Influence of coal tar distillates on coke formation during co-processing of Liaohe heavy crude oil with the distillates
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摘要: 从煤焦油馏分油自身及与辽河稠油共炼生焦规律出发,利用元素分析、核磁共振氢谱、同步荧光光谱及族组成分析等方法对馏分油进行表征,研究了煤焦油馏分油对辽河稠油热生焦性能的影响。结果表明,辽河稠油掺炼煤焦油馏分油可以改善辽河稠油的热生焦性能。实验条件下,掺炼体系加权生焦率为3.3%-6.4%,实验生焦率为0.5%-5.9%,表现出良好的协同效果。不同馏分油的协同作用程度取决于馏分油的化学组成和含量。饱和烃、单环芳烃和缩合四环芳烃会促进生焦,而双环芳烃、三环芳烃和缩合双环芳烃有减缓生焦的作用。Abstract: The influence of coal tar distillates on coke formation during the processing of Liaohe heavy crude oil with the distillates was studied.The composition of feedstock was characterized by the elemental analysis,the proton nuclear magnetic resonance spectrometry,the synchronous fluorescence spectrometry and the group analysis techniques.It has been found that the coke formation of Liaohe heavy crude oil upon heating can be reduced by co-processing with the coal tar distillates.Under the experimental conditions,the coke yields from the co-processing(0.5%-5.9%) are lower than that from the weighted calculation(3.3%-6.4%);a positive synergetic effect was observed.The extent of the synergetic effect depends on the chemical composition and content of the distillates.Saturates,1-ring aromatics and condensed 4-ring aromatics may retard the coke formation,whereas 2-ring and 3-ring aromatics as well as condensed 2-ring aromatics may retard the coke formation.
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Key words:
- Liaohe heavy crude oil /
- coal tar distillates /
- coke formation /
- chemical composition
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图 1 馏分油系列(J、C和N)及稠油(L)的空白实验生焦率
Figure 1 Coke yields of blank experiments for distillates of J,C and N series and Liaohe heavy crude oil (L) under 430℃,3MPa N2 for 1h
图 2 辽河稠油与焦油馏分油掺炼生焦率的实验值(YTHFIS，填充符号)与加权计算值(Y'THFIS，未填充符号)对比
Figure 2 Comparison of experimental (YTHFIS,filled symbols) and calculated (Y'THFIS,unfilled symbols) coke yields of co-processing of Liaohe heavy crude oil with coal tar distillates (430℃,3MPa N2,1h)
图 3 掺炼体系生焦率与组合馏分油中e和f馏分油相对含量me / (me + m)的关系
Figure 3 Relationship between the coke yield of co-processing mixture and the relative content of e and f distillates (me / (me + m)
图 4 掺炼体系生焦率与对应焦油馏分油芳香度(fA)的关系
Figure 4 Relationship between the coke yield of co-processing mixture and the aromaticity (fA) of distillates
图 5 掺炼体系生焦率与对应焦油馏分油族组成分布的关系
Figure 5 Relationship between the coke yield of co-processing mixture and distribution of group compositions
(a): saturates; (b): aromatics; (c): resins
图 6 掺炼体系生焦率与对应焦油馏分油中芳烃组成分布的关系
Figure 6 Relationship between the coke yield of co-processing mixture and the aromatics distribution of distillates:
(a): 1-ring； (b): 2-ring； (c): 3-ring； (d): 2-ring+3-ring
图 7 焦油馏分油的缩合芳环分布
Figure 7 Distribution of the condensed aromatic rings of distillates:
(a): distillate a； (b): distillate d； (c): distillate e； (d): distillate f
表 1 辽河稠油的性质
Table 1 Properties of Liaohe heavy crude oil
Property Elemental analysis w/% H/C Group analysis w/% ρ20a /(kg·m-3) μ100b /(mm2·s-1) wMCRc /% C H N S Od saturates aromatics resins asphaltenes 1000 680 12.6 86.6 10.8 0.9 0.4 1.2 1.5 28.9 27.4 31.3 12.4 a： density at 20℃; b： kinematic viscosity at 100℃; c： carbon residue by micro- method； d： by difference 
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表 2 不同煤焦油馏分油的元素分析
Table 2 Elemental analysis of coal tar distillates
Coal tar distillate Elemental analysis w/% H/C (atomic ratio) J series C H N S Od a 84.3 9.4 0.5 0.2 5.7 1.3 b 84.7 9.2 0.5 0.2 5.3 1.3 c 84.9 8.9 0.5 0.2 5.5 1.3 d 85.8 8.8 0.5 0.2 4.7 1.2 e 86.0 8.9 0.6 0.1 4.4 1.2 f 86.6 8.8 0.6 0.1 3.9 1.2 C series a 83.9 9.6 0.4 0.2 5.9 1.4 b 85.9 9.6 0.4 0.2 4.1 1.3 c 86.2 9.4 0.5 0.1 3.8 1.3 d 86.7 9.1 0.5 0.1 3.7 1.3 e 87.3 9.0 0.7 0.1 3.0 1.2 f 88.1 9.0 0.7 0.1 2.2 1.2 N series a 85.4 9.6 0.5 - 4.5 1.4 b 86.1 9.4 0.6 - 3.9 1.3 c 86.2 9.1 0.5 - 4.3 1.3 d 87.1 8.8 0.5 - 3.6 1.2 e 86.6 8.7 0.6 - 4.1 1.2 f 87.5 8.1 0.7 - 3.7 1.1 d： by difference； -： no detectable
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表 3 组合馏分油的馏分组成分布
Table 3 Distillate composition distribution of blend distillates
Blend distillate Compostion w/% a b c d e f Bt 16.2 10.5 14.8 15.7 23.3 19.5 B1 8.1 5.3 7.4 7.9 61.6 9.8 B2 12.1 7.9 11.1 11.8 42.5 14.6 B3 12.1 7.9 11.1 11.8 17.5 39.6 B4 8.1 5.3 7.4 7.9 11.7 59.4
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