Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides
Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides
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DOI：
10.1039/b611568c
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发表时间：
2007-01-01
期刊：
影响因子：
9.8
通讯作者：
Dumesic, James A.
中科院分区：
文献类型：
--
作者：
Chheda, Juben N.;Roman-Leshkov, Yuriy;Dumesic, James A.
从可再生生物质衍生的碳水化合物获得的呋喃衍生物，如5-羟甲基糠醛（HMF）和糠醛，具有成为用于生产精细化学品和塑料的石油基结构单元的可持续替代品的潜力。我们已经研究了使用两相反应器系统通过果糖、葡萄糖和木糖的脱水来生产HMF和糠醛，所述两相反应器系统包括用DMSO改性的反应性水相，与由7：3（w/w）MIBK-2-丁醇混合物或二氯甲烷（DCM）组成的有机萃取相组合。使用MIBK-2-丁醇混合物的实验在443 K的温度下使用无机酸催化剂（HCl、H2SO 4和H3 PO 4）在1.0至2.0的pH下进行，而使用DCM作为萃取溶剂的实验在413 K下进行并且不需要使用酸催化剂。双相系统的可修改性质允许我们确定每种糖的优选DMSO和pH水平，以在高糖转化率下使HMF选择性最大化，分别导致果糖、木糖和葡萄糖脱水的选择性为89%、91%和53%。对每个单糖单元使用这些反应条件，我们可以在高转化率下以同样良好的选择性加工相应的多糖，如蔗糖（葡萄糖和果糖的二糖）、菊粉（聚果聚糖）、淀粉（聚葡聚糖）、纤维二糖（葡萄糖二聚体）和木聚糖（木糖多糖）。此外，我们表明，双相反应器系统可以处理高进料浓度（10至30重量%）沿着具有良好的再循环能力。通过加工这些廉价且大量可用的高度官能化的多糖，我们消除了通过酸水解作为单独加工步骤获得简单碳水化合物分子的需要。
Furan derivatives, such as 5-hydroxymethylfurfural (HMF) and furfural, obtained from renewable biomass-derived carbohydrates have potential to be sustainable substitutes for petroleum-based building blocks used in production of fine chemicals and plastics. We have studied the production of HMF and furfural by dehydration of fructose, glucose and xylose using a biphasic reactor system, comprised of reactive aqueous phase modified with DMSO, combined with an organic extracting phase consisting of a 7 : 3 (w/w) MIBK-2-butanol mixture or dichloromethane (DCM). Experiments with the MIBK-2-butanol mixture were conducted at a temperature of 443 K using mineral acid catalysts (HCl, H2SO4 and H3PO4) at a pH from 1.0 to 2.0, whereas experiments with DCM as the extracting solvent were conducted at 413 K and did not require the use of an acid catalyst. The modifiable nature of the biphasic system allowed us to identify preferred DMSO and pH levels for each sugar to maximize the HMF selectivity at high sugar conversions, leading to selectivities of 89%, 91%, and 53% for dehydration of fructose, xylose, and glucose, respectively. Using these reaction conditions for each monosaccharide unit, we can process the corresponding polysaccharides, such as sucrose ( a disaccharide of glucose and fructose), inulin ( a polyfructan), starch ( a polyglucan), cellobiose ( a glucose dimer) and xylan ( a xylose polysaccharide), with equally good selectivities at high conversions. In addition, we show that the biphasic reactor system can process high feed concentrations ( 10 to 30 wt%) along with excellent recycling ability. By processing these highly functionalized polysaccharides, that are inexpensive and abundantly available, we eliminate the need to obtain simple carbohydrate molecules by acid hydrolysis as a separate processing step.