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林产化学与工业 ›› 2021, Vol. 41 ›› Issue (2): 39-46.doi: 10.3969/j.issn.0253-2417.2021.02.006

• 研究报告 • 上一篇    下一篇

醇/水体系中混酸催化葡萄糖醇解制备乙酰丙酸甲酯

吴媛1, 王子华1, 常春1,2,*(), 李攀1,2, 徐桂转3   

  1. 1. 郑州大学 化工学院, 河南 郑州 450001
    2. 河南省杰出外籍科学家工作室, 河南 郑州 450001
    3. 河南农业大学 机电工程学院, 河南 郑州 450002
  • 收稿日期:2020-08-08 出版日期:2021-04-28 发布日期:2021-05-08
  • 通讯作者: 常春 E-mail:chunchang@zzu.edu.cn
  • 作者简介:常春, 教授, 博士生导师, 研究领域为生物质能源化工; E-mail: chunchang@zzu.edu.cn
    吴媛(1997-), 女, 贵州贵阳人, 硕士生, 研究方向为生物质资源化利用
  • 基金资助:
    国家自然科学基金资助项目(U1904122);河南省杰出外籍科学家工作室生物质资源加工与高效利用(GZS2018004)

Synthesis of Methyl Levulinate by Glucose Alcoholysis Catalyzed by Mixed Acid in Alcohol/Water System

Yuan WU1, Zihua WANG1, Chun CHANG1,2,*(), Pan LI1,2, Guizhuan XU3   

  1. 1. School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
    2. Henan Outstanding Foreign Scientists'Workroom, Zhengzhou 450001, China
    3. College of Mechanical and Electrical Engineering, Henan Agricultural University, Zhengzhou 450002, China
  • Received:2020-08-08 Online:2021-04-28 Published:2021-05-08
  • Contact: Chun CHANG E-mail:chunchang@zzu.edu.cn

摘要:

以超低酸与硫酸盐为混酸催化剂,研究了葡萄糖在甲醇/水体系中醇解制备乙酰丙酸甲酯(ML)的反应过程。在硫酸盐(Al2(SO43、CuSO4、Fe2(SO43、Ti(SO42、SnSO4、ZnSO4、NiSO4、Cr2(SO43)中,Al2(SO43与超低酸H2SO4的混酸具有良好的催化性能。以混酸作催化剂,考察了葡萄糖初始质量浓度(10~40 g/L)、Al2(SO43的用量(0.12~0.48 g)、反应温度(160~200℃)以及反应时间(2~6 h)对产物生成的影响规律。在甲醇/水(体积比50/50)的溶剂体系下,原料质量浓度20 g/L、反应时间4 h、反应温度170℃、Al2(SO43质量0.24 g,0.02 mL H2SO4(0.01 mol/L)的条件下,乙酰丙酸甲酯的最高产率为46.68%,此时乙酰丙酸(LA)产率为24.20%。葡萄糖经醇解首先生成甲基葡萄糖苷(MLG),继而转化为5-甲氧甲基糠醛(MMF),最终转化生成ML。Al2(SO43催化剂经5次循环使用后仍具有较高的催化活性(ML产率45.92%,LA产率20.58%)。

关键词: 葡萄糖, 硫酸铝, 乙酰丙酸甲酯, 醇解

Abstract:

Methyl levulinate(ML) was prepared by the alcoholysis of glucose in a methanol/water system over mixed acid catalysts comprising extremely low acid and metal sulfates. Al2(SO4)3with ultralow sulfuric acid showed the highest catalytic performance among the studied metal sulfates(Al2(SO4)3, CuSO4, Fe2(SO4)3, Ti(SO4)2, SnSO4, ZnSO4, NiSO4, and Cr2(SO4)3). Moreover, the effects of initial mass concentration of glucose(10-40 g/L), Al2(SO4)3mass in mixed acid catalyst(0.12-0.48 g), reaction temperature(160-200 ℃), and reaction time(2-6 h) on product formation were investigated. The highest yield (46.68%) of ML was obtained in methyl/water(50/50) solvent system with a raw material mass concentration of 20 g/L, 0.02 mL H2SO4(0.01 mol/L), and 0.24 g Al2(SO4)3at 170 ℃ after 4 h; under these conditions, the yield of levulinic acid(LA) was 24.20%. During the alcoholysis process, glucose was first converted to methyl glucoside(MLG), then methoxymethylfurfural(MMF), and ultimately to ML. Al2(SO4)3could be reused at least five times with a slight decrease in catalytic activity(45.92% yield of ML and 20.58% yield of LA).

Key words: glucose, aluminum sulfate, methyl levulinate, alcoholysis

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