何志霞, 纪长浩, 徐贵生. 互花米草在乙醇-水体系中直接液化制备生物油[J]. 农业工程学报, 2016, 32(20): 236-241. DOI: 10.11975/j.issn.1002-6819.2016.20.031
    引用本文: 何志霞, 纪长浩, 徐贵生. 互花米草在乙醇-水体系中直接液化制备生物油[J]. 农业工程学报, 2016, 32(20): 236-241. DOI: 10.11975/j.issn.1002-6819.2016.20.031
    He Zhixia, Ji Changhao, Xu Guisheng. Production of bio-oil by direct liquefaction of Spartina alterniflora in ethanol-water co-solvent[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2016, 32(20): 236-241. DOI: 10.11975/j.issn.1002-6819.2016.20.031
    Citation: He Zhixia, Ji Changhao, Xu Guisheng. Production of bio-oil by direct liquefaction of Spartina alterniflora in ethanol-water co-solvent[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2016, 32(20): 236-241. DOI: 10.11975/j.issn.1002-6819.2016.20.031

    互花米草在乙醇-水体系中直接液化制备生物油

    Production of bio-oil by direct liquefaction of Spartina alterniflora in ethanol-water co-solvent

    • 摘要: 生物质因其储量丰富、来源广泛、碳中和等优势被认为是最具有应用前景的生产替代燃料的原料。在容积50 mL的小型高温高压反应釜中,利用醇-水共溶剂直接液化互花米草制备生物油,考察反应温度、醇-水共溶剂中乙醇体积分数、液料比对液化产物分布的影响,分析了原料的热重特性及生物油的主要成分。结果表明:随着升温速率的增加,互花米草的热失重曲线(thermogravimetric,TG)和微分热重曲线(differential thermogravimetric,DTG)基本保持不变,但却发生了不同程度的横向移动,出现明显的滞后现象,这是由温度和时间共同作用的结果;正交优化操作条件为温度340 ℃、乙醇体积分数50%、液料比10 mL/g,此时生物油产率高达44.2%,而残渣率仅为12%;与单一溶剂相比,醇-水共溶剂对互花米草的液化具有明显的协同作用,在提高产油率的同时能够显著改善生物油的品质;生物油的气相色谱-质谱分析表明生物油是一种组分复杂的含氧有机混合物,包括酸类、酚类、酯类、呋喃等,主要成分为酚类和酯类,相对含量分别为29.62%和11.27%;乙醇能够与酸发生酯化反应生成酯类,而酚类主要来自原料中木质素的降解;以乙醇体积分数为50%的醇-水共溶剂作为液化介质时,生物油的能量回收率为76.5%,明显高于以水或乙醇作为单一溶剂时液化所得生物油的能量回收率,因而醇-水共溶剂是生物质直接液化中非常有前景的液化介质。

       

      Abstract: Abstract: Biomass is considered to the most promising feedstock with low carbon intensity for producing renewable and clean alternative fuels due to their abundant reserves, wide distribution and carbon neutral. In this study, direct liquefaction of Spartina alterniflora was performed in a 50 mL bath reactor with ethanol and water as a co-solvent. Experiments for optimal operating conditions such as reaction temperature, ethanol volume fraction in ethanol-water co-solvent and solvent to biomass ratio were conducted to understand its influence on liquefaction product distribution. Raw material and bio-oil were analyzed by thermogravimetry analysis and gas chromatography-mass spectrometry (GC-MS). Results showed that thermogravimetric (TG) and differential thermogravimetric (DTG) curves of Spartina alterniflora were almost the same with the increase of heating rate from 10 to 40 ℃/min. However, the temperature where the maximum rate of weight loss occurred, tended to move to higher value. This suggested that there was a hysteresis phenomenon on thermogravimetric characteristics of Spartina alterniflora with respect to the heating rate, which was caused by the combination of time and temperature. The bio-oil yield tended to increase but the solid residue yield tended to decrease with increasing temperature up to 340 ℃, while further increasing temperature increased the residue yield but decreased the bio-oil yield. The similar tendency for bio-oil yield and solid residue yield was observed when increasing ethanol volume fraction in ethanol-water co-solvent between 0 and 100%. As the solvent to biomass ratio increased from 6 to 10 mL/g, the bio-oil yield increased obviously and after that the trend went opposite. Meanwhile, the solid residue yield reduced gradually with the solvent to biomass ratio in the range of 6-10 mL/g and leveled after higher than about 15 mL/g. Optimal operating conditions were reaction temperature of 340℃, ethanol volume fraction in co-solvent of 50% and solvent to biomass ratio of 10 mL/g, resulting the highest bio-oil yield of 44.2% and minimum solid residue yield of 12%, respectively. Compared with single solvent like pure water or ethanol, ethanol-water co-solvent showed an obvious synergistic effect during direct liquefaction of Spartina alterniflora. Not only the yield of bio-oil was enhanced but also the quality of bio-oil was improved with ethanol-water co-solvent as the reaction medium. The result of GC-MS analysis indicated that the bio-oil obtained from direct liquefaction of Spartina alterniflora at optimal operating conditions was a complex and oxygen-containing organic mixture, mainly including acids, phenols, esters and ketones. The major components of bio-oil were phenols (29.62%) and esters (11.27%). The presence of ethanol could promote the formation of esters by reacting with acids through esterification while the majority of phenols were derived from the decomposition of lignin. Ester compounds were similar to biodiesel in composition. Thus, it was desirable to increase the amount of esters in bio-oil for a better bio-oil quality. The energy recover rate of bio-oil obtained from direct liquefaction in ethanol-water co-solvent with 50% ethanol volume fraction reached up to 76.5%, which was significantly higher than that in single solvent. Therefore, ethanol-water co-solvent was a potential medium with higher bio-oil energy recover during direct liquefaction of biomass.

       

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