选取非极性有机溶剂正乙烷在高压反应釜内对印尼褐煤进行加压提质改性,分析印尼褐煤在改性前后煤质特性、孔隙结构、微观形貌以及煤中化学组分和结构的变化规律,阐明有机溶剂加压提质改性褐煤的作用机理。结果表明,褐煤改性后的固产率随改性温度的升高而降低,在改性温度为300℃,压力为12 MPa时,褐煤经正己烷改性后的固产率为74.4%。印尼褐煤改性后水分含量显著降低,固定碳含量升高,[O]/[C]和[H]/[C]降低,热值大幅度提高,表明印尼褐煤经有机溶剂改性后煤阶升高。随着改性温度的升高,褐煤中大孔数量迅速增加,褐煤表面轮廓和线条逐渐清晰,煤的致密程度增加。通过13C核磁共振波谱分析,发现印尼褐煤经正己烷加压提质改性后,煤中的羰基碳和羧基碳,氧化的脂肪碳以及甲氧基碳的相对强度均减少约20%,而与氧相邻的芳香碳和质子化芳香碳的相对强度分别增加45%和14%,说明大部分含氧官能团被脱除,芳构化程度加深,煤阶提升。含氧官能团的脱除主要发生在化学位移δ147处的二羟基酚,δ55处的甲氧基和δ173处的羧基。
Upgrading of Indonesian lignite with non-polar organic solvent (n-hexane) at elevated pressure was carried out in a 1L autoclave. Characteristics of lignite, pore structure, morphology and chemical functional groups before and after upgrading were analyzed. Mechanism of the upgrading process for lignite was elucidated. The results show that solid yield of modified lignite decreases with the increase of reaction temperature. The solid yield of lignite modified by n-hexane at 300 ℃ and 12 MPa is 74.4%. Moisture content in modified lignite is significantly lowered, fixed carbon content raises, atomic ratio of [O]/[C] and [H]/[C] descends, and calorific value is greatly promoted, indicating that coal rank is upgraded after Indonesia lignite is modified by organic solvent. The number of large holes increases quickly after treatment, surface contours and lines turn to be gradually clear, coal structure becomes compact and densified. From the 13C NMR spectnun, it is found that relative percent of carbonyl and carboxyl C, oxygenated aliphatic C and methoxyl C decreased by almost 20%, while relative percent of C-substituted and protonated aromatic C (δ 120-135) and protonated aromatic C (δ 90- 120) increased by 45% and 14%, respectively. Most of the oxygen-containing functional groups were removed, and the degree of aromatization was deepened, which indicates that coal rank has been improved after modified by n-hexane under pressurized atmosphere. It also indicates the removal of oxygen-containing functional groups occurs mainly at δ147 (dihydroxyphenol), δ55 (methoxyl) and δ173 (Carboxyl).