Micro-structure and micro-strength of coke from co-carbonization of lean coal and thermal extract from low rank coal
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摘要: 以众唯瘦煤作为主炼焦煤，大同长焰煤萃取物作为添加剂，进行共炭化处理制备坩埚焦。利用偏光显微镜法定量研究焦炭光学显微组分，获得焦炭的各向异性指数（DRAS）；采用XRD及分峰拟合的方法研究了焦炭的微晶粒径（Lc）、芳香缩合度（Ia）、石墨化度（g）；利用Raman光谱结合分峰拟合的方法研究了焦炭中理想石墨微晶含量（Ig）。对所得焦炭的光学显微组分进行定量分析发现：大同长焰煤热解萃取产物的添加对共炭化焦炭的光学显微组分有显著的影响，利用偏光显微镜法计算出焦炭的DRAS与XRD和Raman计算的焦炭微晶参数呈现很好一致性。并且，焦炭的显微强度与其微观结构关联性极大。Abstract: Crucible cokes were obtained by co-carbonization of Zhongwei lean coal as main coking coal and thermal extract from Datong long-flame coal as additive. The degree of regularization on anisotropic structure (DRAS) of coke was obtained by quantitative calculation of optical tissue from polarized microscopy. The crystallite size (Lc), aromatic condensation (La) and degree of graphitization (g) have been quantitative calculated by combination of XRD and curve-fitted method. Furthermore, Raman spectrum and curve-fitted method have been used to obtain content of ideal graphite microcrystalline of coke. The quantitative analysis of optical micro-component on obtained cokes shows that addition of thermal extract from Datong long-flame coal has a significant influence on optical micro-component of coke. There is good consistency on DRAS and microcrystalline parameters, which is calculated by the method of polarized microscopy and XRD and Raman spectrum, respectively. Moreover, the micro-strength index of coke is highly correlated with its microstructure.
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图 1 焦炭的偏光显微结构
(a): F+Fi+Mf+I; (b): L+Mf+Fi+Mm+Mm; (c): I+F+Mm+Mf; (d): L+F+Fi+I; (e): I+F+FF+Mc; (f): L+F
Figure 1 Optical structure of cokes
图 3 共炭化焦炭的XRD谱图(a)和拟合谱(b)
Figure 3 XRD images of co-carbonization cokes (a) and curve-fitted images (b)
图 4 焦炭的Raman光谱(a)和拟合谱图(b)
Figure 4 Raman spectra of cokes (a) and curve-fitted spectrum (b)
表 1 DTLFPE的工业分析和元素分析
Table 1 Proximate and ultimate analyses of DTLFPE
Proximate analysis Ultimate analysis w/% Vdaf /% SP/℃ TI /% QI /% CV/% C H N S O* 76.02 86.8 6.65 0.6 44.54 84.20 5.35 0.41 - 10.04 Vdaf: volatile component; SP: softening point; TI: toluene insoluble; QI: quinoline insoluble; CV: coke value; *: by difference 
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表 2 LC的指标分析
Table 2 Parameters of LC sample
Proximate analysis w/% Conventional index for coal Mad Ad Vdaf FCdaf St, d Y X G a/% b/% 0.67 11.17 19.95 80.05 0.24 8.4 21.1 47 25.7 - St, d: total sulfur; X: plastometric shrinkage; Y: maximum thickness of colloidal matter layer; a: maximum contraction; b: maximum dilatation
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表 3 焦炭的显微强度
Table 3 Micro-strength of each coke
Sample No. LC-0 LC-1% LC-3% LC-5% LC-7% MSa/% 0 13.95 28.25 44.79 42.84 a: means for micro-strength of coke
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表 4 焦炭的光学组织分布
Table 4 Optical structure parameters of cokes
Sample Optical microstructure/% I Mf Mm Mc Fi F L FF LC-0 50.96 11.13 7.02 6.86 10.03 6.68 6.15 1.17 LC-1% 47.83 10.47 8.63 6.35 11.80 6.01 8.22 0.69 LC-3% 39.49 12.66 9.64 6.66 14.49 6.39 9.96 0.71 LC-5% 37.48 13.57 8.92 5.42 14.46 7.79 11.43 0.93 LC-7% 32.52 13.74 10.44 6.05 15.31 7.14 13.15 1.65
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表 5 焦炭微晶参数
Table 5 Structural parameters of the carbon stacking structure
Sample γ/(°) π/(°) Aγa Aπb Ia/% d002/nm Lc/nm N n g/% LC-0% 22.70289 25.99353 949.78 962.38 50.33 0.3425 2.18 7.36 17.33 17.28 LC-1% 23.06678 26.05383 879.01 989.17 52.95 0.3417 2.26 7.60 18.48 26.34 LC-3% 23.38885 26.07317 829.53 1090.85 56.80 0.3415 2.35 7.88 19.86 29.24 LC-5% 23.31953 26.19762 763.71 1265.83 62.37 0.3399 2.40 8.06 20.77 47.77 LC-7% 23.40742 26.15587 702.94 1120.60 61.45 0.3404 2.32 7.82 19.56 41.58 a: integrate area of γ band; b: integrate area of π band
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Band Raman shift δ/cm-1 Vibration mode G 1580 ideal graphitic lattice (E2g-symmetry) D1 1350 disordered graphitic lattice (graphene layer edges, A1g symmetry) D2 1620 disordered graphitic lattice (surface graphene layers, E2g-symmetry) D3 1500 amorphous carbon (gaussion line shape) D4 1200 disordered graphitic lattice (A1g symmetry), polyenes, ionic impurities
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表 7 焦炭的Raman参数
Table 7 Raman parameters of each coke
Sample Integrate area Ratio/% ID1 ID2 ID3 ID4 IG IG/ IAll ID3/ IAll LC-0% 23146.95 225765.7 48950.46 22578.54 29579.66 8.45 13.98 LC-1% 23457.88 143800.4 34096.55 19822.03 27014.69 10.88 13.74 LC-3% 28095.09 176781.5 40719.01 21135.77 34306.77 11.40 13.53 LC-5% 30693.6 200197.3 44021.84 20315.49 44365.68 13.06 12.96 LC-7% 22841.11 174445.4 38702.16 16398.72 34135.82 11.91 13.51
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