预测框架和碳氢化合物结构对沸石催化β-分裂的影响。

IF 4.4 3区 化学 Q2 CHEMISTRY, PHYSICAL
Yannick Ureel , Konstantinos Alexopoulos , Kevin M. Van Geem , Maarten K. Sabbe
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引用次数: 0

摘要

开发改良型沸石对于新型可持续工艺(如塑料废弃物的催化热解)至关重要。本研究利用密度泛函理论研究了烷基链长度、不饱和键和分支如何影响四种沸石框架中的β-裂解动力学,这是碳氢化合物裂解过程中的一个关键反应。在 FAU、MFI、MOR 和 TON 中,对 6 至 12 个碳原子的 23 种碳氢化合物的活化焓进行了评估。对支链和线性烯烃和二烯烃反应物进行β-裂解的考虑表明了反应物结构如何影响内在裂解动力学,这与塑料废料原料的催化裂解尤其相关。研究发现,共振稳定、感应效应和孔隙稳定等内在化学效应对活化焓有重要影响。此外,为了快速预测四种沸石中各种分子的β-裂解活化势垒,还开发了一种预测性基团相加模型,其中包含一种新的所谓 "孔隙限制描述符"。所获得的模型可作为沸石催化裂解反应详细动力学模型的输入。在碳氢化合物裂解过程中获得的基本见解与实验观察结果非常吻合,有助于改进沸石的合理设计。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Predicting the effect of framework and hydrocarbon structure on the zeolite-catalyzed beta-scission†

Predicting the effect of framework and hydrocarbon structure on the zeolite-catalyzed beta-scission†
Developing improved zeolites is essential in novel sustainable processes such as the catalytic pyrolysis of plastic waste. This study used density functional theory to investigate how alkyl chain length, unsaturated bonds, and branching affect β-scission kinetics in four zeolite frameworks, a key reaction in hydrocarbon cracking. The activation enthalpy was evaluated for a wide variety of 23 hydrocarbons, with 6 to 12 carbon atoms, in FAU, MFI, MOR, and TON. The consideration of both branched and linear olefin and diolefin reactants for the β-scission indicates how the reactant structure influences the intrinsic cracking kinetics, which is especially relevant for the catalytic cracking of plastic waste feedstocks. Intrinsic chemical effects, such as resonance stabilization, the inductive effect, and pore stabilization were found to provide an essential contribution to the activation enthalpy. Additionally, a predictive group additive model incorporating a novel so-called “pore confinement descriptor” was developed for fast prediction of the β-scission activation barrier of a wide range of molecules in the four zeolites. The obtained model can serve as an input for detailed kinetic models in zeolite-catalyzed cracking reactions. The acquired fundamental insights in the cracking of hydrocarbons, relevant for renewable feedstocks, correspond well with experimental observations and will facilitate an improved rational zeolite design.
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来源期刊
Catalysis Science & Technology
Catalysis Science & Technology CHEMISTRY, PHYSICAL-
CiteScore
8.70
自引率
6.00%
发文量
587
审稿时长
1.5 months
期刊介绍: A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis. Editor-in-chief: Bert Weckhuysen Impact factor: 5.0 Time to first decision (peer reviewed only): 31 days
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