Chemical and Environmental Engineering Group, ESCET, Universidad Rey Juan Carlos, C/Tulipán s/n, E-28933, Móstoles, Madrid (Spain).
ChemSusChem. 2015 Mar;8(6):1088-94. doi: 10.1002/cssc.201402965. Epub 2015 Feb 20.
Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling.
木糖到木酮糖的异构化在两步甲醇-水过程中被大孔沸石高效催化,显著提高了产物产率。该反应途径涉及木糖异构化为木酮糖,部分木酮糖随后与甲醇反应形成甲基木糖苷(步骤 1),然后在加水后进行水解形成额外的木酮糖(步骤 2)。用(13)C 标记的木糖进行的 NMR 光谱研究证实了所提出的反应途径。考察的最活跃的催化剂是沸石 Y,它比沸石β、ZSM-5 和丝光沸石更活跃。在 100°C 反应 1 小时后,H-USY(Si/Al=6)得到的木酮糖产率为 39%。在第二个反应步骤中进行水水解后,产率增加到 47%。吡啶吸附研究的结果证实,H-USY(6)是一种同时具有 Brønsted 和 Lewis 酸位的催化剂,可在醇介质中将木糖异构化为木酮糖,在低温下进行反应。所应用的沸石是商业上可获得的;不包含任何辅助四价金属,例如锡、钛或锆;高效异构化木糖;易于再生;并且易于回收。