高效有机无模板铜交换丝光沸石上甲醇羰基化生成乙酸甲酯的机理见解,Catalysis Science & Technology

当前位置： X-MOL 学术 › Catal. Sci. Technol. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

高效有机无模板铜交换丝光沸石上甲醇羰基化生成乙酸甲酯的机理见解
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2023-11-15 , DOI: 10.1039/d3cy01271a
L. A. Luque-Álvarez ₁ , J. González-Arias ₁ , F. Romero-Sarria ₁ , T. R. Reina ₁ , L. F. Bobadilla ₁ , J. A. Odriozola ₁

Affiliation

目前，乙酸是通过甲醇的羰基化反应生产，主要路线是使用均相贵金属基催化剂，但存在一定的局限性，包括使用污染性的卤代烷助催化剂以及催化剂回收困难等。为了克服这些挑战，利用非均相催化剂，特别是以铜作为氧化还原中心的沸石的替代方法的探索引起了人们的关注。尽管如此，仍追求所获得的转化率和选择性以与均相路线竞争。因此，需要更深入地了解反应和机理，以确定薄弱环节并克服它们。在本研究中，我们建议使用时间分辨操作DRIFTS-MS 来研究 Cu-H-MOR 催化剂上的甲醇羰基化反应。该研究旨在通过研究催化剂的行为提出反应机制，包括确定沸石中铜氧化还原中心的位置。还评估了 Cu-H-MOR 催化剂的催化性能，证明了其在甲醇羰基化反应中的活性和稳定性。原位DRIFTS -MS 结果提供了对反应机制以及酸和氧化还原中心在该过程中的参与的深入了解。基于这些发现，我们提出了 Cu-H-MOR 沸石上甲醇羰基化的反应机理：（i）甲醇脱水，（ii）CO 插入甲醇基团，（iii）二甲醚和乙酰基之间的反应，以及（iv） ) 乙酸甲酯的水解。总的来说，我们相信这项工作有助于更深入地了解乙酸生产的非均相路线，并为优化工艺提供了潜在的途径。

"点击查看英文标题和摘要"

Mechanistic insights into methanol carbonylation to methyl acetate over an efficient organic template-free Cu-exchanged mordenite

Currently, acetic acid is produced via the carbonylation reaction of methanol with the main route entailing the use of homogeneous noble metal-based catalysts, which has certain limitations, including the use of polluting alkyl halide promoters and difficulty in catalyst recovery. To overcome these challenges, the exploration of alternative methods utilizing heterogeneous catalysts, particularly zeolites with copper as a redox center, has gained attention. Nonetheless, the conversion and selectivity obtained are sought after to compete against the homogeneous route. Therefore, a deeper understanding of the reaction and mechanism is needed to determine the weak points and overcome them. In this study, we propose the use of time-resolved operando DRIFTS-MS to study the methanol carbonylation reaction over a Cu–H-MOR catalyst. The study aimed to propose a reaction mechanism through an investigation of the behavior of the catalyst, including potential identification of the location of the copper redox center in the zeolite. The catalytic performance of the Cu–H-MOR catalyst was also evaluated, demonstrating its activity and stability in the methanol carbonylation reaction. The operando DRIFTS-MS results provide insights into the reaction mechanism and the involvement of the acid and redox centers in the process. Based on the findings, we propose a reaction mechanism for methanol carbonylation on Cu–H-MOR zeolite: (i) methanol dehydration, (ii) CO insertion into methoxide groups, (iii) reaction between dimethyl ether and acetyl groups, and (iv) hydrolysis of methyl acetate. Overall, we believe that this work contributes to a deeper understanding of the heterogeneous route for acetic acid production and offers potential avenues for optimizing the process.

更新日期：2023-11-15

点击分享查看原文

点击收藏

公开下载

阅读更多本刊最新论文本刊介绍/投稿指南

全部期刊列表>>