王立新,吕喜蕾,阮厚航,吕秀阳

• 1:浙江大学生物质化工教育部重点实验室，浙江大学 化学工程与生物工程学院，浙江 杭州 310027

摘要(Abstract)：

生物质化学催化制备乳酸甲酯是一条有工业化应用前景的途径。论文在不同来源NiO筛选基础上，开展了近临界甲醇中NiO催化生物质糖转化制备乳酸甲酯的工艺优化，结合催化剂表征，对NiO催化生物质糖转化为乳酸甲酯的机理进行了探索。结果表明，不同来源的NiO对葡萄糖催化转化制备乳酸甲酯反应的影响很大，购自Aladdin的NiO催化效果最好。在较佳工艺条件下，近临界甲醇中NiO催化葡萄糖转化为乳酸甲酯的摩尔收率可达46.2%。同时催化剂重复使用试验表明Aladdin的NiO具有良好的重复使用性能。中等强度的酸性可能是影响乳酸甲酯收率的核心因素，中等强度酸含量越高，乳酸甲酯的摩尔收率就越高。研究工作将促进生物质化学催化制备乳酸甲酯非均相催化体系的开发。

关键词(KeyWords)： 乳酸甲酯;氧化镍;生物质糖;近临界甲醇

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（21676243，21476204）；浙江省自然科学基金重点项目（LZ14B060002）；中央高校基本科研业务费专项资金。

作者(Author): 王立新,吕喜蕾,阮厚航,吕秀阳

DOI: 10.3969/j.issn.1003-9015.2017.04.012

参考文献(References)：

• [1] Ragauskas A J, Williams C K, Davison B H, et al. The path forward for biofuels and biomaterials[J]. Science, 2006, 311(5760):484-489.
  [2] Vennestrøm P N R, Osmundsen C M, Christensen C H, et al. Beyond petrochemicals:the renewable chemicals industry[J]. Angewandte Chemie International Edition, 2011, 50(45):10502-10509.
  [3] Christensen C H, Rass-Hansen J, Marsden C C, et al. The renewable chemicals industry[J]. ChemSusChem, 2008, 1(4):283-289.
  [4] Datta R, Tsai S P, Bonsignore P, et al. Technological and economic potential of poly(lactic acid) and lactic acid derivatives[J]. FEMS Microbiology Reviews, 1995, 16(2-3):221-231.
  [5] SHEN Xue-liang (沈雪亮), XIA Li-ming (夏黎明). Simultaneously saccharification and lactic acid fermentation for using cellulosic material as raw material in a coupling bioreactor (利用纤维原料在串联式生物反应器中协同酶解发酵乳酸)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2005, 19(3):356-361.
  [6] SHEN Jie-fa (沈介发), ZHANG Yue (张跃), YAN Sheng-hu (严生虎), et al. Study on synthesis of methyl lactate (乳酸甲酯的合成研究)[J]. Fine Chemical Intermediates (精细化工中间体), 2007, 37(4):22-23, 31.
  [7] Nemoto K, Hirano Y, Hirata K, et al. Cooperative In-Sn catalyst system for efficient methyl lactate synthesis from biomass-derived sugars[J]. Applied Catalysis B:Environmental, 2016, 183:8-17.
  [8] Zhou L, Wu L, Li H, et al. A facile and efficient method to improve the selectivity of methyl lactate in the chemocatalytic conversion of glucose catalyzed by homogeneous Lewis acid[J]. Journal of Molecular Catalysis A:Chemical, 2014, 388-389:74-80.
  [9] Holm M S, Saravanamurugan S, Taarning E. Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts[J]. Science, 2010, 328(5978):602-605.
  [10] Tolborg S, Sadaba I, Osmundsen C M, et al. Tin-containing silicates:alkali salts improve methyl lactate yield from sugars[J]. ChemSusChem, 2015, 8(4):613-617.
  [11] Guo Q, Fan F, Pidko E A, et al. Highly active and recyclable Sn-MWW zeolite catalyst for sugar conversion to methyl lactate and lactic acid[J]. ChemSusChem, 2013, 6(8):1352-1356.
  [12] Murillo B, Sanchez A, Sebastian V, et al. Conversion of glucose to lactic acid derivatives with mesoporous Sn-MCM-41 and microporous titanosilicates[J]. Journal of Chemical Technology and Biotechnology, 2014, 89(9):1344-1350.
  [13] Yang L, Yang X, Tian E, et al. Mechanistic insights into the production of methyl lactate by catalytic conversion of carbohydrates on mesoporous Zr-SBA-15[J]. Journal of Catalysis, 2016, 333:207-216.
  [14] Murillo B, Zornoza B, de la Iglesia O, et al. Chemocatalysis of sugars to produce lactic acid derivatives on zeolitic imidazolate frameworks[J]. Journal of Catalysis, 2016, 334:60-67.
  [15] LIU Zhen (刘镇). Catalytic conversion of biomass-derived carbohydrates to methyl lactate (生物质基碳水化合物催化转化制乳酸甲酯)[D]. Hangzhou (杭州):Zhejiang University (浙江大学), 2012.
  [16] LIU Zhen (刘镇), FENG Gang (冯刚), PAN Chun-yan (潘春燕), et al. Conversion of biomass-derived carbohydrates to methyl lactate using Sn-MCM-41 and SnO₂/SiO₂(Sn-MCM-41与SnO₂/SiO₂催化转化生物质基碳水化合物制乳酸甲酯)[J]. Chinese Journal of Catalysis (催化学报), 2012, 33(10):1696-1705.
  [17] Liu Z, Li W, Pan C, et al. Conversion of biomass-derived carbohydrates to methyl lactate using solid base catalysts[J]. Catalysis Communications, 2011, 15(1):82-87.
  [18] RUAN Hou-hang (阮厚航), LÜ Xi-lei (吕喜蕾), WANG Li-xin (王立新), et al. Catalytic transfer hydrogenation of furfural to furfuryl alcohol on Cu-Pd/Al₂O₃ catalysts in near-critical isopropanol (近临界异丙醇中Cu-Pd/Al₂O₃催化转移氢化糠醛制备糠醇)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2017, 31(3):586-591.