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·2300·                            精细化工   FINE CHEMICALS                                 第 37 卷

            道 [8-9,22] ,催化剂催化活性降低可能是由于积炭附着                         [J]. Energy Environ Sci, 2013, 6: 1415-1442.
                                                               [3]  JIA  B  (贾冰), XIN K (辛坤), YU J S (于记生),  et al.  Progress
            于催化剂表面,降低了催化活性。本文改进了催化
                                                                   in synthesis of dihydroxyacetone (DHA) from formose reaction[J].
            剂回收处理方法,每次反应结束后,过滤回收的催化                                Modern Chemical Industry (现代化工), 2017, 37(1): 23-27.
            剂用乙醇清洗两次,然后在 300  ℃下煅烧处理 2 h,                      [4]   JIA B (贾冰), XIN K (辛坤), YU Y M (于英民), et al. Synthesis
                                                                   of 1,3-dihydroxyacetone by  montmorillonite supported thiazolium
            处理后的催化剂能有效催化 DHA 制备乳酸酯,如                               catalysts[J]. Fine Chemicals (精细化工), 2018, 35(2): 261-266.
            图 8 所示。催化剂循环使用 4 次,催化活性只有小                         [5]   HAYASHI Y, SASAKI Y. Tin-catalyzed conversion of trioses to alkyl
            幅降低,乳酸甲酯收率为 86.9%~92.3%,说明 300  ℃                      lactates in alcohol solution[J]. Chem Commun, 2005, 21: 2716-2718.
                                                               [6]   PESCARMONA P P, JACOBS P  A,  SELS B F. Zeolite-catalysed
            处理能够除去负载在催化剂表面的残余物,使催化                                 conversion of C3 sugars to alkyl lactates[J]. Green Chem, 2010, 12(6):
            剂重新获得较高的活性。由图 8 可知,改性催化剂                               1083-1089.
                                                               [7]   YANG X M, WU U L, XU U J, et al. Conversion of dihydroxyacetone
            具有良好的循环性和稳定性,可有效催化 DHA 与醇                              to methyl lactate catalyzed by highly active hierarchical Sn-USY at
            反应制备乳酸酯。                                               room temperature[J]. Catal Sci Technol, 2016, 6: 1757-1763.
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                      图 8  M-3 催化剂循环利用性能                       [13]  GODARD N, COLLARD X, APRILEA  C,  et al. Rapid room
                      Fig. 8    Reusability of M-3 catalyst        temperature synthesis of tin-based mesoporous solids: Influence of the
                                                                   particle size on the production of ethyl lactate[J]. Appl Catal A-Gen,
            3   结论                                                 2018, 556(25): 73-80.
                                                               [14]  WANG J C, MASUI Y M, ONAKA M. Conversion of triose sugars
                 改性 Sn-MCM-22 催化剂用于催化 DHA 与醇制                      with alcohols  to alkyl lactates catalyzed by Brønsted acid tin ion-
                                                                   exchanged montmorillonite[J]. Appl Catal B-Environ, 2011, 107(1/2):
            备乳酸酯表现出较好的催化性能。催化剂通过硝酸                                 135-139.
            脱 MCM-22 骨架铝,然后经过 SnCl 4 •5H 2 O 和 HMI             [15]  DE CLIPPEL F, DUSSELIER M, SELS B F, et al. Fast and selective
                                                                   sugar conversion  to alkyl lactate and lactic acid with bifunctional
            水热晶化法制备得到;Sn 以嵌入和 SnO 2 接枝方式                           carbon-silica  catalysts[J]. J  Am  Chem Soc, 2012, 134(24): 10089-
            改性 MCM-22;改性 Sn-MCM-22(M-3)催化剂有效                       10101.
            调控了 Lewis 和 Brønsted 酸性位点比例,提高了催                   [16]  LYU X L, XU L, LU X Y, et al. New insights into the NiO catalytic
                                                                   mechanism on the conversion of fructose to methyl lactate[J]. Catal
            化剂对 DHA 制备乳酸酯的催化性能。当选用催化剂                              Commun, 2019, 119: 46-50.
            M-3 60 mg,DHA 醇溶液浓度 0.25 mol/L,反应时                 [17]  TEMPELMAN C H, PORTILLA L M T, HENSEN E J M, et al. One-
                                                                   pot synthesis of nano-crystalline MCM-22[J]. Micropor Mesopor
            间 7~15 h,DHA 与甲醇、乙醇、正丙醇、正丁醇反                           Mater, 2016, 220: 28-38.
            应制备相应乳酸酯收率为 86.4%~96.3%。改性催化                       [18]  WANG Z D (王振东), ZHANG Y X (张云贤), YANG W M (杨为
            剂 M-3 容易回收,在 300  ℃下煅烧处理 2 h 可除去                       民), et al. Synthesis and catalytic properties  of MCM-22 zeolites
                                                                   with different morphologies[J]. Acta Petrolei Sinica (Petroleum
            负载在表面的残余物,催化剂重新获得较高的活性,                                Processing Section) (石油学报:  石油加工), 2014, 30(1): 110-114.
            循环使用 4 次,乳酸甲酯收率为 86.9%~92.3%。此                     [19]  KIM K  D, WANG Z  C, HUANG J,  et al. The cooperative effect  of
                                                                   Lewis  and Brønsted acid sites on Sn-MCM-41 catalysts for the
            后研究应着重于简化催化剂的制备方法,降低催化
                                                                   conversion of  1,3-dihydroxyacetone  to ethyl  lactate[J]. Green Chem,
            反应温度,减少反应时间,进一步提高乳酸酯的收                                 2019, 21(9): 3383-3393.
            率,提供更丰富的应用研究。                                      [20]  NIE L Y (聂丽影). Properties of zeolites catalyze dihydroxyacetone
                                                                   synthesis of  methyl lactate[D]. Changchun: Jilin University (吉林大
                                                                   学), 2012.
            参考文献:
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                 of sugars to  lactic acid derivatives  using  heterogeneous zeotype   ChemistrySelect, 2017, 2(1): 309-314.
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            [2]   DUSSELIER M, WOUWE P V, DEWAELE A, et al. Lactic acid as a   methyl lactate catalyzed by highly active hierarchical Sn-USY at room
                 platform chemical in the biobased economy: The role of chemocatalysis   temperature[J]. Catal Sci Technol, 2016, 6: 1757-1763.
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