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Catalytic activity of zeolitic and mesostructured catalysts in the cracking of pure and waste polyolefins

机译:沸石和介孔结构催化剂在纯聚烯烃和废聚烯烃裂解中的催化活性

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Six acid solids of varying acid and textural characteristics has been investigated for their catalytic activity in the degradation of plastic polymers using thermogravimetric and differential thermal analysis. The polymers included pure low-density polyethylene, pure high-density polyethylene and two samples of recycled polyethylene of urban and agricultural origins. The catalysts were three zeolitic materials (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and three mesostructured solids (sol-gel Al-MCM-41 (sg), hydrothermal Al-MCM-41 (hy) and Al-SBA-15). The catalytic activity of each acid solid has been related to its capacity to shift the degradation reaction to lower temperatures. Despite showing strong acid properties, standard ZSM-5 zeolite exhibited a very low catalytic activity on most plastics, which was attributed to diffusional impediments that affected the access of the bulky polymer molecules to its internal active sites. These impediments were partly overcome in the case of Beta zeolite and even more markedly with nanocrystalline n-ZSM-5, which exhibited the strongest catalytic activity due to a combination of strong acid properties and large external surface area. Owing to their non-crystalline nature, mesostructured solids showed weaker acid properties than their zeolitic counterparts. However, this disadvantage was partly compensated by the presence of larger pores that reduced diffusional hindrances. Thus, Al-MCM-41 (hy) exhibited one of the highest catalytic activities, largely surpassing the performance of crystalline solids with stronger acid properties. The catalytic activity of all the acid solids tested in this work was significantly reduced when they were used on waste plastics. This deactivating effect was more notable in mesostructured solids.
机译:使用热重分析和差热分析研究了六种具有不同酸和质地特性的酸固体在塑料聚合物降解中的催化活性。这些聚合物包括纯低密度聚乙烯,纯高密度聚乙烯和两个城市和农业来源的回收聚乙烯样品。催化剂是三种沸石材料(标准ZSM-5,纳米晶体n-ZSM-5和Beta)和三种介孔结构固体(溶胶-凝胶Al-MCM-41(sg),水热Al-MCM-41(hy)和Al- SBA-15)。每种酸固体的催化活性与其将降解反应转移至较低温度的能力有关。尽管显示出强酸性质,标准ZSM-5沸石在大多数塑料上仍显示出非常低的催化活性,这归因于扩散障碍,影响了大分子聚合物分子进入其内部活性位。这些障碍在Beta沸石的情况下得到了部分克服,而纳米晶n-ZSM-5则更为明显,由于强酸性质和较大的外表面积相结合,纳米晶显示出最强的催化活性。由于它们的非晶体性质,介孔结构的固体显示出比其沸石对应物弱的酸性质。但是,此缺点已通过减小扩散障碍的较大孔的存在而得到部分补偿。因此,Al-MCM-41(hy)表现出最高的催化活性之一,大大超过了具有更强酸性的结晶固体的性能。当将这些酸性固体用于废塑料时,其催化活性均大大降低。这种减活作用在介孔结构固体中更为明显。

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