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布朗斯特酸和路易斯酸位点在木糖转化为糠醛中的作用。

Function of Brønsted and Lewis acid sites in xylose conversion into furfural.

作者信息

Cabrera-Munguia Denis A, Gutiérrrez-Alejandre Aída, Romero-Galarza Adolfo, Morales-Martínez Thelma K, Ríos-González Leopoldo J, Sifuentes-López Jesús

机构信息

Facultad de Ciencias Químicas, Universidad Autónoma de Coahuila Ing. J. Cárdenas s/n Saltillo Coahuila 25280 Mexico

UNICAT, Depto. de Ingeniería Química, Facultad de Química, UNAM Ciudad de México 04510 Mexico.

出版信息

RSC Adv. 2023 Oct 18;13(44):30649-30664. doi: 10.1039/d3ra05774g.

Abstract

In this work, the xylose conversion and the selectivity to furfural were assessed over mesoporous sulfonic silica SBA-15-(X)SOH catalysts doped with metal ions (X = Al(iii), Ti(iv) or Zr(iv)). The type and amount of acid sites were analyzed by adsorption of pivalonitrile. The SBA-15-(X)SOH materials show Lewis acid sites (LAS) and two types of Brønsted acid sites (BAS) with different strengths. Type I (BAS I) belongs to terminal silanol groups, type II (BAS II) is ascribed to hydroxyl groups bonded to sulfur or transition metal, and the LAS is related to M-O bonds. Optimal reaction conditions for the most active catalyst (SBA-15-(Zr)SOH) were 120 minutes of reaction at 160 °C, 20 wt% of catalyst, and 2.5% of xylose/solvent. Additionally, a kinetic study was carried out to calculate the rate constants, the activation energy, and the pre-exponential factor for the xylose dehydration reaction. It was found that the selectivity to furfural in sulfonic silica SBA-15-(X)SOH catalysts was directly related to the BAS II fraction. While LAS negatively impacts the selectivity to furfural leading to the undesired reaction between furfural and xylose obtaining humins as secondary products.

摘要

在本工作中,研究了负载金属离子(X = Al(iii)、Ti(iv) 或 Zr(iv))的介孔磺酸硅 SBA-15-(X)SOH 催化剂上木糖的转化以及对糠醛的选择性。通过新戊腈吸附分析了酸位点的类型和数量。SBA-15-(X)SOH 材料具有路易斯酸位点(LAS)和两种不同强度的布朗斯特酸位点(BAS)。I 型(BAS I)属于末端硅醇基团,II 型(BAS II)归因于与硫或过渡金属键合的羟基,而 LAS 与 M-O 键有关。最具活性的催化剂(SBA-15-(Zr)SOH)的最佳反应条件为在 160 °C 下反应 120 分钟、催化剂用量为 20 wt%以及木糖/溶剂比例为 2.5%。此外,进行了动力学研究以计算木糖脱水反应的速率常数、活化能和指前因子。结果发现,磺酸硅 SBA-15-(X)SOH 催化剂对糠醛的选择性与 BAS II 分数直接相关。而 LAS 对糠醛的选择性产生负面影响,导致糠醛与木糖之间发生不期望的反应,生成腐殖质作为副产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9fa9/10583826/a22c6407db91/d3ra05774g-f1.jpg

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