Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst

HOU Lianxia; YUAN Zhaoping; QIAO Hongchang; ZHOU Jinghong; ZHOU Xinggui

doi:10.11949/j.issn.0438-1157.20181426

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Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst
- CIESC Journal Vol. 70, Issue 4, Pages: 1390-1400(2019)
- 作者机构：
  
  华东理工大学化学工程联合国家重点实验室，上海 200237
- 作者简介：
- 基金信息：
- DOI：10.11949/j.issn.0438-1157.20181426
  CLC： TQ 352.6;TQ 352.2
- Received：29 November 2018，
  
  Revised：2019-01-22，
  
  Online First：15 June 2020，
  
  Published：12 April 2019
- 稿件说明：
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侯莲霞, 袁兆平, 乔鸿昌, 周静红, 周兴贵. Ni-W₂C催化葡萄糖氢解制备低碳二元醇反应机理研究[J]. 化工学报, 2019, 70(4): 1390-1400 DOI: 10.11949/j.issn.0438-1157.20181426.

HOU Lianxia, YUAN Zhaoping, QIAO Hongchang, ZHOU Jinghong, ZHOU Xinggui. Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst[J]. CIESC Journal, 2019, 70(4): 1390-1400
侯莲霞, 袁兆平, 乔鸿昌, 周静红, 周兴贵. Ni-W₂C催化葡萄糖氢解制备低碳二元醇反应机理研究[J]. 化工学报, 2019, 70(4): 1390-1400 DOI: 10.11949/j.issn.0438-1157.20181426. DOI：

HOU Lianxia, YUAN Zhaoping, QIAO Hongchang, ZHOU Jinghong, ZHOU Xinggui. Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst[J]. CIESC Journal, 2019, 70(4): 1390-1400 DOI： 10.11949/j.issn.0438-1157.20181426.

摘要

采用HPLC、LC-MS、GC-MS等分析手段对不同工艺条件下Ni/W

C催化葡萄糖加氢转化的中间产物及终产物进行定性定量分析，研究了葡萄糖加氢转化过程的反应机制和历程。研究发现：葡萄糖加氢转化过程中同时平行发生了加氢、异构和逆向羟醛缩合（氢解）三类反应；葡萄糖发生加氢反应能够得到六元醇且其不会再进一步转化，发生逆向羟醛缩合反应主要生成乙二醇（C

产物），发生异构反应则可生成果糖，其进行逆向羟醛缩合的产物则为1

2-丙二醇和甘油（C

产物）；高浓度葡萄糖条件下，其异构产物果糖发生脱水反应生成的5-HMF浓度过高发生聚合，进而导致结焦。根据葡萄糖加氢转化的反应网络，提出了调控反应过程中C

产物和C

产物分布的策略，并通过增加催化剂用量来加快果糖脱水的竞争反应速率(加氢、氢解)，进而实现了高浓度（10%，质量分数）葡萄糖的加氢转化。此外，葡萄糖加氢转化过程中存在明显的浓度效应，反应物浓度越低，越有利于发生逆向羟醛缩合反应，反之则有利于发生加氢反应。

Abstract

The HPLC and LC-MS

GC-MS and other analytical methods were used to qualitatively and quantitatively analyze th

e intermediates and final products of Ni/W

C catalyzed glucose hydrotreating under different process conditions. Ni-W

C was recently reported as a promising catalyst for the hydrogenolysis of cellulose or glucose to EG with the highest yield of 75%

yet this was achieved at the substrate concentration less than 1% because the concentrated substrate will lead to coking. This meant low productivity and high cost for commercial production

thus hinder this promising process from industry application. Therefore

insights into the reaction network to elucidate the coking mechanism and to optimize the process are needed. In this work

the mechanistic study on the glucose conversion

especially with the concentrated glucose substrate

over 2%Ni-30%W

C/AC was systematically carried out. The reaction parameters including temperature

initial glucose concentration and H

pressure have been investigated and the results

in combination with the intermediate analysis by LC

LCMS and GCMS

showed that three parallel reaction pathways including retro-aldol reaction

isomerization and hydrogenation were involved in the reaction. C

product (EG) was originated from glucose hydrogenolysis while the C

products (1

2-PG and glycerol) were originated from fructose hydrogenolysis

and the dehydration of fructose led to 5-HMF and finally to coke in concentrated glucose conversion. Based on these understanding

the ratio of C

products to C

on the one hand

has been manipulated by tuning of isomerization of glucose into fructose with base additive and on the other hand

coking has been avoided by accelerating its competing reactions even at the glucose concentration of 10%（mass）. More interestingly

it was indicated that glucose of low concentration favors retro-aldol reaction while the one of high concentration tends to hydrogenate.

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references

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