雙氧水液相氧化系統之設計用於5-羥甲基糠醛(HMF)氧化反應

Hydrogen Peroxide-Assisted Liquid Phase Oxidation of 5-Hydroxymethylfurfural (HMF) in Aqueous System

陳靖天(Ching-Tien Chen)

指導教授 ： 吳嘉文

國立臺灣大學/工學院/化學工程學研究所/碩士(2015年)

https://doi.org/10.6342/NTU.2015.02254

摘要

5-羥甲基糠醛 (5-Hydroxymethylfurfural, HMF) 為一個木質纖維素衍生之生質物，並可做為許多高價值化合物之前驅物。近年來HMF的氧化反應越來越被重視，原因在於其氧化後的最終產物2,5-呋喃二甲酸 (2,5-Furandicarboxlic acid, FDCA) 具有取代傳統石油煉製而得的對苯二甲酸之潛力，而做為未來製造塑膠時的單體化合物，同時也是一種可再生的物質。
本論文設計了HMF的液相氧化反應系統，並以雙氧水為氧化劑、以活性碳搭載釕金屬 (Ruthenium, Ru) 為催化劑。此系統的特點在於反應條件溫和，溫度為攝氏75度，壓力為一大氣壓。重量百分濃度10% 的雙氧水在反應過程中以連續滴入的方式滴加至系統，並加入與HMF等當量之碳酸鈉以提供鹼性環境。
透過調控HMF對釕金屬的莫耳比 (HMF/Ru)以及反應時間，我們可以控制產物的組成成分。當HMF/Ru為50，我們可以在1小時之內得到85%產率之2-甲酰基-呋喃-2-甲酸 (5-Formyl-2-furoic acid, FFCA) ，而當HMF/Ru為10的時候，可以在反應6小時之後得到高達91%產率之FDCA。

關鍵字

5-羥甲基糠醛 ； 2,5-呋喃二甲酸 ； 氧化 ； 雙氧水 ； 釕

並列摘要

5-Hydroxymethylfurfural (HMF) is a lignocellulosic-derived compound which can be the platform chemical of many value compounds. The oxidation of HMF has received great attention in recent years since the final product, 2,5-furandicarboxlic acid (FDCA), is a renewable building block chemical with the potential of replacing terephthalic acid to be the monomer in plastic manufacturing.
In this thesis, we propose an aqueous oxidation system for HMF with hydrogen peroxide (H2O2) as liquid phase oxidant and activated carbon supported ruthenium (Ru/AC) as catalyst. 10 wt% H2O2 solution was injected to the system dropwisely during the whole process under 75ºC and atmospheric pressure. Sodium carbonate (Na2CO3) was used to provide basic environment, and only an equivalent amount as HMF was needed.
By changing the molar ratio of HMF to Ru (HMF/Ru) and the reaction time, we could control the product compositions. The HMF/Ru of 50 gives 5-formyl-2-furoic acid (FFCA) in 85% yields within 1 hour, and HMF/Ru of 10 gives FDCA in 91% yields after reacting for 6 hours.

並列關鍵字

HMF ； FDCA ； oxidation ； H2O2 ； ruthenium

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