Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Proc Natl Acad Sci U S A. 2010 Apr 6;107(14):6164-8. doi: 10.1073/pnas.1002358107. Epub 2010 Mar 22.
The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (150 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].
葡萄糖异构化为果糖是生产高果糖玉米糖浆(HFCS;由酶催化剂进行的反应)的大规模反应,最近它被认为是生物质转化为燃料和化学品的可能途径中的中间步骤。在这里,研究表明含有锡(Sn-Beta)的大孔沸石能够在水相介质中以高活性和选择性将葡萄糖异构化为果糖。具体来说,在 383 K 和 413 K 下反应 30 分钟和 12 分钟后,含有催化量 Sn-Beta(Sn:葡萄糖摩尔比为 150)的 10%(wt/wt)葡萄糖溶液的产物收率分别约为 46%(wt/wt)葡萄糖、31%(wt/wt)果糖和 9%(wt/wt)甘露糖。当使用 45 wt%葡萄糖溶液时,也可以实现这种反应性。大孔沸石的特性极大地影响了反应行为,因为反应不会在中孔沸石中进行,并且当金属中心被纳入有序介孔硅(MCM-41)时,异构化活性会显著降低。Sn-Beta 催化剂可以重复使用多个循环,当固体被移除时,反应停止,这清楚地表明催化是在异相进行的。最重要的是,Sn-Beta 催化剂能够在高度酸性的水相环境中进行异构化反应,具有与无外加酸的介质中相当的活性和产物分布。这使得 Sn-Beta 能够将异构化反应与其他酸催化反应相结合,包括水解/异构化或异构化/脱水反应序列[此处展示了从淀粉到果糖和葡萄糖到 5-羟甲基糠醛(HMF)的转化]。