污泥基生物炭结构的共焦显微拉曼技术应用

采用共焦显微拉曼光谱仪探索不同热解温度(500~900)℃条件下所制备的污泥基生物炭结构变化的表征方法.结果表明,拉曼信号的荧光干扰与生物炭的理化特性有较强的相关性.随着热解温度升高,拉曼漂移系数减小,这与污泥基生物炭挥发分含量、H/C和O/C比变化趋势一致.其中,漂移系数与挥发分含量和H/C的相关性指数分别是0.97和0.94,其变化规律可用来准确评估生物炭挥发分含量和H/C的变化.同时,生物炭在拉曼光谱中的特征峰强度比D/G随着热解温度升高而增强,代表了污泥基生物炭无序化程度增加的过程.谷区域(V)与D峰强度比IV/ID随热解温度升高而减小,表明具有缺陷的稠合芳环结构的比例增加;另外,经分峰拟合后得到的ID1/IG1变化较小,而ID2/IG2呈增加趋势,证实了小分子侧链基团断裂形成的化合物部分沉积在炭表面,形成缺陷和非晶结构;IG1/IG2随着热解温度升高而减小,表明了炭基材料键角有序与无序比随着热解温度的升高而降低.因此,拉曼光谱可用于表征污泥基生物炭的微观结构变化,反映其结构演变规律.

Application of confocal Raman microscopy on the structure of sludge-based biochar

Confocal Raman microscopy method was utilized to analyze the structure changes of sludge-based biochar prepared at different pyrolysis temperatures (500~900 ). The results showed that there was a strong correlation between the fluorescence ℃ interference of Raman signal and the physicochemical properties of biochar. The Raman drift coefficient decreased with the pyrolysis temperature increasing, which was consistent with the changing trend of the volatile content, H/C and O/C ratio of sludge-based biochar. The correlation indices of the drift coefficient with the volatile content and the H/C ratio were 0.97 and 0.94, respectively, which revealed that the change of drift coefficient could be utilized to evaluate the change of volatile content and H/C ratio of biochar. In addition, the ratio of characteristic peak of biochar (D/G ratio) in the Raman spectra enhanced with the pyrolysis temperature increasing, which could represent the increasing process of the disorder degree of sludge-based biochar. The ratio of the valley region (V) to the D peak (IV/ID ratio) decreased with the pyrolysis temperature increasing, indicating that the proportion of defective fused aromatic ring structures increased. In addition, the ratio of ID1/IG1obtained by peak fitting was unobvious, while ID2/IG2 showed an increasing trend. The trend confirmed that the defects and amorphous structures were formed by the depositing compounds on the surface of carbon from low molecule fracture of side chain group. The ratio of IG1/IG2 decreased with the pyrolysis temperature increasing, indicating that the ratio of order to disorder of bond angle decreased following the increasing pyrolysis temperature. Therefore, Raman spectroscopy could be applied to characterize the sludge-based biochar, and reflect the evolution of its microstructure.