Clean Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid by Aqueous Phase Conversion of Levoglucosenone over Solid Acid Catalysts
Clean Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid by Aqueous Phase Conversion of Levoglucosenone over Solid Acid Catalysts
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DOI：
10.1021/acssuschemeng.8b05873
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发表时间：
2019-03-18
影响因子：
8.4
通讯作者：
Hayashi, Jun-ichiro
中科院分区：
文献类型：
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作者：
Huang, Xin;Kudo, Shinji;Hayashi, Jun-ichiro
左旋葡萄糖酮（LGO）是一种新兴的生物可再生平台，用于精细化工和商品化工行业。在此，我们报道了在固体酸催化剂上，LGO水相转化为5-羟甲基糠醛（HMF）和乙酰丙酸（LA）。研究了沸石、强酸性离子交换树脂和磺化活性炭等固体酸催化剂对该反应的催化作用。在所测试的催化剂中，ZSM-5和Amberlyst 70在选择性生成目标产物方面表现出最好的性能，HMF和LA的摩尔总收率最高，为72.2%。通过对催化剂的比较和对孔隙形态、路易斯酸位点的存在以及LGO或其水合产物直接降解产物的形成的动力学分析，确定了降低反应选择性的因素。经过单批次实验，ZSM-5和Amberlyst 70含有降解产物的沉积物，但可以重复使用，活性损失很小，尽管ZSM-5需要煅烧。该催化系统采用LGO作为原料和可回收固体酸催化剂，仅使用水作为反应介质，因此有可能成为生产关键构件HMF和LA的清洁途径。
Levoglucosenone (LGO) is an emerging bio-renewable platform for the fine and commodity chemical industries. Herein, we report an aqueous phase conversion of LGO to 5-hydroxylmethylfurfural (HMF) and levulinic acid (LA) over solid acid catalyst. Several types of solid acid catalysts such as zeolites, strongly acidic ion-exchange resin, and sulfonated activated carbon were investigated for this reaction. Among the tested catalysts, ZSM-5 and Amberlyst 70 showed the best performances for selectively producing the target products, resulting in the highest total yield of HMF and LA at 72.2% on a molar basis. Factors decreasing the reaction selectivity were identified through the comparison of catalysts and kinetic analysis to the pore morphology, presence of Lewis acid sites, and formation of degradation products directly from LGO or its hydrated product. ZSM-5 and Amberlyst 70, after a single-batch experiment, contained deposits from the degradation products but could be reused with little loss in activity, although calcination was required for ZSM-5. The catalytic system, employing LGO as feedstock and recyclable solid acid catalysts, uses only water as reaction media and thus has the potential to be a clean route for producing the key building blocks HMF and LA.