能源化学(英文版)

能源化学(英文) ›› 2013, Vol. 22 ›› Issue (6): 895-901.

• ARTICLES • 上一篇    下一篇

Synthesis, isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

Hui Lia, Lincai Penga,c, Lu Linb, Keli Chena, Heng Zhanga   

  1. a. Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, Yunnan, China;
    b. School of Energy Research, Xiamen University, Xiamen 361005, Fujian, China;
    c. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • 收稿日期:2013-02-28 修回日期:2013-03-14 出版日期:2013-11-20 发布日期:2013-11-28
  • 通讯作者: Lincai Peng, Lu Lin
  • 基金资助:

    This work was supported by the National Key Basic Research Program (2010CB732201) from the Ministry of Science and Technology of China, and the State Key Laboratory Open Foundation of Pulp and Paper Engineering of China (201225).

Synthesis, isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

Hui Lia, Lincai Penga,c, Lu Linb, Keli Chena, Heng Zhanga   

  1. a. Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, Yunnan, China;
    b. School of Energy Research, Xiamen University, Xiamen 361005, Fujian, China;
    c. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • Received:2013-02-28 Revised:2013-03-14 Online:2013-11-20 Published:2013-11-28
  • Supported by:

    This work was supported by the National Key Basic Research Program (2010CB732201) from the Ministry of Science and Technology of China, and the State Key Laboratory Open Foundation of Pulp and Paper Engineering of China (201225).

摘要： A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition (180-210 ℃) catalyzed by extremely low concentration sulfuric acid (≤0.01 mol/L) and the product isolation were developed in this study. Effects of different process variables towards the catalytic performance were performed as a function of reaction time. The results indicated that sulfuric acid concentration, temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate. An optimized yield of around 50% was achieved at 210 ℃ for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L. The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction. The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate. The chemical composition and structural of lower heavy fraction were characterized by GC/MS, FTIR, 1H-NMR and 13C-NMR techniques. Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%. This pathway is efficient, environmentally benign and economical for the production of pure levulinate esters from cellulose.

关键词: cellulose, methyl levulinate, extremely low acid, catalysis, alcoholysis, isolation

Abstract: A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition (180-210 ℃) catalyzed by extremely low concentration sulfuric acid (≤0.01 mol/L) and the product isolation were developed in this study. Effects of different process variables towards the catalytic performance were performed as a function of reaction time. The results indicated that sulfuric acid concentration, temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate. An optimized yield of around 50% was achieved at 210 ℃ for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L. The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction. The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate. The chemical composition and structural of lower heavy fraction were characterized by GC/MS, FTIR, 1H-NMR and 13C-NMR techniques. Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%. This pathway is efficient, environmentally benign and economical for the production of pure levulinate esters from cellulose.

Key words: cellulose, methyl levulinate, extremely low acid, catalysis, alcoholysis, isolation