Page 29 - 《精细化工》2021年第12期

第 12 期 唐 兴，等: 水相和无溶剂体系中生物质基乙酰丙酸制备 γ-戊内酯的研究进展 ·2391·

（1）对于水相体系中催化 LA 加氢合成 GVL， [8] WINOTO H P, AHN B S, JAE J. Production of γ-valerolactone from
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the catalyst acid properties and process conditions[J]. Journal of
容易造成催化剂活性金属的流失，进而导致催化剂 Industrial and Engineering Chemistry, 2016, 40: 62-71.
部分失活。通过创新催化剂合成方式可以提高活性 [9] TANG X (唐兴), HU L (胡磊), SUN Y (孙勇), et al. Conversion of
biomass to novel platform chemical γ-valerolactone by selective
金属位点的水热稳定性。例如，设计合成具有核壳 reduction of levulinic acid[J]. Progress in Chemistry (化学进展),
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另一方面，催化剂载体如金属氧化物等在高温水热
of novel biomass-derived platform molecule γ-valerolactone[J].
条件下会发生水解，也会造成催化剂结构破坏，进 Progress in Chemistry (化学进展), 2016, 28(11): 1672-1681.
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催化活性的非贵金属加氢催化剂也是水相 LA 加氢
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合成 GVL 的重要研究方向之一。 gamma-valerolactone (GVL) through hydrogenation of biomass-
（2）对于无溶剂体系催化 LA 加氢合成 GVL， derived levulinic acid using non-noble metal catalysts: A critical
review[J]. Chemical Engineering Journal, 2019, 372: 992-1006.
由于 LA 具有一定的酸性，所以无溶剂体系中催化 [14] WANG J T (王京拓), ZHANG M H (张明慧). Catalytic reactions of
LA 加氢的催化剂需要具有较强的耐酸性。更重要的 levulinic acid as a biomass-derived platform molecule[J]. Petrochemical
Technology (石油化工), 2016, 45(5): 513-520.
是，LA 分子结构中包含了羰基和羧基两个主要的有 [15] ZHU L Y (朱龙云), YANG W X (杨文霞), LIU Y X (刘迎新).
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争吸附是影响催化效率的关键。LA 加氢合成 GVL
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的决速步骤是 LA 中羰基的加氢还原，然而由于羧 [16] JIANG K, SHENG D, ZHANG Z, et al. Hydrogenation of levulinic
基在固体催化剂表面具有更强的吸附能力，无溶剂 acid to γ-valerolactone in dioxane over mixed MgO-Al 2O 3 supported
Ni catalyst[J]. Catalysis Today, 2016, 274: 55-59.
体系中需要通过高温促进羧基从催化剂表面脱附或 [17] OSATIASHTIANI A, LEE A F, WILSON K. Recent advances in the
延长反应时间，以此保证比较高的 GVL 产率。为了 production of γ-valerolactone from biomass-derived feedstocks via
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在无溶剂体系中促进 LA 高效还原合成 GVL，一方
Chemical Technology & Biotechnology, 2017, 92(6): 1125-1135.
面需要设计对羰基吸附更具选择性的催化剂；另一 [18] GIRISUTA B, JANSSEN L P B M, HEERES H J J G C. A kinetic
方面可以在 LA 中加入少量能与羧基具有强相互作 study on the decomposition of 5-hydroxymethylfurfural into levulinic
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用的组分，进而弱化 LA 中羧基与羰基在催化剂表 [19] ALONSO D M, WETTSTEIN S G, MELLMER M A, et al. Integrated
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化效率。
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