褐煤腐植酸的超临界CO2萃取及增效作用机制

Supercritical CO2 extraction of lignite humic acid and its synergistic mechanism

  • 摘要: 超临界CO2(ScCO2)萃取技术是煤炭中可溶性有机质提取的有效途径之一,其强大的溶解及萃取能力可改变煤样形貌特征及孔隙结构。以内蒙古某地褐煤及用10%过氧化氢溶液预处理后的褐煤为原料,以乙醇为共溶剂,进行褐煤的ScCO2萃取腐植类物质实验。利用ICP-MS电感耦合等离子体质谱仪、傅里叶红外光谱仪、扫描电子显微镜、紫外−可见分光光度计等对腐植类产物进行分析;利用扫描电子显微镜、比表面积及孔径分析仪等探究在ScCO2萃取过程中煤样的形貌特征及孔隙的变化,揭示ScCO2萃取技术对腐植类物质提取的作用机制。研究结果表明,过氧化氢溶液预处理后的煤样会让有乙醇共溶的ScCO2更有效地渗透到褐煤的孔隙中,与黄腐酸官能团之间通过氢键等作用发生相互作用,使得黄腐酸从褐煤基质中大量溶解到超临界流体中,萃取后的煤样整体疏松孔隙更多有利于后续腐植酸的提取。萃取出的黄腐酸溶液中Mg、P、K和Fe等植物营养必需元素的离子质量浓度大幅度提高,分别为21 432.77、148.83、8 823.84、415.12 μg/L。萃取后的煤样具有最大的总孔容为0.017 9 cm3/g及比表面积为3.374 3 m2/g,以其为原料制备出的腐植酸产率高(49.38%)、O/C高(0.74)、N/C高(0.12)、含硫量低(1.11%)、富含羰基和羧基、芳香度低、分子量较小、表面多孔粗糙。这表明ScCO2萃取技术对黄腐酸及腐植酸的有效提取及品质提高具有重要启示作用。

     

    Abstract: Supercritical CO2 (ScCO2) extraction technology is one of the effective ways to extract soluble organic matter from coal. Its strong dissolution and extraction ability can change the morphology and pore structure of coal samples. The experiment of extracting humic substances from lignite by ScCO2 was carried out with lignite from Inner Mongolia and lignite pretreated with 10% hydrogen peroxide solution as raw materials and ethanol as cosolvent. The humic products were analyzed by ICP-MS inductively coupled plasma mass spectrometer, Fourier transform infrared spectrometer, scanning electron microscope and ultraviolet-visible spectrophotometer. Scanning electron microscopy, specific surface area and pore size analyzer were used to explore the morphological characteristics and pore changes of coal samples during ScCO2 extraction, and to reveal the mechanism of ScCO2 extraction technology on the extraction of humic substances. The results show that the coal sample pretreated with hydrogen peroxide solution will make ScCO2 co-dissolved with ethanol more effectively penetrate into the pores of lignite, and interact with fulvic acid functional groups through hydrogen bonding and other interactions, so that fulvic acid is dissolved in a large amount from lignite matrix to supercritical fluid. The overall loose pores of the extracted coal sample are more conducive to the subsequent extraction of humic acid. The ion concentrations of Mg, P, K and Fe in the extracted fulvic acid solution were significantly increased, which were 21432.77 μg/L, 148.83 μg/L, 8823.84 μg/L and 415.12 μg/L, respectively. The maximum total pore volume and specific surface area of the coal sample after extraction are 0.0179 cm3/g and 3.3743 m2/g, respectively. The humic acid prepared from it has high yield (49.38%), high O/C (0.74), high N/C (0.12), low sulfur content (1.11%), rich in carbonyl and carboxyl groups, low aromaticity, small molecular weight and rough surface. This indicates that ScCO2 extraction technology has important implications for the effective extraction and quality improvement of fulvic acid and humic acid.

     

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