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    木质素水热解聚耦合水相重整制高品质生物油

    High-quality bio-oil production via lignin hydrothermal depolymerization coupled with aqueous phase reforming

    • 摘要: 木质素作为生物质资源中唯一富含芳香族结构的可再生组分,其高效解聚与高值利用是生物质能利用领域重点内容。研究以乙醇–水混合溶剂为反应介质实现木质素水热解聚,并耦合水相重整反应实现解聚产物(生物油)的提质。通过探究反应条件对解聚产物收率的影响,发现在反应温度260 ℃、时间60 min及固液比(木质素/溶剂)(1.5∶20) g/mL时,木质素水热解聚所得生物油重油收率最高,达52.47%。通过对解聚生物油轻质与重质组分的分析发现,重油中以G型酚类(相对含量32.40%)为主,同时富含S型酚类(相对含量17.12%)和酮类化合物(相对含量19.27%),而H型酚类相对含量较低(8.61%);轻油组分则呈现G型酚类高度富集(相对含量50.11%)和醛类产物占比显著(相对含量38.29%)的特点。在320 ℃、20 min条件下,水相重整后生物油的热值达到最大值34.21 MJ/kg,有效氢碳物质的量比(H/Ceff)达到最大值1.02,能量回收率(Re)高达86.31%。重油/水相比对产物的选择性具有明显的影响,GC-MS结果表明,当重油/水相比从(1∶40) g/mL增大到(2∶40) g/mL,重整生物油中酚类和酮类产物相对含量整体呈增长趋势,酚类产物由50.08%增加到63.88%,酮类产物由1.19%增加到14.63%;醚类和酯类产物整体呈下降趋势,醚类产物由12.57%降低到1.37%,酯类产物由21.42%降低到11.96%。研究表明,乙醇–水复合溶剂不仅可实现木质素的高效解聚,其反应后水相还可循环用于生物油水相重整,提升生物油的品质,为木质素资源的高值利用提供了可行路径。

       

      Abstract: Lignin, as the only renewable component rich in aromatic structures within biomass resources, presents efficient depolymerization and high-value utilization as key challenges in biomass energy applications. The research is aimed at achieving the hydrothermal depolymerization of lignin by using an ethanol-water mixed solvent as the reaction medium, coupled with an aqueous phase reforming reaction to enhance the quality of the depolymerized product (bio-oil). Through investigation the influence of reaction conditions on the yield of depolymerization products, it is found that the highest yield of heavy oil of 52.47% from hydrothermal depolymerization of lignin is achieved at a temperature of 260 ℃, a reaction time of 60 min, and a solid-liquid ratio (lignin/solvent) of (1.5∶20) g/mL. Analysis of the light and heavy fractions of the depolymerized bio-oil shows that the heavy oil fraction predominantly contains G-type phenols (32.40%), while also being rich in S-type phenols (17.12%) and ketone compounds (19.27%), with a relatively low content of H-type phenol content (8.61%). The light oil fraction is characterized by a high enrichment of G-type phenols (50.11%) and a significant proportion of aldehyde products (38.29%). Furthermore, under optimal reforming conditions of 320 ℃ and 20 min, the aqueous phase reforming of heavy bio-oil achieves a maximum HHV of 34.21 MJ/kg, an effective hydrogen-to-carbon ratio (H/Ceff) of 1.02, and an energy recovery (Re) as high as 86.31%. GC-MS analysis is employed to investigate the influence of varying heavy oil/water ratios on the component distribution of the reformed bio-oil. Results indicate that the heavy oil/aqueous ratio significantly influenced the product selectivity. As the ratio is increased from (1∶40) to (2∶40) g/mL, the relative content of phenolic and ketone products in the reformed bio-oil shows an overall upward trend. The phenolic product content rises from 50.08% to 63.88%, while ketone products increase from 1.19% to 14.63%. Conversely, ether and ester products exhibit a decreasing trend, with ether products decreasing from 12.57% to 1.37% and ester products decreasing from 21.42% to 11.96%. The study demonstrates that the ethanol-water co-solvent system not only facilitates efficient lignin depolymerization but also allows the aqueous phase to be recovered and reused in subsequent aqueous phase reforming processes. This integrated approach is shown to contribute to improved bio-oil quality and to offer a promising route for the high-value utilization of lignin resources.

       

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