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使用负载型铱基催化剂将5-羟甲基糠醛直接还原胺化制备5-(氨甲基)-2-呋喃甲醇

Direct Reductive Amination of HMF to 5-(Aminomethyl)-2-furanmethanol Using Supported Iridium-based Catalysts.

作者信息

Ruiz Doris, Morales Karen, Mäki-Arvela Päivi, Chimentão Ricardo J, Murzin Dmitry Yu

机构信息

Physical Chemistry Department, Faculty of Chemical Sciences, University of Concepcion, Casilla 160-C, Concepción, Chile.

Johan Gadolin Process Chemistry Centre, Laboratory of Industrial Chemistry and Reaction Engineering, Åbo Akademi University, Turku/Åbo, Finland.

出版信息

Chempluschem. 2024 Dec;89(12):e202400453. doi: 10.1002/cplu.202400453. Epub 2024 Oct 4.

Abstract

In this work, partial reductive amination of 5-hydroxymethylfurfural (HMF) with gaseous ammonia over iridium supported on γ-AlO, TiO, SiO and carbon has been studied. The influence of the support and pressure was investigated in the valorization under mild conditions of HMF to 5-(aminomethyl)-2-furanmethanol (AMFM). The catalysts were characterized by TEM, SEM-EDS, N sorption Isotherms, TGA, CO-Chemisorption, TPR, XRD, NH-TPD, ICP-AES and XPS. The maximum activity and high rates were obtained for all catalytic systems. At 50 minutes of the reaction the Ir/C catalyst achieved 93 % of conversion and exhibited the highest yield and selectivity of 92 % and 99 % respectively, to the desired product 5-(aminomethyl)-2-furanmethanol. The main properties that influence activity and selectivity are related to the amount of iridium on the surface and catalyst acidity. After the third cycle, 63 % and 59 % of selectivity and yield to AMFM respectively at 93 % of conversion were obtained.

摘要

在本工作中,研究了5-羟甲基糠醛(HMF)与气态氨在负载于γ-AlO、TiO、SiO和碳上的铱催化剂上进行的部分还原胺化反应。在温和条件下将HMF转化为5-(氨甲基)-2-呋喃甲醇(AMFM)的过程中,研究了载体和压力的影响。通过透射电子显微镜(TEM)、扫描电子显微镜-能谱仪(SEM-EDS)、氮吸附等温线、热重分析(TGA)、一氧化碳化学吸附、程序升温还原(TPR)、X射线衍射(XRD)、氨程序升温脱附(NH-TPD)、电感耦合等离子体发射光谱(ICP-AES)和X射线光电子能谱(XPS)对催化剂进行了表征。所有催化体系均获得了最高活性和高反应速率。在反应50分钟时,Ir/C催化剂实现了93%的转化率,对目标产物5-(氨甲基)-2-呋喃甲醇的产率和选择性分别高达92%和99%。影响活性和选择性的主要性质与表面铱含量和催化剂酸度有关。在第三个循环后,在转化率为93%时,对AMFM的选择性和产率分别达到63%和59%。

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