麦秸在亚、超临界四氢萘中的热化学液化

S. N. Evstaf‘ev, E. S. Fomina, N. P. Tiguntceva
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引用次数: 1

摘要

本文研究了小麦秸秆生物质在亚超临界四氢萘介质中的热化学转化。实验在285、330、380、420和460℃的间歇式反应器中进行,时间为10分钟。在亚临界四氢萘条件下进行秸秆液化具有效率较高的特点。420℃时,生物质转化率达98.2% a.d.m, 380℃时液化液产率最高(81.6% a.d.m)。用正己烷、水和乙醇连续萃取,对液体产物进行分馏。GC-MS数据显示,可溶于己烷的液化产物由秸秆组分的低分子量降解产物和四氢化萘衍生物组成,包括脂肪酸甲酯、芳香族化合物、烷烃、少量醇类和酮类。当工艺温度升高时,酯类化合物含量降低,随后芳香族化合物的比例增加到50%,在460℃时获得的可溶于己烷的液化产物中不存在酯类和酚类化合物。在给定条件下,四氢萘发生脱氢、烷基化和异构化反应,生成萘、1,4-二氢萘以及四氢萘、萘和茚的烷基衍生物。通过对秸秆和固体液化产物红外光谱的对比分析发现,在330℃以下,秸秆生物质中多糖破碎化过程更为明显,而在更高温度下,木质素破碎化过程更为明显。结果表明,固体产物在380℃时的红外光谱显示出较弱的烷基芳体结构碎片吸收带。同时,在420℃下获得的固体产物的红外光谱中,只观察到秸秆灰和吸附水中矿物成分的吸收带。
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Thermochemical liquefaction of wheat straw in sub- and supercritical tetralin
The present work investigates the thermochemical conversion of wheat straw biomass in a suband supercritical tetralin medium. The experiment was carried out in a batch reactor at 285, 330, 380, 420 and 460 °C for 10 minutes. The process of straw liquefaction in subcritical tetralin was characterised by relatively high efficiency. At 420 °C, the biomass conversion rate amounted to 98.2% a.d.m. The maximum yield of liquid products during liquefaction (81.6% a.d.m.) was obtained at 380 °C. The liquid products were fractionated by successive extraction with hexane, water and ethanol. According to GC-MS data, the liquefaction products soluble in hexane comprised a mixture of low-molecular weight degradation products of straw components and tetralin derivatives, including methyl esters of fatty acids, aromatic compounds, alkanes and minor alcohols and ketones. When the process temperature increased, the content of esters diminished, followed by an increment in the proportion of aromatic compounds up to 50% rel. No esters and phenolic compounds were present in the liquefaction products soluble in hexane obtained at 460 °C. Dehydrogenation, alkylation and isomerisation of tetralin with the formation of naphthalene, 1,4-dihydronaphthalene and alkyl derivatives of tetralin, naphthalene and indane occurred under the given conditions. The conducted comparative analysis of infrared spectra for straw and solid products of liquefaction suggested that, at temperatures of up to 330 °C, the process of polysaccharide fragmentation is more pronounced in the straw biomass, while, at higher temperatures, the process of lignin fragmentation prevails. As a result, the IR-spectrum of the solid product obtained at 380 °C revealed weakly pronounced absorption bands of alkylaromatic structural fragments. At the same time, only the absorption bands of mineral components in straw ash and adsorbed water were observed in the IR-spectrum of the solid product obtained at 420 °C.
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