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不同溶劑下葡萄糖制取5-羥甲基糠醛的動(dòng)力學(xué)研究
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國(guó)家自然科學(xué)基金資助項(xiàng)目(51476142)


Kinetic Study on Conversion of Glucose to 5-hydroxymethylfurfural in Different Solvents
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    摘要:

    為了研究溶劑效應(yīng)對(duì)單糖轉(zhuǎn)化制取5-羥甲基糠醛 (HMF)的影響,考察了葡萄糖在3種不同溶劑(水、二甲亞砜(DMSO)、水-DMSO)下較寬溫度范圍內(nèi)(100~200℃)無(wú)催化條件下的降解行為,實(shí)驗(yàn)結(jié)果顯示,在175℃水-DMSO混合溶劑下,HMF的產(chǎn)率可達(dá)到20.7%,遠(yuǎn)高于水溶劑下的11.86%和DMSO溶劑下的10.0%。采用涉及5-羥甲基糠醛(HMF)、乙酰丙酸(LA)和腐殖質(zhì)(humin)生成的反應(yīng)模型分析了葡萄糖降解動(dòng)力學(xué),該模型較好地吻合了實(shí)驗(yàn)結(jié)果。動(dòng)力學(xué)分析表明,DMSO的存在改變了葡萄糖的異構(gòu)化途徑并生成了果糖和半乳糖,同時(shí)抑制了HMF進(jìn)一步發(fā)生再水合反應(yīng)生成LA和發(fā)生聚合反應(yīng)生成humin。此外,針對(duì)humin的結(jié)構(gòu)表征進(jìn)一步揭示了水和DMSO對(duì)humin生成的不同作用機(jī)制。

    Abstract:

    As a high value-added platform chemical in biorefinery, 5-hydroxymethylfurfural (HMF) can undergo conversion to various fine chemicals and high quality liquid fuels. Glucose decomposition in liquid-phase system is the conventional route for HMF production. To get insights into the effects of different solvents on HMF formation, the conversion of glucose in three different solvents, including water, dimethylsulfoxide (DMSO), and water-DMSO mixture, was performed over the temperature range of 100℃ to 200℃. The results showed that the yield of HMF in water-DMSO mixture at 175℃ was up to 20.7%, which was much higher than that in pure water (11.86%) and DMSO (10.0%). A reaction model involving the formation pathways of HMF, levulinic acid (LA) and humin was used to analyze the kinetics of glucose decomposition, and the obtained kinetic parameters predicted experimental results very well. It was found that DMSO altered the path of glucose isomerization, resulting in the formation of fructose and galactose. Compared with the enhancement of HMF activity in water, DMSO suppressed the further reaction of HMF to form LA and humin. Moreover, the properties of the humins generated in the three solvents were characterized, and the corresponding formation mechanisms were discussed.

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林海周,孫武星,茹 斌,陳景平,王樹(shù)榮.不同溶劑下葡萄糖制取5-羥甲基糠醛的動(dòng)力學(xué)研究[J].農(nóng)業(yè)機(jī)械學(xué)報(bào),2015,46(11):201-207. Lin Haizhou, Sun Wuxing, Ru Bin, Chen Jingping, Wang Shurong. Kinetic Study on Conversion of Glucose to 5-hydroxymethylfurfural in Different Solvents[J]. Transactions of the Chinese Society for Agricultural Machinery,2015,46(11):201-207.

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  • 收稿日期:2015-03-14
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  • 在線(xiàn)發(fā)布日期: 2015-11-10
  • 出版日期: 2015-11-10