Microstructure evolution characteristics of Shengli lignite during combustion process
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摘要: 对胜利脱灰褐煤的燃烧反应性进行了测试，并利用FT-IR、XPS、XRD和Raman等对不同条件下的未反应残留物进行了表征，以分析胜利脱灰褐煤在燃烧过程中微结构演变特性。结果表明，在燃烧反应过程中，煤样的脂肪族官能团不断消耗，碳氧官能团和芳烃骨架的消耗与生成交替进行，褐煤表面C-C/C-H键合结构所占比例先增加后减少，碳-氧键合结构所占比例先减小后增加，未反应残留物的芳香度不断升高，褐煤的石墨缺陷指数先增加后降低，而脂肪族侧链指数则呈现先减少后增加的变化规律，表明随着燃烧反应进行对褐煤未反应残留物的石墨化程度逐渐提高，特别是在燃烧反应后期，石墨化程度显著提高。Abstract: The combustion of Shengli lignite demineralized with hydrochloric acid was carried and residues from different reaction conditions were obtained. The microstructural properties of the lignite and residues were examined by FT-IR, XRD, XPS and Raman, respectively. The results indicate that aliphatic functional groups were consumed during combustion, while oxygen-containing groups and aromatic structure were consumed and generated alternatively. The proportion of C-C/C-H structure decreased after increasing, while the content of carbon-oxygen structure was increased following decrease. The aromaticity of residues increased and ID/IG increased before decrease, while IS/IG decreased before increase. This indicated that graphitization transformation degree of lignite obviously increased during combustion, especially in the late stage of reaction.
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图 3 煤样和未反应残留物的红外光谱谱图
Figure 3 FT-IR spectra of SL+ and solid residues
a: SL+-0; b: SL+-5; c: SL+-10; d: SL+-20; e: SL+-40
图 4 煤样和未反应残留物的XPS谱图
Figure 4 XPS spectra of SL+ and solid residues
a: SL+-0; b: SL+-5; c: SL+-10; d: SL+-20; e: SL+-40
图 5 煤样和未反应残留物的XPS谱图C 1s拟合谱图
Figure 5 XPS C 1s fitting and results of SL+ and solid residues
a: SL+-0; b: SL+-5; c: SL+-10; d: SL+-20; e: SL+-40
图 6 煤样和未反应残留物的XRD谱图
Figure 6 XRD spectra of SL+ and solid residues
a: SL+-0; b: SL+-5; c: SL+-10; d: SL+-20; e: SL+-40
图 7 煤样和未反应残留物的Raman谱图及拟合
Figure 7 Raman spectra and fitting of SL+ and solid residues
a: SL+-0; b: SL+-5; c: SL+-10; d: SL+-20; e: SL+-40
表 1 煤样的工业分析和元素分析
Table 1 Proximate analysis and ultimate of coal samples
Sample Proximate analysis wd/% Ultimate analysis wd/% A V FC C H N S+O* SL 13.92 33.37 52.71 66.90 4.16 1.03 27.90 SL+ 7.53 39.77 52.70 66.43 3.61 0.93 29.03 note: d: dried basis; A: ash content; V: volatile content; FC: fixed carbon; O*: by difference 
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表 2 煤样及煤灰中金属组分分布
Table 2 Percentage of metal components in coal samples and ash
Sample Coal based/Ash based w/% Al Na Ca Si Fe Mn K SL 2.40/35.50 0.58/8.59 0.41/6.08 3.11/46.09 0.11/0.69 0.08/1.18 0.06/0.88 SL+ 0.90/32.94 0.00/0.16 0.01/0.19 2.89/64.58 0.03/0.92 0.03/1.18 0.00/0.03
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表 3 煤样及未反应残留物的晶体结构参数
Table 3 Crystalline structure parameters of SL+ and solid residues
Sample fa d002/nm Lc/nm La/nm N SL+-0 0.447 0.363 2 0.817 4 0.961 2 2.248 1 SL+-5 0.463 0.359 0 0.976 7 1.279 6 2.720 6 SL+-10 0.492 0.365 4 0.932 1 1.795 9 2.550 9 SL+-20 0.573 0.363 0 0.964 2 1.696 9 2.656 2 SL+-40 0.631 0.356 5 0.920 9 1.496 4 2.583 2
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表 4 煤样及未反应残留物的Raman谱图拟合参数
Table 4 Raman spectra fitting parameters of SL+ and solid residues
Sample ID/IG ID/(ID+IG) IG/(ID+IG) (ID+IG)/Iall ID/I(GR+VR+VL) IS/IG SL+-0 0.897 0.473 0.527 0.486 1.216 0.419 SL+-5 0.918 0.479 0.521 0.539 1.670 0.385 SL+-10 1.607 0.616 0.384 0.615 2.845 0.343 SL+-20 1.335 0.571 0.428 0.513 1.591 0.418 SL+-40 0.964 0.491 0.509 0.480 1.174 0.464
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