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Study on the Conversion of Glucose to 5-hydroxymethylfurfural and Furan-2, 5-dicarboxylic Acid
Author: ChenTianMing
Tutor: LinLu
School: South China University of Technology
Course: Pulp and Paper Engineering
Keywords: glucose 5-hydroxymethylfurfural furan-2, 5-dicarboxylic CPL-LiCl
CLC: TQ251.1
Type: Master's thesis
Year: 2011
Downloads: 499
Quote: 0
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Abstract
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Mounting global environmental and energy problems have stimulated increased efforts towards synthesizing biofuels and high-value chemicals from renewable biomass resources, especially woody biomass.Woody biomass usually have to be changed to micromolecule (such as glucose) before they are converted to biofuels and high-value chemicals. Therefore, the study on how glucose can converted to biofuels and high-value chemicals in high yield is significatively.The dehydration of glucose to 5-hydroxymethylfurfural; the oxidation of 5-hydroxymethylfurfural to produce furan-2, 5-dicarboxylic acid were studied in this paper.A method for the determination of 5-hydroxymethylfurfural by an ion chromatograp in the glucose hydrolyzate was developed. After handling samples simply, 5-hydroxymethylfurfural was analyzed using Dionex ICS-3000 ion-exchange chromatography with electrochemical detector. The glucose hydrolyzates were separated on a CarboPacTM PA1 column (i.d.2×250mm) by using isocratic elution consisting of 70mmol/L sodium hydroxide at a flow rate of 0.35 mL/min. The experimental results showed that linear correlations of glucose and HMF were observed, and the correlation coefficient r2 was over 0.999. The recoveries were 100.4%、98.1%, respectively. The relative standard deviation is 0.82%、0.61%, respectively. The minimum determination limit was 0.02 mg/L and 0.01 mg/L. This method had the advantages of rapid analysis, high sensitivity, good precision, small sample use quantity and no derivatization reaction.A pathway from glucose to prepare 5-Hydroxymethylfurfural (HMF) with cation exchange resin and Al2O3 as catalyst and DMSO as reaction medium was dealt with. It was found that under the reaction temperature, can promote the formation of HMF from glucose. Glucose conversion, the HMF yield and selectivity can reach 90.19%, 44.53% and 49.37% for a 12 h reaction time at 130℃with 10wt% concentration. Influences of concentrations on reaction were studied, and the most perfect concentration was 10wt%. The stability of the ion-exchange resin and Al2O3 used as the catalyst was confirmed. The method has the advantages of moderate reaction condition, inexpensive raw material, simple operation and friendly to environment. 5-Hydroxymethylfurfural (HMF), an important versatile sugar derivative, is also considered a key intermediate between petroleum-based industrial organic chemistry and bio-based carbohydrate chemistry. Here, we report that caprolactam (CPL) containing lithium chloride (LiCl) is a privileged solvent that enables the synthesis of the renewable platform chemical 5-hydroxymethylfurfural (HMF) from purified glucose. Metal halides in CPL-LiCl are catalysts, among which CrCl3, CrCl2, SnCl4, and SnCl2 are found to be uniquely effective, leading to the conversion of glucose to HMF with yields of 55-67%. The simplicity of this chemical transformation of glucose contrasts markedly with the complexity of extant processes and provides a new paradigm for the use of biomass as a raw material for a renewable energy and chemical industries.The furan-2, 5-dicarboxylic acid was synthesized with potassium permanganate and 5-hydroxymethylfurfural. The influence of the reaction conditions, such as the sodium hydroxide concentration of the reaction system, the reactant ratio, the reaction time, upon the yield of furan-2, 5-dicarboxylic acid, was investigated. The result showed that the optimal reaction conditions are in acidic condition when the sodium hydroxide concentration of the reaction system is 2.2mol/L, the reachtant ratio at 2.4:1, and the reaction time 10min. The method for producing furan-2, 5-dicarboxylic acid is provided which can efficiently and quantitatively producing furan-2, 5-dicarboxylic acid under mild conditions, without employing an expensive catalyst and with a reduced energy consumption.
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CLC: > Industrial Technology > Chemical Industry > Basic Organic Chemistry Industry > The production of heterocyclic compounds > Five heterocycles containing a single different atoms > Oxa -mao ( furans) family
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