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Acta Chimica Sinica ›› 2014, Vol. 72 ›› Issue (4): 502-507.DOI: 10.6023/A14010067 Previous Articles    

Article

果糖一步水热合成碳微球固体酸催化纤维素水解

廉优芬, 闫碌碌, 王羽, 漆新华   

  1. 天津市生物质类固废资源化技术工程中心 南开大学环境科学与工程学院 天津 300071
  • 投稿日期:2014-01-25 发布日期:2014-03-29
  • 通讯作者: 漆新华 E-mail：qixinhua@nankai.edu.cn E-mail:qixinhua@nankai.edu.cn
  • 基金资助:

    项目受国家自然科学基金（No.21350110210）、教育部新世纪人才计划和天津市自然科学基金（No.12JCYBJC13000）资助.

One-step Preparation of Carbonaceous Solid Acid Catalysts by Hydrothermal Carbonization of Fructose for Cellulose Hydrolysis

Lian Youfen, Yan Lulu, Wang Yu, Qi Xinhua   

  1. Tianjin Biomass Solid Waste Reclamation Technology and Engineering Center, College of Environmental Science and Engineering, Nankai University, Tianjin 300071
  • Received:2014-01-25 Published:2014-03-29
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21350110210), the Program for New Century Excellent Talents in University, and the Natural Science Foundation of Tianjin (No. 12JCYBJC13000).

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Supporting Info.

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Hydrolysis of cellulose plays a key role in the biomass utilization. As a commonly used solid acid in cellulose hydrolysis, sulfated activated carbon normally prepared from the impregnation of activated carbon by sulfuric acid does not meet the principles of green chemistry and leads to environmental issues. In this work, carbonaceous microshperes bearing COOH, OH groups were synthesized by hydrothermal carbonization of fructose at 150 ℃ for 4 h, and the obtained carbonaceous material could be used directly for the catalytic hydrolysis of cellulose without any post-modification or in-situ functionalization, where a reducing sugar yield of 45.6% was obtained at 130 ℃ in 3 h in ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). To improve the catalytic activity of the carbonaceous solid acid catalyst, sulfonic groups were grafted onto the carbonaceous microspheres by one-step hydrothermal carbonization of fructose in the presence of sulfosalicylic acid as co-monomer. The effects of reaction temperature, reaction time, catalyst dosage, water content and initial cellulose concentration on the hydrolysis of cellulose were systematically investigated in the presence of the as-prepared sulfonated carbonaceous solid acid catalyst, and the reducing sugar yield for cellulose hydrolysis was improved to 60.7% at 130 ℃ in 90 min in [BMIM][Cl]. An appropriate water content of around 1% in the ionic liquid could promote the formation of the reducing sugars, whereas a water content of greater than 1% lead to a decrease in the yield of reducing sugars. No large decrease in the yield of reducing sugars could be observed for initial cellulose concentration (w) of up to 10%. The catalyst could be reused and exhibited constant stability for at least five successive trials. The method developed offers a new way for the preparation and in-situ functionalization of carbonaceous solid acid catalysts, and provides a renewable strategy for the sustainable biomass utilization.

Key words: hydrothermal carbonization, carbonaceous microspheres, solid acid, hydrolysis, cellulose