Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts

L. Patrylak, S. Konovalov, A. Yakovenko, O. Pertko, V. Povazhnyi, O. Melnychuk
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Abstract

Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength.
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葡萄糖在颗粒沸石催化剂上转化为5-羟甲基糠醛
生物质衍生的5-羟甲基糠醛(5-HMF)是生产多种有价值的化学品和生物燃料的潜在原料。以己糖为原料,在固体催化剂上工业化生产5-羟甲基糠醛是很有前途的。酸性沸石作为糖脱水催化剂具有很大的应用潜力。这项工作的目的是获得具有最佳酸度的颗粒沸石催化剂,并根据所使用的粘合剂的性质评估其有效性。制备了无粘结剂的沸石催化剂和高岭土/氧化铝质量分数为10%的样品。采用氮气低温吸附/脱附、氨热程序脱附、红外控制吡啶吸附等方法研究了其孔隙特性和酸性。研究了在160℃二甲亚砜介质中葡萄糖合成5-羟甲基糠醛催化剂的活性和选择性。证实了颗粒样品在葡萄糖转化为5-羟甲基糠醛方面的高效率。它们不仅不劣于,甚至优于粉末样品。本文详细讨论了沸石的Brønsted和Lewis酸度的组成来源,尽管其Lewis中心数量较少,但仍具有可接受的活性(对5-HMF的选择性为34%)。氧化铝的效率最高,不仅没有明显恶化催化剂的微孔特性,而且还提高了催化剂的介孔性能。对5-羟甲基糠醛的选择性达到44%。然而,氧化铝样品的介孔发育程度对其活性并不是决定性的。中等强度酸中心的存在是影响5-羟甲基糠醛催化剂合成效果的主要因素。
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