氧化钽及钽钨复合氧化物固体酸催化己糖脱水制备5-羟甲基糠醛以及非等计量比的甲酸和乙酰丙酸

doi:10.1016/S1872-2067(19)63519-9

摘要/Abstract

摘要： 5-羟甲基糠醛（HMF）是最具应用前景的平台化合物之一，HMF制备的研究越来越成为热点，并且已经取得了令人瞩目的研究成果.尽管如此，在现阶段利用固体酸催化剂催化碳水化合物制备HMF的研究仍然面临许多挑战，以葡萄糖为原料制备HMF时产物选择性普遍较低.因此，合成制备高活性催化糖类化合物脱水制HMF的固体酸催化剂，并且研究固体酸催化剂表面酸性质比如酸密度、酸强度以及Brönsted/Lewis酸比值等对糖类化合物制HMF反应中各反应产物选择性的影响，对新型高效催化剂的开发设计具有重要意义.
本文通过溶剂挥发自组装法合成了一系列介孔Ta及Ta-W氧化物固体酸催化剂，并用于催化果糖和葡萄糖脱水制备5-羟甲基糠醛.以三甲基膦（TMP）为探针分子，利用³¹P固体核磁共振谱技术表征催化剂表面酸性质，考察复合金属氧化物固体酸催化剂酸量、酸强度以及酸类型对催化果糖和葡萄糖制备HMF反应性能的影响，为高效催化剂的设计提供一定的理论指导.另外，我们还通过引入2-丁醇构建有机溶剂/水体系，考察有机溶剂对葡萄糖脱水制HMF反应中所用催化剂活性和产物选择性的影响.³¹P固体核磁共振技术表征样品的酸性质发现，随着W掺杂量的增加，系列Ta及Ta-W氧化物的酸强度和Brönsted/Lewis酸量比值逐渐增加.催化反应结果表明，以介孔Ta及Ta-W复合氧化物为催化剂时，果糖和葡萄糖脱水制HMF反应的催化活性和HMF选择性与所用催化剂的酸量、酸类型和酸强度有关.介孔Ta及Ta-W复合氧化物催化剂表面的B/L比值越高，催化反应过程中的己糖转化率也越高，HMF选择性也普遍越高.具有较高Brönsted酸强度的催化剂在水溶液中更易降低HMF产物选择性，归结于HMF的再水解和葡萄糖的非选择性脱水等副反应.实验结果发现，产物甲酸（FA）的选择性远高于乙酰丙酸（LA），说明过量FA很可能来自果糖在Lewis酸位上的分解.2-丁醇的引入能够提高己糖转化率和HMF选择性，并且在B/L比值越高的催化剂上提升的效果越显著.其中，Ta₇W₃氧化物为催化剂时，HMF选择性最高可达54%，并且该催化剂具有良好的催化稳定性，这主要是因为2-丁醇的加入能够有效地抑制反应中胡敏素等聚合物的生成，防止后者在催化剂表面附着导致催化活性降低，进而提高了催化剂在催化反应中的稳定性.

关键词: 葡萄糖, 果糖, 5-羟甲基糠醛, 固体酸, 氧化钽, Ta-W氧化物

Abstract: A series of mesoporous Ta and Ta-W oxides have been prepared and employed as solid acid catalysts for the dehydration of fructose and glucose to 5-hydroxymethylfurfural (HMF). Solid state ³¹P MAS NMR spectroscopic results using trimethylphosphine (TMP) as a probe molecule show that the acid strength and the ratio of Brönsted to Lewis acid sites increase gradually with the addition of tungsten in tantalum oxide. It is found that high sugar conversion and HMF selectivity are achieved over catalyst with relatively high ratios of Brönsted to Lewis acid sites. Unexpected stoichiometric excess of formic acid relative to levulinic acid can be observed mainly because of direct decomposition of fructose over Lewis acid sites. The addition of 2-butanol leads to the increase of sugars conversion and the HMF selectivity, especially for the catalyst with high ratio of Brönsted to Lewis acid sites. Among them, Ta₇W₃ oxide catalyst shows 54% HMF selectivity and good reusability with the addition of 2-butanol by extracting HMF from aqueous phase and removing humins deposed on the surface of the catalyst.

Key words: Glucose, Fructose, HMF, Solid acid, Tantalum oxide, Ta-W oxide

郭斌, 贺露露, 唐钢锋, 张丽, 叶林, 岳斌, 曾适之, 贺鹤勇. 氧化钽及钽钨复合氧化物固体酸催化己糖脱水制备5-羟甲基糠醛以及非等计量比的甲酸和乙酰丙酸[J]. 催化学报, 2020, 41(8): 1248-1260.

Bin Guo, Lulu He, Gangfeng Tang, Li Zhang, Lin Ye, Bin Yue, Shik Chi Edman Tsang, Heyong He. Dehydration of sugars to 5-hydroxymethylfurfural and non-stoichiometric formic and levulinic acids over mesoporous Ta and Ta-W oxide solid acid catalysts[J]. Chinese Journal of Catalysis, 2020, 41(8): 1248-1260.

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