Page 176 - 《精细化工》2021年第11期

第 38 卷第 11 期 精 细 化 工 Vol.38, No.11
2021 年 11 月 FINE CHEMICALS Nov. 2021

催化与分离提纯技术
造纸污泥基固体酸催化 D-果糖转化为 5-羟甲基糠醛

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刘润东 ，邢立艳 ，敬凡尘 ，王英飒 ，何 静 ，徐 明
〔1. 北京林业大学 林木生物质化学北京市重点实验室，北京 100083；2. 秾源科技（北京）有限公司，
北京 100031〕
摘要：通过高温煅烧造纸污泥制备了生物炭（SBC），然后用对氨基苯磺酸对 SBC 进行接枝，制备了一种碳基
固体酸（S-SBC）催化剂。采用 FTIR、XRD、SEM、N 2 吸附-脱附、XPS 对催化剂进行了表征。将该催化剂用
于 D-果糖转化为 5-羟甲基糠醛（HMF）反应，考察了反应时间、反应温度、催化剂用量及溶剂种类、D-果糖含
量对 HMF 收率的影响，并与用杨木为原料且采用相同方法制备的杨木碳基对氨基苯磺酸接枝生物炭催化剂
（S-PBC）进行比较。结果表明，S-SBC 的催化活性优于 S-PBC。S-SBC 同时含有由金属离子形成的 Lewis 酸
位点以及—SO 3 H 等形成的 Brönsted 酸位点，两种酸位点在催化 D-果糖脱水制备 HMF 的过程中具有协同作用。
S-SBC 在 V(H 2 O)∶V(二甲基亚砜)=0.5∶4.5 混合溶液中 130 ℃下催化反应 40 min，HMF 收率高达 95.2%，连续
使用 4 次后，催化活性没有明显下降。
关键词：造纸污泥；D-果糖；生物炭固体酸；5-羟甲基糠醛；绿色催化；催化技术
中图分类号：TQ251.11；TQ426 文献标识码：A 文章编号：1003-5214 (2021) 11-2322-09

Papermaking sludge-derived solid acid as catalyst for D-fructose
dehydration into 5-hydroxymethylfurural

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LIU Rundong , XING Liyan , JING Fanchen , WANG Yingsa , HE Jing , XU Ming
[1. Beijing Key Lab of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China; 2. Nong Yuan
Technology (Beijing) Co., Ltd., Beijing 100031, China]
Abstract: Biochar (SBC) was prepared by high-temperature calcination of papermaking sludge and then
modifided by p-aminobenzenesulfonic acid to obtain a carbon-based solid acid catalyst (S-SBC). The
catalyst was characterized by FTIR, XRD, SEM, N 2 adsorption-desorption and XPS. The catalyst was
used to catalyze D-fructose into 5-hydroxymethylfurfural (HMF). The factors affecting the yield of HMF,
such as reaction time, reaction temperature, catalyst dosage, solvent type and D-fructose content were
investigated. Poplar carbon-based p-aminobenzenesulfonic acid modified biochae (S-PBC) prepared by the
same method was compared with S-SBC. The results showed that the catalytic activity of S-SBC was better
than that of S-PBC. S-SBC contained both Lewis acid sites formed by metal ions and Brönsted acid sites
formed by —SO 3H. The two acid sites exhibited a synergistic effect in the process of catalyzing the
dehydration of D-fructose to HMF. The yield of HMF was as high as 95.2% under the conditions of mixture
solution with V(H 2O)∶V(dimethyl sulfoxide)=0.5∶4.5 as solvent, S-SBC as catalyst, reaction temperature
130 ℃ and reaction time 40 min. The catalytic activity of S-SBC did not decrease significantly after being
used for four times.
Key words: paper sludge; D-fructose; biochar solid acid; 5-hydroxymethylfurfural; green catalysis; catalysis
technology

收稿日期：2021-04-28; 定用日期：2021-07-14; DOI: 10.13550/j.jxhg.20210444
基金项目：国家重点研发计划项目（2017YFD0601205）
作者简介：刘润东（1995—），男，硕士生，E-mail：1253886145@qq.com。联系人：何 静（1961—），教授，E-mail：hejing2008@
sina.com。