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用于将聚乙烯回收转化为燃料的铁/超稳Y型分子筛催化剂上焦炭物种的鉴定

Identification of coke species on Fe/USY catalysts used for recycling polyethylene into fuels.

作者信息

Wang Yongli, Yan Na, Chen Zezhou

机构信息

Department of Engineering, Huzhou University 759 Erhuan North Road Huzhou 313000 China

出版信息

RSC Adv. 2024 Jul 12;14(31):22056-22062. doi: 10.1039/d4ra03608e.

Abstract

The Fe/USY catalyst used for converting plastic waste into fuels faces coking problems. A comprehensive understanding of coke distribution and structure is crucial for catalyst design, enabling resistance to coke deposition and facilitating regeneration. In this study, we analyze the coke deposition on Fe/USY catalysts after catalytic pyrolysis of polyethylene for fuel oil, and present insights into the coke distribution over the metal and acid sites, as well as its specific molecular structure. The coke distributes over both the metal and acid sites, exhibiting distinct TPO peaks corresponding to metal-site coke (370 °C) and acid-site coke (520 °C). The total coke yields range from 2.0% to 2.4%, with distribution on metal and acid sites dependent on Fe loading and acidity. Structurally, the coke is highly-condensed, containing more than four aromatic rings with limited alkyl groups. The acid-site coke is more condensed than the metal-site coke, showing lower H/C ratios (0.5-0.75) relative to the acid-site coke (0.75-0.9). Identified by MALDI-TOF mass analysis, the predominant molecular structures of the coke located on metal and acid sites are illustrated. The metal-site cokes typically exhibit 4-7 aromatic rings, while the acid-site cokes display even greater condensation with 5-12 aromatic rings.

摘要

用于将塑料废物转化为燃料的铁/超稳Y型分子筛(Fe/USY)催化剂面临着积炭问题。全面了解焦炭的分布和结构对于催化剂设计至关重要,这有助于提高催化剂对积炭的抗性并促进其再生。在本研究中,我们分析了聚乙烯催化热解制燃料油后铁/超稳Y型分子筛催化剂上的积炭情况,并深入探讨了焦炭在金属和酸性位点上的分布及其具体分子结构。焦炭分布在金属和酸性位点上,分别在370℃和520℃出现对应于金属位点焦炭和酸性位点焦炭的明显程序升温氧化(TPO)峰。总焦炭产率在2.0%至2.4%之间,其在金属和酸性位点上的分布取决于铁负载量和酸度。在结构上,焦炭高度缩合,含有四个以上的芳香环且烷基有限。酸性位点焦炭比金属位点焦炭缩合程度更高,相对于金属位点焦炭(H/C比为0.75 - 0.9),其H/C比更低(0.5 - 0.75)。通过基质辅助激光解吸电离飞行时间质谱(MALDI - TOF)分析确定了位于金属和酸性位点上的焦炭的主要分子结构。金属位点焦炭通常具有4 - 7个芳香环,而酸性位点焦炭则具有5 - 12个芳香环,缩合程度更高。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0042/11240219/96924c2e3bb3/d4ra03608e-f1.jpg

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