A meta-analysis and experimental comparison of the deactivation behavior of Mo/H-ZSM-5 and related catalysts under methane dehydroaromatization conditions

IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL
Jordy Ramos-Yataco , Xinrui Zhang , Geunho Han , Tobin J. Marks , Justin M. Notestein
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Abstract

CH4 exists in great abundance and is used primarily as an energy source. Methane dehydroaromatization (MDA) is a promising route for its direct transformation into liquid hydrocarbons and H2. Mo/H-ZSM-5 is the benchmark catalyst, but it deactivates rapidly by carbonaceous species formation. Here, we evaluated Mo/H-ZSM-5 formulations as a function of MoOx loading, SiO2/Al2O3 ratio, and Mo loading method for their impact on one-pass catalyst deactivation and after cycles of isothermal oxidative regeneration. The profiles of the rate of methane transformation to hydrocarbons vs. contact time show similar values for all catalysts with Mo/Al< 0.5. Similarly, the catalytic profiles of C6H6 selectivity vs. conversion overlap for all the formulations tested, indicating a non-selective deactivation pathway intrinsic to these Mo/H-ZSM-5 and giving the same active sites regardless of preparation method. Similar trends are observed after multiple rounds of isothermal oxidative regeneration. We then reanalyzed results from three decades of MDA studies. C6H6 selectivity vs. conversion profiles are very similar across most studies with Mo/H-ZSM-5 and related supports. While the rate at which catalysts might traverse the induction, activation, and deactivation phases may be highly dependent on materials properties, only a few pre-treatment or reaction conditions gave fundamentally different behavior. Finally, we broaden the scope to review and experimentally test other transition metals on ZSM-5, highlighting the anomalously-high C6H6 selectivities at low CH4 conversion for Zn and Mn under catalytic conditions similar to those of the benchmark Mo/H-ZSM-5 catalyst. This meta-review combined with experimental validation helps identify leads for further investigation with respect to reaction conditions and/or catalyst formulation.
甲烷脱氢芳构化条件下Mo/H-ZSM-5及相关催化剂失活行为的meta分析与实验比较
CH4大量存在,主要用作能源。甲烷脱氢芳构化(MDA)是甲烷直接转化为液态烃和氢气的一条很有前途的途径。Mo/H-ZSM-5是基准催化剂,但由于碳质物质的形成而迅速失活。在这里,我们评估了Mo/H-ZSM-5配方对MoOx负载、SiO2/Al2O3比例和Mo加载方式对催化剂一次失活和等温氧化再生循环后的影响。对于Mo/Al<; 0.5的所有催化剂,甲烷转化为碳氢化合物的速率随接触时间的变化曲线显示出相似的值。同样,所有测试配方的C6H6选择性和转化率的催化谱重叠,表明这些Mo/H-ZSM-5固有的非选择性失活途径,无论制备方法如何,都具有相同的活性位点。在多轮等温氧化再生后观察到类似的趋势。然后,我们重新分析了三十年来MDA研究的结果。在Mo/H-ZSM-5和相关支持的大多数研究中,C6H6选择性与转化概况非常相似。虽然催化剂通过诱导、活化和失活阶段的速率可能高度依赖于材料的性质,但只有少数预处理或反应条件会产生根本不同的行为。最后,我们扩大了对ZSM-5上其他过渡金属的回顾和实验测试范围,强调了在类似于基准Mo/H-ZSM-5催化剂的催化条件下,在低CH4转化率下对Zn和Mn具有异常高的C6H6选择性。结合实验验证的meta综述有助于确定进一步研究反应条件和/或催化剂配方的线索。
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来源期刊
Applied Catalysis A: General
Applied Catalysis A: General 化学-环境科学
CiteScore
9.00
自引率
5.50%
发文量
415
审稿时长
24 days
期刊介绍: Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.
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