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使用负载在钛改性二氧化硅上的与三齿配体络合的铬催化剂对乙烯进行选择性三聚。

Selective trimerization of ethylene using chromium catalysts complexed with tridentate ligands supported on titanium modified silica.

作者信息

Habibi Younes, Marefat Mohamadreza, Gharajedaghi Sajjad, Mohamadhoseini Masoumeh, Mohamadnia Zahra, Ahmadi Ebrahim

机构信息

Department of Chemistry, Institute for Advanced Studies in Basic Science (IASBS), Gava Zang, Zanjan, 45137-66731, Iran.

Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan, Iran.

出版信息

Sci Rep. 2025 May 25;15(1):18193. doi: 10.1038/s41598-025-02844-9.

DOI:10.1038/s41598-025-02844-9
PMID:40415013
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12104422/
Abstract

Alpha-olefins like 1-hexene play a crucial role in petrochemical industries. This study investigates the development of chromium-based catalysts featuring tridentate ligands for selective 1-hexene production via ethylene trimerization under optimized conditions: 80 °C, 25 bar ethylene, 40 mL anhydrous toluene, and MMAO (Al/Cr = 700/1) as the co-catalyst. Both homogeneous catalysts (Cr-SNS-D and Cr-SNS-B) and heterogeneous catalysts supported on SBA-15, including titanium-modified SBA-15 (Ti-SBA-15), were examined. The homogeneous catalysts exhibited remarkable selectivity (99.9%) and high catalytic activity, reaching 60,772 and 53,344 g 1-C₆ g Cr⁻¹ h⁻¹, respectively. Upon immobilization onto SBA-15 supports, a slight reduction in activity was observed; however, the introduction of titanium into the SBA-15 framework led to a 1.5-fold enhancement in catalytic performance (35,115 g 1-C₆ g Cr⁻¹ h⁻¹) and a significant reduction in polyethylene by-product formation. This study highlights the critical influence of support modification on catalytic behavior, demonstrating how tailored electronic interactions between the active sites and the support can optimize performance. The findings provide a valuable framework for designing more efficient chromium-based catalysts, bridging the gap between homogeneous and heterogeneous systems for improved 1-hexene production.

摘要

像1-己烯这样的α-烯烃在石化工业中起着至关重要的作用。本研究考察了具有三齿配体的铬基催化剂的开发,用于在优化条件下通过乙烯三聚反应选择性生产1-己烯:80°C、25巴乙烯、40毫升无水甲苯,以及甲基铝氧烷(Al/Cr = 700/1)作为助催化剂。研究了均相催化剂(Cr-SNS-D和Cr-SNS-B)以及负载在SBA-15上的非均相催化剂,包括钛改性的SBA-15(Ti-SBA-15)。均相催化剂表现出显著的选择性(99.9%)和高催化活性,分别达到60,772和53,344克1-C₆克Cr⁻¹小时⁻¹。负载到SBA-15载体上后,活性略有降低;然而,在SBA-15骨架中引入钛导致催化性能提高了1.5倍(35,115克1-C₆克Cr⁻¹小时⁻¹),并且聚乙烯副产物的形成显著减少。本研究突出了载体改性对催化行为的关键影响,证明了活性位点与载体之间定制的电子相互作用如何优化性能。这些发现为设计更高效的铬基催化剂提供了有价值的框架,弥合了均相和非均相体系之间的差距,以提高1-己烯的生产。

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