include light and heavy fraction oil containing carbon, hydrogen, oxygen, and nitrogen. The heating value of the pyrolytic oil derived from ABS is ranged between 3,354 kcal/kg and 4,548 kcal/kg. Meanwhile, the moisture content of pyrolytic oil is approximately 0.11%–4.98%. Based on the analysis results of pyrolytic oil viscosity, the light fraction oil viscosity (4.52 cP–12.90 cP) is lower than that of heavy fraction oil (16.47 cP–124.97 cP). It implied that the viscosity is related to the speciation of pyrolytic oil. On the other hand, in the pyrolytic oil derived from 1:1 ABS: PMMA blending, the heating value is ranged between 3,354 kcal/kg and 4,382 kcal/kg. It is similar to the pyrolytic oil derived from ABS and/or PMMA. According to the speciation of light fraction oil derived from ABS, the carbon number of light fraction oil compounds dominates in C7-C9. Meanwhile, aromatic compounds are the main speciation. The carbon number of compounds partitioning is increasing with the catalyst addition increasing. In addition, the heavy fraction oil derived from ABS is mainly C10-C16. The aromatic compounds are also the main speciation. However, the PMMA monomer (methyl methacrylate, MMA) derived from PMMA is approximately 90%. It implied that the MMA monomer compound could resynthesized the new polymer during further refining and purifying. In summary, this study has successfully verified the feasibility of catalytic pyrolysis of ABS and PMMA. Meanwhile, based on the speciation identification of pyrolytic oils, the relevant results should be helpful for the subsequent selection of pyrolysis technologies and references for engineering applications.
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