A combined DFT and kMC study of reaction kinetics for the acetoxylation of propylene to allyl acetate on PdCu catalysts

IF 3.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Molecular Catalysis Pub Date : 2025-03-15 DOI:10.1016/j.mcat.2025.115026
Weiwei Zhang , Liangfeng An , Yingzhe Yu , Minhua Zhang
{"title":"A combined DFT and kMC study of reaction kinetics for the acetoxylation of propylene to allyl acetate on PdCu catalysts","authors":"Weiwei Zhang ,&nbsp;Liangfeng An ,&nbsp;Yingzhe Yu ,&nbsp;Minhua Zhang","doi":"10.1016/j.mcat.2025.115026","DOIUrl":null,"url":null,"abstract":"<div><div>Allyl acetate is a vital intermediate in organic synthesis, which is produced by the acetoxylation of propylene on PdCu catalysts and mainly used for the synthesis of allyl alcohol and a range of derivatives, including 1,4-butanediol. Nevertheless, the absence of reaction kinetics in this process imposes limitations on the reactor design and process optimization. By combining Density Functional Theory and kinetic Monte Carlo simulations, the reaction kinetics were systematically studied. The critical oxygen concentration of the reaction system was calculated, and the feed molar ratio of oxygen was determined to be 8 %. The feed molar ratio of acetic acid was set to be 16 % to keep higher turnover frequency of allyl acetate and lower energy consumption. The preferential formation route of allyl acetate was obtained and the turnover frequency and space-time yield of allyl acetate were calculated. The apparent activation energy was determined to be 62.35 kJ⋅mol<sup>-1</sup>. Finally, the reaction kinetic equation was derived and the kinetic parameters were obtained by fitting the data of space-time yield. This work provides theoretical guidance for reactor design and technological process improvement on microscopic and mesoscopic scales. Of particular significance is the contribution of a novel approach to the acquisition of reaction kinetic equations, which has a good application prospect.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115026"},"PeriodicalIF":3.9000,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Molecular Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2468823125002123","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

Allyl acetate is a vital intermediate in organic synthesis, which is produced by the acetoxylation of propylene on PdCu catalysts and mainly used for the synthesis of allyl alcohol and a range of derivatives, including 1,4-butanediol. Nevertheless, the absence of reaction kinetics in this process imposes limitations on the reactor design and process optimization. By combining Density Functional Theory and kinetic Monte Carlo simulations, the reaction kinetics were systematically studied. The critical oxygen concentration of the reaction system was calculated, and the feed molar ratio of oxygen was determined to be 8 %. The feed molar ratio of acetic acid was set to be 16 % to keep higher turnover frequency of allyl acetate and lower energy consumption. The preferential formation route of allyl acetate was obtained and the turnover frequency and space-time yield of allyl acetate were calculated. The apparent activation energy was determined to be 62.35 kJ⋅mol-1. Finally, the reaction kinetic equation was derived and the kinetic parameters were obtained by fitting the data of space-time yield. This work provides theoretical guidance for reactor design and technological process improvement on microscopic and mesoscopic scales. Of particular significance is the contribution of a novel approach to the acquisition of reaction kinetic equations, which has a good application prospect.

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
求助全文
约1分钟内获得全文 去求助
来源期刊
Molecular Catalysis
Molecular Catalysis Chemical Engineering-Process Chemistry and Technology
CiteScore
6.90
自引率
10.90%
发文量
700
审稿时长
40 days
期刊介绍: Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods
期刊最新文献
Promoting effect of alkaline earth metals on Ni/CeO2 catalysts for ammonia decomposition reaction A combined DFT and kMC study of reaction kinetics for the acetoxylation of propylene to allyl acetate on PdCu catalysts Nano UiO-66 and UiO-66-NH2 MOFs as Bifunctional Electrocatalysts for Water-Splitting: A Comparative Study Swelling poly(ionic liquid)s supported silver N-heterocyclic carbene for efficient conversion of propargyl alcohols with CO2 Ethylene glycol partial oxidation on Co3O4 (001) surface: Interplay between solute’s surface coverage and aqueous solvation
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1