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摘要: 以四种劣质渣油为原料，研究组成性质对其热转化过程初期生焦特性的影响。结果表明，不同油样生焦诱导期受温度改变的影响程度可以用敏感度参数衡量，生焦诱导期越短的油样，敏感度参数越大，反应温度升高其生焦诱导期降低率越大。相同反应条件下，劣质渣油的生焦特性取决于其自身的基本性质，且各个性质对其生焦特性的影响程度不一。残炭、灰分、分子量、沥青质沉淀点和稳定性参数与其生焦诱导期相关性较强，其中，沥青质沉淀点和稳定性参数均反映的是油样胶体稳定性的突出影响。劣质渣油自身的胶体稳定性与其生焦密切相关，胶体稳定性越差的渣油，越容易生焦，油样的生焦过程是热反应过程中胶体体系逐渐被破坏的过程。Abstract: Using 4 inferior residual oils as raw materials, the effect of feedstock properties on the characteristics of coke formation during initial thermal conversion process was studied.The results show that the influence for coke induction period of different oils affected by temperature can be measured with the sensitivity parameters.The shorter the coke induction period of the residue, the bigger the sensitivity parameter.The coke induction period has a higher decrease rate with the reaction temperature rising.The coke formation property generally depends on feedstock's basic properties, and the influence of various properties of inferior residual oils on coke formation is different under the same reaction conditions.Carbon residue, ash, relative molecular mass, asphaltene precipitation onset point and stability parameter have strong correlations with the coke induction period, especially for the colloidal stability of oil reflected by asphaltene precipitation onset point and stability parameter.The colloidal stability of the inferior residual oils is related to the coke formation characteristics.The worse the stability of the residue, the more likely the coke is to form.The coke forming process is a gradual destruction of the colloid system during thermal reaction.
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Key words:
- inferior residue /
- delayed coking /
- characteristic /
- coke induction period /
- colloidal stability
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图 2 四种油样在400 ℃条件下的生焦趋势
Figure 2 Coke yield for four heavy oils at 400 ℃
■： A； ●： B； ▲： C； ◆： D
图 4 油样C不同反应时间反应体系物相变化序列图
Figure 4 Coke yields of oil C at different reaction times
(a)： 0 min； (b)： 20 min； (c)： 35 min； (d)： 45 min
图 5 四种劣质渣油的生焦诱导期与其基本性质之间的关系曲线
Figure 5 Correlation curves between coke yields and properties of four heavy oils
Correlation curves between coke yields and density (a),viscosity (b),carbon residue (c),ash (d),relative molecular mass (e),asphaltenes (f),H/C atomic ratio (g),asphaltene precipitation onset point (h),and stability parameter (i) of four heavy oils
表 1 四种油样的基本性质
Table 1 Properties of four heavy oils
Item A B C D Density ρ20/(g·cm-3) 1.016 3 0.997 8 1.004 7 0.999 7 Viscosity μ100/(Pa·s) 250.0 65.10 192.3 68.50 Carbon residue w/% 18.22 15.43 17.89 16.49 Ash w/% 0.24 0.16 0.21 0.18 Relative molecular mass 1 470 966 1 218 1 178 H/C (atomic ratio) 1.57 1.59 1.56 1.59 Ni/(μg·g-1) 29 19 26 20 V/(μg·g-1) 0.25 0.12 0.19 0.15 
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表 2 四种油样的四组分组成
Table 2 SARA compositions of four heavy oils
Item A B C D Saturates w/% 6.16 9.78 6.37 9.01 Aromatics w/% 29.39 30.59 30.56 30.12 Resins w/% 55.30 56.85 55.95 56.48 Asphaltenes w/% 9.15 2.78 7.12 4.39
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表 3 反应温度对四种油样生焦诱导期的影响
Table 3 Effect of reaction temperature on coke induction period of four heavy oils
Sample A B C D Induction period at 400 ℃/min 15 75 34 39 Induction period at 380 ℃/min 28 85 46 50 Sensitivity parameter of 46 12 26 22 induction period β*/% note: *β= (t380 ℃-t400 ℃) / t380 ℃×100%
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表 4 四种油样的沥青质沉淀点
Table 4 Asphaltene precipitation onset point of four heavy oils
Item A B C D Asphaltene precipitation 4.3 6.6 5.5 6.0 onset point
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表 5 四种油样的稳定性参数
Table 5 Stability parameter of four heavy oils
Item A B C D Stability parameter K* 5.53 6.96 6.41 6.46 note: *K=m(resins+ aromatics)/m(saturates+ asphaltenes)
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