Analysis of solid residues from the co-processing of different rank coals and oils
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摘要: 选取安徽褐煤、辽宁褐煤和贵州烟煤三种煤为原料，以油溶性环烷酸钼为催化剂，分别与马瑞常渣（MRAR）、克炼常渣（KAR）以及催化裂化油浆（FCCS）在高压釜内模拟悬浮床加氢共炼反应。结果表明，不同的油体系下，两种褐煤都能达到83%以上的转化率，而对于贵州烟煤，转化率最高的FCCS体系与最低的KAR体系分别为67.75%和50.31%，相差很大。采用FT-IR和SEM分析反应后固体残渣，计算了固体残渣中脂肪族和芳香族中各个基团的相对含量，并对比了不同体系反应后固体残渣的微观形貌。结果表明，KAR体系的固体残渣脂肪链较长，支链化程度高，取代度较低。转化率较高的褐煤反应后固体残渣结构松散，分散度高；转化率较低的烟煤固体残渣随着转化率降低，残渣颗粒逐渐变大，表面更加光滑，板结程度加深。Abstract: Anhui lignite, Liaoning lignite and Guizhou bitumite were co-processed with Murray residue (MRAR), Karamay residue (KAR) and FCC slurry (FCCS) in an autoclave with molybdenum naphthenate as catalyst, simulating the slurry-phase hydrogenation co-processing. The results show that for two lignites under different oil systems, the conversion of coal exceeds 83%. However, for Guizhou bitumite, a great difference is observed in the coal conversion between FCCS (67.75%) and KAR (50.31%) for co-processing. The solid residues after co-processing were analyzed by FT-IR and SEM, to determine the relative content of aliphatic and aromatic groups and the micro morphology. It is found that the solid residue derived from the KAR system possesses a low content of CH2/CH3 and a low substitution degree. Moreover, the solid residues obtained from two lignites with high coal conversion exhibit a looser structure and a higher dispersion of solid particles than that from bitumite with a low coal conversion.
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图 1 反应后煤转化率及气体、液体、固体收率
Figure 1 Coal conversion and gas liquid solid yields after co-processing
图 2 反应后固体残渣的红外拟合谱图
Figure 2 FT-IR spectra of solid residues with curve fitting ---: original peak; —: calculated profile; .....: fitting peak
图 3 反应后固体残渣的SEM照片
Figure 3 SEM images of various solid residues
(a): MRAR-AH; (b): KAR-AH; (c): FCCS-AH; (d): MRAR-LN; (e): KAR-LN; (f): FCCS-LN; (g): MRAR-GZ; (h): KAR-GZ; (i): FCCS-GZ
表 1 原料煤的工业分析和元素分析
Table 1 Proximate analysis and ultimate analysis of coals
Coal type Proximate analysis w/% Ultimate analysis wdaf/% Mad Aad Vdaf FCdaf C H N S Anhui lignite 0.75 3.97 56.24 43.76 58.70 5.15 0.51 0.35 Liaoning lignite 0.76 18.06 49.02 50.98 55.31 4.78 1.29 0.59 Guizhou bitumite 0.13 9.29 34.07 65.93 71.60 4.65 0.95 0.41 
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表 2 原料油的性质分析
Table 2 Properties of oils
Oil type Density (20 ℃) ρ/(g·mL-1) Viscosity (50 ℃) μ/(mm2·s-1) Carbon residue w/% Chemical composition w/% Ultimate analysis w/% saturates aromatics resins C7-asphaltenes C H S N MRAR 0.997 6 2 272.4 15.33 31.49 39.44 12.06 9.29 84.82 10.87 2.89 0.63 KAR 0.967 0 1 964.1 10.01 25.44 39.20 35.10 0.26 86.68 11.66 0.63 0.77 FCCS 1.093 6 12.41 5.84 12.69 84.28 2.11 0.09 88.38 7.34 3.96 0.25
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表 3 反应后固体残渣不同基团的相对含量
Table 3 Relative contents of different groups in the solid residues
System CH3 CH2 CH Relative contents /% CH2/CH3 5 adjacent H deformation 4 adjacent H deformation 2 or 3 adjacent H deformation MRAR-AH 33.81 41.76 24.43 13.83 17.02 69.15 1.24 KAR-AH 23.85 50.18 25.97 15.34 13.07 71.59 2.10 FCCS-AH 29.76 47.06 23.18 29.89 12.64 57.47 1.58 MRAR-LN 27.00 42.00 31.00 15.37 19.26 65.37 1.56 KAR-LN 25.77 51.53 22.70 13.25 14.31 72.44 2.00 FCCS-LN 28.93 51.51 19.56 19.86 15.44 64.70 1.78
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表 4 贵州煤反应后固体残渣不同基团的相对含量
Table 4 Relative contents of different groups in GZ solid residues
System CH3 CH2 CH Relative contents /% CH2/CH3 5 adjacent H deformation 4 adjacent H deformation 2 or 3 adjacent H deformation MRAR-GZ 20.27 39.86 39.86 52.86 15.00 62.14 1.97 KAR-GZ 23.79 50.80 25.40 47.97 14.86 66.89 2.14 FCCS-GZ 26.76 48.59 24.65 54.74 11.58 56.84 1.82
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