Integrated conversion of cellulose and methanol to<italic style="font-style: italic"> γ</italic>‑valerolactone catalyzed by Ru@ZSM-5

GAO Xiaoqing; ZHU Shanhui; ZHENG Hongyan

doi:10.12434/j.issn.2097-2547.20250305

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Integrated conversion of cellulose and methanol to γ‑valerolactone catalyzed by Ru@ZSM-5

更新时间：2025-11-25

- Integrated conversion of cellulose and methanol to γ‑valerolactone catalyzed by Ru@ZSM-5
- Vol. 50, Issue 11, Pages: 52-63(2025)
- 作者机构：
  
  1.太原工业学院化学与化工系生物质绿色甲醇转化及氢能利用厅市共建山西省重点实验室培育基地，山西太原 030008
  2.中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室，山西太原 030001
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250305
  CLC： TQ426;TQ203.2;O643.3
- Received：22 July 2025，
  
  Revised：2025-08-20，
  
  Published：25 November 2025
- 稿件说明：
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高晓庆,朱善辉,郑洪岩.Ru@ZSM-5催化纤维素和甲醇耦合转化制γ-戊内酯[J].低碳化学与化工,2025,50(11):52-63.

GAO Xiaoqing,ZHU Shanhui,ZHENG Hongyan.Integrated conversion of cellulose and methanol to γ‑valerolactone catalyzed by Ru@ZSM-5[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(11):52-63.
高晓庆,朱善辉,郑洪岩.Ru@ZSM-5催化纤维素和甲醇耦合转化制γ-戊内酯[J].低碳化学与化工,2025,50(11):52-63. DOI： 10.12434/j.issn.2097-2547.20250305.

GAO Xiaoqing,ZHU Shanhui,ZHENG Hongyan.Integrated conversion of cellulose and methanol to γ‑valerolactone catalyzed by Ru@ZSM-5[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(11):52-63. DOI： 10.12434/j.issn.2097-2547.20250305.

摘要

-戊内酯（GVL）是重要的生物质衍生物，由纤维素的“水解-加氢”路线生产，然而现阶段主要使用液体酸和负载金属混合催化剂，具有GVL收率低等问题。因此，提出了纤维素和甲醇的“醇解-加氢”新路线，利用“配体保护策略”原位水热法设计了具有金属和酸双功能活性位的ZSM-5分子筛孔道限域Ru基催化剂（Ru@ZSM-5），将Ru团簇包覆在ZSM-5分子筛孔道内。TEM表征和封装度测试证实Ru团簇平均粒径仅为0.57 nm，大量Ru团簇（92.7%）被限域在ZSM-5分子筛的十元环交叉孔道内。结果表明，Ru@ZSM-5在纤维素和甲醇耦合转化制

-戊内酯中表现出优异的催化性能，在230 ℃、3 MPa H

和水与甲醇体积比为10%条件下，GVL收率高达51.1%（反应6 h），远优于传统负载型Ru/ZSM-5、Ru/SiO

+ ZSM-5和Ru/Al

+ ZSM-5催化剂。由于ZSM-5分子筛孔道的限域效应，Ru@ZSM-5具有非常高的稳定性，5次循环反应后GVL收率为51.5%，且Ru团簇平均粒径仍保持在0.59 nm。然而，Ru/ZSM-5经历了严重的失活，分散在ZSM-5分子筛外表面的Ru纳米粒子发生明显烧结，其平均粒径为6.57 nm。

Abstract

-valerolactone (GVL) is an important biomass derivative

which is produced by “hydrolysis-hydrogenation” route of cellulose. However

at present

liquid acid and suppo

rted metal mixed catalysts are mainly used

which have the problem of low GVL yield. Therefore

a new route of “alcoholysis-hydrogenation” of cellulose and methanol was proposed. ZSM-5 molecular sieve pore confined Ru catalyst (Ru@ZSM-5) was designed with dual functional active sites of metal and acid by “ligand protection strategy” in-situ hydrothermal method

and Ru nanoclusters were encapsulated within the pore channels of ZSM-5 molecular sieve. TEM characterization and encapsulation degree test confirm that the average diameter of Ru clusters is only 0.57 nm

and a large number of Ru clusters (92.7%) are confined within the ten-membered ring cross pore channels of ZSM-5 molecular sieve. The results show that Ru@ZSM-5 exhibits excellent catalytic performance in the integrated conversion of cellulose and methanol to

‑valerolactone. Under the conditions of 230 °C

3 MPa H

and volume ratio of water to methanol of 10%

the GVL yield is 51.1% (reaction for six hours)

far superior to traditional supported Ru/ZSM-5

Ru/SiO

+ ZSM-5

and Ru/Al

+ ZSM-5 catalysts. Due to the confinement effect of ZSM-5 molecular sieve pores

Ru@ZSM-5 shows high stability

with the GVL yield of 51.5% and the particle size of Ru clusters remains 0.59 nm after five reaction cycles. However

Ru/ZSM-5 undergoes severe deactivation

and the Ru nanoparticles dispersed on the outer surface of ZSM-5 molecular sieve suffer from significant sintering

with the average particle size of 6.57 nm.

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references

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Integrated conversion of cellulose and methanol to γ‑valerolactone catalyzed by Ru@ZSM-5

DOI：10.12434/j.issn.2097-2547.20250305

摘要

Abstract

关键词

Keywords

references