Experimental study on pre-hydrogenation of catalytic slurry oil and co-carbonization of middle distillate and high boiling point distillate
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摘要: 采用缓和预加氢对某催化油浆（SO）进行稳定化处理，通过多种分析表征对加氢前后SO的结构组成、热稳定性、蒸馏收率和于蒸馏过程中的生焦行为进行研究，并对加氢后SO（HSO）中间馏分（350−500 ℃）和高沸点馏分（500−550 ℃）的炭化性能以及两者的共炭化性能进行考察。结果表明，HSO的环烷烃和氢化芳烃含量增多，而不稳定组分烯烃含量显著降低，由2.71%降低为0.97%。由此，HSO的热稳定性显著增强，并且其中间馏分和高沸点馏分的蒸馏收率较SO分别提高了25.8%和23.1%。更为重要的是，HSO蒸馏过程中无明显生焦现象。炭化实验结果表明，HSO中间馏分所得焦炭的光学纹理结构最优，为广域流线型，CTE值最低，为2.25 × 10−6 ℃−1。HSO高沸点馏分炭化性能相对较差，而与中间馏分共炭化可以显著改善其炭化性能。当高沸点馏分与中间馏分调配质量比例不高于2∶1时，组合馏分所得焦炭为广域流线型结构，CTE值低于2.30 × 10−6 ℃−1。Abstract: A catalytic slurry oil (SO) was treated by moderate pre-hydrotreating, and the structural compositions, the thermal stability, the distillate oil yield, and the coking behavior of SO before and after hydrotreating were analyzed. The carbonization performance as well as the co-carbonization performance of the middle distillate (350−500 ℃) and the high boiling point distillate (500−550 ℃) derived from the hydrogenated SO (HSO) were investigated. The results show that the content of naphthenes and hydrogenated aromatics of HSO increases, while the olefin content decreases, and the olefinic hydrogen content of HSO decreases from 2.71% to 0.97%. Thus, the thermal stability of HSO is fundamentally improved. Additionally, compared with SO, the yields of the middle distillate and the high boiling point distillate of HSO increased by 25.8% and 23.1%, respectively. More importantly, there is no significant coke formation during distillation of HSO. The carbonization experimental results show that the anisotropic textural structure of the coke obtained from the middle distillate derived from HSO is the large flow domain structure, and the coke has the lowest coefficient of thermal expansion (CTE) value of 2.25 × 10−6 ℃−1. The carbonization performance of the high boiling point distillate derived from HSO is poor, while the co-carbonization with the middle distillate significantly improves the carbonization performance of the high boiling point distillate. The anisotropic textural structure of the coke derived from carbonization of combined fraction is the large flow domain structure and the CTE value is less than 2.30 × 10−6 ℃−1, when the mass ratio of aromatic fraction to middle fraction is not higher than 2∶1.
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图 1 SO和HSO的（a） 1H NMR谱图及（b）氢分布
Figure 1 (a) 1H NMR spectra and (b) hydrogen distributions of SO and HSO
图 3 SO和HSO（a）在410 ℃下的生焦趋势和（b）不同蒸馏深度下的生焦率
Figure 3 (a) Coke formation trend curves of SO and HSO under 410 ℃, and (b) coke yields during vacuum distillation of SO and HSO under 500 and 550 ℃
图 4 SO和HSO经减压蒸馏后中间馏分和高沸点馏分收率
Figure 4 Middle distillate (350−500 ℃) yields and high boiling point distillate (500−550 ℃) yields after vacuum distillation of SO and HSO
图 5 MDO、HDO、H-MDO与H-HDO经炭化所得半焦偏光显微照片
Figure 5 Polarized-light microscopic images of green cokes derived from carbonization of MDO, HDO, H-MDO, and H-HDO
图 6 MDO、HDO、H-MDO和H-HDO所制备煅烧焦的SEM照片
Figure 6 SEM images of calcined cokes prepared from MDO, HDO, H-MDO, and H-HDO
图 7 MDO、HDO、H-MDO和H-HDO所制备煅烧焦的（a）XRD谱图和（b）微晶结构参数
Figure 7 (a) XRD spectra, and (b) crystal parameters of calcined cokes prepared from MDO, HDO, H-MDO, and H-HDO
图 8 MDO、HDO、H-MDO和H-HDO所制备煅烧焦的热膨胀系数
Figure 8 CTE of calcined cokes prepared from MDO, HDO, H-MDO, and H-HDO
图 9 H-MDO/H-HDO组合馏分经炭化所得半焦偏光显微照片
Figure 9 Polarized-light microscopic images of green cokes derived from carbonization of H-MDO/H-HDO combined fractions
图 10 H-MDO/H-HDO组合馏分所制备煅烧焦的SEM照片
Figure 10 SEM images of calcined cokes derived from carbonization of H-MDO/H-HDO combined fractions
图 11 H-MDO/H-HDO组合馏分所制备煅烧焦的（a）XRD谱图和（b）微晶结构参数
Figure 11 (a) XRD spectra, and (b) crystal parameters of calcined cokes prepared from H-MDO/H-HDO combined fractions
图 12 H-MDO/H-HDO组合馏分所制备煅烧焦的热膨胀系数
Figure 12 CTE values of calcined cokes prepared from H-MDO/H-HDO combined fractions
表 1 SO和HSO的主要性质
Table 1 Main properties of the SO and HSO
Item SO HSO Density ρ20 /(g·cm−3) 0.9773 0.9746 Viscosity η100 /(mm2·s−1) 50.10 47.72 Residual carbon w/% 10.76 9.94 Ash /(μg·g−1) 1667 1598 C w/% 88.02 87.91 H w/% 11.25 11.32 S w/% 0.41 0.35 N w/% 0.32 0.30 H/C atomic ratio 1.53 1.55 Saturates w/% 34.64 35.36 Aromatics w/% 45.23 44.44 Resins w/% 19.49 19.64 Asphaltenes w/% 0.64 0.56 Molecular weight 593.4 585.7 
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表 2 SO和HSO的平均结构参数
Table 2 Average structural parameters of SO and HSO
Oil sample fa fN RA RN RT SO 0.32 0.14 2.94 1.57 4.51 HSO 0.30 0.17 2.73 1.79 4.52
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表 3 SO和HSO的红外结构参数对比
Table 3 FT-IR structural parameters of SO and HSO
Oil sample fa ICHS IA SO 0.35 0.34 0.49 HSO 0.32 0.36 0.47
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