Page 90 - 201808

第 35 卷第 8 期 精 细 化 工 Vol.35, No.8
201 8 年 8 月 FINE CHEMICALS Aug. 2018

催化与分离提纯技术
纳米多孔钌催化纤维素高效转化制备甲烷

1*
1
2
1
1
吕金昆 ，孙立明 ，荣泽明 ，王 越 ，曲景平
（1.大连理工大学 精细化工国家重点实验室，辽宁 大连 116024；2. 中国石油天然气股份有限公司 石油
化工研究院，北京 102206）
摘要：以钌、铝两种金属制备了纳米多孔钌催化剂，并将其应用于催化纤维素制甲烷反应中。对纤维素和催化
剂进行了 XRD、SEM、TEM 和 XPS 表征，并对催化过程进行了温度和压力考察。结果表明：在反应温度 220 ℃、
初始氢气压力 0.5 MPa 下反应 8 h，纤维素转化率为 75.8%，甲烷选择性达到 82.2%。具有纳米多孔结构的催化
剂稳定性良好，可循环套用 10 次，甲烷收率保持在 73.2%~79.5%。考察了纤维素的转化历程和反应前后纤维素
结构变化。结果表明：纤维素制备甲烷反应分为酸催化的水解过程和纳米多孔钌催化的加氢过程两个阶段。钒
改性纳米多孔钌双功能催化体系可以提高纤维素向甲烷转化，纤维素的转化率及甲烷的收率分别达到了 49.3%
和 38.8%。
关键词：纳米多孔钌；纤维素；甲烷；催化
中图分类号：TQ032.4 文献标识码：A 文章编号：1003-5214 (2018) 08-1338-08

Highly Efficient Conversion of Cellulose into
Methane over Nanoporous Ru Catalyst

1*
1
1
1
2
LÜ Jin-kun , SUN Li-ming , RONG Ze-ming , WANG Yue , QU Jing-ping
（1. State Key Laboratory of Fine Chemicals, Dalian university of technology, Dalian 116024, Liaoning, China;
2. Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, China）
Abstract: Nanoporous Ru was prepared with two kinds of metal (ruthenium and aluminum), and employed
as catalyst in the transformation of cellulose to methane. The cellulose and catalyst were characterized by
XRD, SEM, TEM and XPS. The effects of temperature and H 2 pressure on the hydrogenation of cellulose
were studied. The results showed that under the following reaction conditions: reaction temperature 220 ℃,
initial H 2 pressure 0.5 MPa, reaction time 8 h, the conversion of cellulose (75.8%) and selectivity of
methane (82.2%) were obtained. The catalyst with nanoporous structure still remained good stability after
being reused ten times, and the yield of CH 4 ranged from 73.2% to 75.9%. The reaction mechanism of
cellulose transformation and structure change of cellulose in the process were investigated. It was found that
cellulose transformation into methane was consisted of acid-catalyzed hydrolysis process and nanoporous
Ru-catalyzed hydrogenation process. Vanadium modified nanoporous Ru bifunctional catalyst could
significantly promote the transformation of cellulose into methane. The conversion of cellulose and yield of
methane were 49.3% and 38.8%, respectively.
Key words: nanoporous Ru; cellulose; methane; catalysis
Foundation item: Fundamental Research Funds for the Central Universities (DUT16LK21)

随着化石资源的不断减少及环境污染问题的日 最丰富的非粮生物质资源，广泛存在于农林废弃物
益严重，生物质因其可再生性、二氧化碳零排放等 中，如玉米秸秆、甘蔗渣及废弃木屑等。将纤维素
优势逐渐成为全球关注的焦点。纤维素是自然界中 通过化学或生物法水解制备葡萄糖，进而生产乙醇、

收稿日期：2017-08-15; 定用日期：2017-12-04; DOI: 10.13550/j.jxhg.20170664
基金项目：中央高校基本科研专项资金（DUT16LK21）
作者简介：吕金昆（1987—），男，博士生。联系人：荣泽明（1979—），男，副教授，E-mail：zeming@dlut.edu.cn。