Deciphering the reaction-diffusion coupling by dual-scale simulation for regulating selectivity of methyl glycolate in dimethyl oxalate hydrogenation

TANG Haoyuan; ZHOU Jinghong; LI Wei; CAO Yueqiang; ZHOU Xinggui

doi:10.11949/0438-1157.20260606

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Deciphering the reaction-diffusion coupling by dual-scale simulation for regulating selectivity of methyl glycolate in dimethyl oxalate hydrogenation

更新时间：2026-07-30

- Deciphering the reaction-diffusion coupling by dual-scale simulation for regulating selectivity of methyl glycolate in dimethyl oxalate hydrogenation
- CIESC Journal (2026)
- 作者机构：
  
  华东理工大学化学工程与低碳技术全国重点实验室，上海200237
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260606
  CLC： TQ 203.2
- Received：29 April 2026，
  
  Revised：2026-07-29，
  
  Accepted：30 July 2026，
- 稿件说明：
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TANG Haoyuan, ZHOU Jinghong, LI Wei, et al. Deciphering the reaction-diffusion coupling by dual-scale simulation for regulating selectivity of methyl glycolate in dimethyl oxalate hydrogenation[J/OL]. CIESC Journal, 2026.
DOI：

TANG Haoyuan, ZHOU Jinghong, LI Wei, et al. Deciphering the reaction-diffusion coupling by dual-scale simulation for regulating selectivity of methyl glycolate in dimethyl oxalate hydrogenation[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260606.

摘要

草酸二甲酯（DMO）加氢制乙醇酸甲酯（MG）属于典型串联反应体系，目标产物选择性受反应动力学与传递过程协同控制。针对工业固定床反应器中颗粒内扩散及床层尺度传递耦合作用机制尚不明确的问题，本文建立了床层-颗粒双尺度二维模型，系统研究了催化剂粒径、径向温度梯度及操作条件对反应性能的影响。结果表明，催化剂粒径可通过耦合调控颗粒内扩散与床层内反应物分布，改变主、副反应竞争关系，其中5 mm颗粒表现出较优综合性能；径向温度梯度通过强化主、副反应对温度的响应差异，在截面上形成有利于MG保留的选择性分区；操作条件通过影响反应速率、停留时间及组分分布调控反应与传递匹配，在进料温度483.15 K、液时空速0.75 h

-1

和氢酯比20条件下能获得最高MG收率。研究揭示了DMO选择性加氢过程中多尺度反应-扩散耦合规律，可为工业反应器内的催化床层结构设计及操作过程优化提供理论依据。

Abstract

The hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) is a typical tandem reaction system

in which the selectivity of the target product is governed by the interplay between reaction kinetics and transport processes. To clarify the coupled effects of intraparticle diffusion and bed-scale transport in industrial fixed-bed reactors

a two-dimensional bed-particle dual-scale model was developed. The effects of catalyst particle size

radial temperature gradient

and operating conditions on reaction performance were systematically investigated. The results show that catalyst particle size alters the competiti

on between the main and the side reactions by coupling intraparticle diffusion with reactant distribution along the bed

with 5 mm particles exhibiting optimal overall performance. The radial temperature gradient enhances the differential temperature sensitivity of the main and side reactions

leading to a spatial selectivity distribution favorable for MG preservation across the reactor cross-section. Operating conditions influence the matching between reaction and transport processes by altering reaction rate

residence time

and component distribution; optimal performance is achieved at a feed temperature of 483.15 K

a liquid hourly space velocity of 0.75 h

-1

and a relatively low hydrogen-to-ester ratio. This study elucidates the multiscale reaction-diffusion coupling in DMO selective hydrogenation and provides a theoretical basis for catalyst bed design and operation optimization in industrial fixed-bed reactors.

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references

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