稻秆粉末醇解产物的分析和醇解机理研究
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摘要
分别以甲醇和乙醇作为溶剂与湖北红安产的稻秸粉末(以下简称RSP)在磁力搅拌不锈钢高压反应釜内进行了超临界醇解反应,并在索氏萃取器中依次用甲醇(或乙醇)、丙酮、二硫化碳和丙酮/二硫化碳混合溶剂对醇解产物进行分级萃取,用气相色谱/质谱联用仪(GC/MS)分析了醇解产物,考察了反应温度、时间和压力对RSP超临界醇解的影响。实验结果表明,反应温度和压力达到醇溶剂的超临界条件时,RSP的降解较彻底,且醇解产物收率与反应时间成正比。在醇解产物中检测出百余种有机化合物,主要是含氧有机化合物,尤其是含甲氧基或乙氧基的有机化合物。超临界甲醇解产物中含甲氧基的有机化合物的相对含量高达40%以上;超临界乙醇解产物中含乙氧基的有机化合物的相对含量接近20%,同时还检测出含甲氧基苯的有机化合物(相对含量为17.6%),说明应该有部分甲氧基是源自秸秆的木质素成分。在醇解产物中检测出大量的苯酚衍生物,这些化合物可以作为精细化学品利用。此外,在醇解产物中还检测出多种长链脂肪酸酯,这些化合物可用于制备高级润滑油和高品质的生物柴油等。通过对愈创木基丙烷单元的可能反应分析,提出RSP的解聚涉及其中有机质大分子含氧桥键的热解与醇分解所得烷基和羟基游离基诱导而断裂的机理。
本文的研究结果表明,在相对温和的条件下(≤300 oC)采用超临界醇解技术可使秸秆中有机质大分子选择性地解聚,提供了了解秸秆分子结构信息的重要手段,也为开发农作物秸秆高效利用的新工艺提供理论依据。
Rice-stalk powder was alkanolyzed with sub- and supercritical methanol or ethanol in a magnetically stirred, stainless-steel autoclave under different conditions. The reaction mixtures were sequentially extracted with methanol (or ethanol), acetone, carbon disulfide and an acetone/carbon disulfide mixed solvent. The extracts were analyzed with a Hewlett-Packard 6890/5973 gas chromatograph/mass spectrometry system. The effects of reaction temperature, time and hydrogen pressure on the RSP alkanolysis of were examined. The experimental results show that RSP was significantly alkanolyzed under supercritical conditions and the total yield of the alkanolyzed products increased with prolonging reaction time. More than 100 organic compounds were detected from products, most of which are oxygen-containing ones, especially methoxy- and/or ethoxy-containing ones. The relative content of methoxy-containing organic compounds is more than 40% in the products from supercritical methanolysis of RSP, whereas that of ethoxy-containing ones is near 20% and methoxyphenyl-containing ones were also detected with 17.6% of relative content in the products from supercritical ethanolysis of RSP, indicating that the methoxyphenyl-containing moieties is originated from lignin in RSP. A number of phenol derivatives, which can be used as fine chemicals, were detected. In addition, a lot of fatty acid esters were also detected. They can be used to produce advanced lubricants and high quality diesel. According to the analysis of the possible reaction of guaiacyl propane, the mechanism of the RSP’s alkanolysis under supercritical conditions has been proposed, which involved pyrolysis and induced breaking of oxygen-containing bridge bond in organic macromolecule. And the inducing groups are the free alkyl and hydroxyl coming from the decomposition of alkanols.
The above results show that the organic macromolecules in RSP can be selectively deploymerized under relatively mild conditions (≤300 oC) by using supercritical alcoholysis. The related techniques provides an important approach to the understanding of information on molecular structures of crop stalks and establishes theoretical basis of developing new technology for the effective utilization of crop stalks.
本文的研究结果表明,在相对温和的条件下(≤300 oC)采用超临界醇解技术可使秸秆中有机质大分子选择性地解聚,提供了了解秸秆分子结构信息的重要手段,也为开发农作物秸秆高效利用的新工艺提供理论依据。
Rice-stalk powder was alkanolyzed with sub- and supercritical methanol or ethanol in a magnetically stirred, stainless-steel autoclave under different conditions. The reaction mixtures were sequentially extracted with methanol (or ethanol), acetone, carbon disulfide and an acetone/carbon disulfide mixed solvent. The extracts were analyzed with a Hewlett-Packard 6890/5973 gas chromatograph/mass spectrometry system. The effects of reaction temperature, time and hydrogen pressure on the RSP alkanolysis of were examined. The experimental results show that RSP was significantly alkanolyzed under supercritical conditions and the total yield of the alkanolyzed products increased with prolonging reaction time. More than 100 organic compounds were detected from products, most of which are oxygen-containing ones, especially methoxy- and/or ethoxy-containing ones. The relative content of methoxy-containing organic compounds is more than 40% in the products from supercritical methanolysis of RSP, whereas that of ethoxy-containing ones is near 20% and methoxyphenyl-containing ones were also detected with 17.6% of relative content in the products from supercritical ethanolysis of RSP, indicating that the methoxyphenyl-containing moieties is originated from lignin in RSP. A number of phenol derivatives, which can be used as fine chemicals, were detected. In addition, a lot of fatty acid esters were also detected. They can be used to produce advanced lubricants and high quality diesel. According to the analysis of the possible reaction of guaiacyl propane, the mechanism of the RSP’s alkanolysis under supercritical conditions has been proposed, which involved pyrolysis and induced breaking of oxygen-containing bridge bond in organic macromolecule. And the inducing groups are the free alkyl and hydroxyl coming from the decomposition of alkanols.
The above results show that the organic macromolecules in RSP can be selectively deploymerized under relatively mild conditions (≤300 oC) by using supercritical alcoholysis. The related techniques provides an important approach to the understanding of information on molecular structures of crop stalks and establishes theoretical basis of developing new technology for the effective utilization of crop stalks.
引文
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