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摘要: 以加拿大油砂沥青大于420℃的减压渣油（BVR）为原料，对比研究其在CO/H2-H2O和N2体系中的热改质特性，通过系统分析BVR在H2-H2O、CO-H2O、N2-H2O等不同氢源下的热改质特性以揭示CO/H2-H2O对渣油热改质的作用机制，最后探讨合成气压力、含水量以及温度对BVR临CO/H2-H2O改质生焦倾向的影响。结果表明，与临氮改质相比，相同反应条件下，合成气和水可使BVR热改质的生焦诱导期延长3.5-6.5 min；相同生焦率（约0.1%）时，合成气和水可显著提升BVR热改质降黏率，410℃时相对临氮改质的降黏率为29.1%，而420℃时可达54.6%。比较不同氢源下BVR热改质的生焦诱导期、改质油黏度和安定性、渣油转化率发现，H2-H2O、CO-H2O、N2-H2O等均对BVR热改质表现出与CO/H2-H2O相同的促进效果，各氢源作用活性的大小顺序为H2-H2O > CO/H2-H2O > CO-H2O > N2-H2O。由此可知，CO/H2-H2O对渣油热改质的促进作用可归因于氢气、CO水热变换新生氢和水热裂解的综合效应，且其中氢气的作用仍最显著。合成气压力、含水量和反应温度可通过影响不同氢源的贡献而调控BVR临CO/H2-H2O改质生焦倾向。低成本易获取的合成气可以提供BVR热降黏改质所需氢源，水能够通过CO水热变换反应供出新生活泼氢而协同合成气实现BVR高效改质。Abstract: The upgrading of the vacuum residue from Canadian oil sand bitumen was performed in a batch reactor with the syngas (CO/H2) and H2O. The effect of CO/H2-H2O for residue upgrading was verified. In the presence of CO/H2-H2O, the coke induction period is postponed by 3.5-6.5 min. When the coke yield is about 0.1%, the viscosity reduction efficiency can be raised by 29.1% at 410℃ and even 54.6% at 420℃. The upgrading experiments were also carried out in the presence of N2-H2O, CO-H2O, and H2-H2O, respectively. The results show that the capability to inhibit the coke formation was in the order of H2-H2O > CO/H2-H2O > CO-H2O > N2-H2O. The impetus of CO/H2-H2O to BVR upgrading could be attributed to the active hydrogen mainly from H2, nascent hydrogen by water-gas shift reaction as well as aqua-thermolysis. The thermal conditions such as the pressure of syngas, water content and reaction temperature could influence the coking propensity of BVR under CO/H2-H2O by affecting the three different attributions. These results indicate that the more accessible and low-cost syngas could provide the necessary hydrogen for BVR upgrading. Water presents a synergism with syngas for further promoting the BVR upgrading process.
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Key words:
- oil sand bitumen /
- syngas /
- aqua-thermolysis /
- active hydrogen /
- thermal upgrading
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图 1 不同温度下BVR临CO/H2-H2O和临N2热改质过程的生焦趋势线
Figure 1 Coke yield curves during BVR upgrading process at different temperatures
(a): with CO/H2-H2O; (b): with N2
图 2 BVR临CO/H2-H2O和临N2热改质油的性质随反应时间的变化
Figure 2 Properties of products from BVR upgrading process with CO/H2-H2O and N2 versus reaction time
(a): υ50; (b): oAPI; (c): spot test rank
图 3 不同氢源作用下BVR热改质的生焦趋势线
Figure 3 Coke yield curves during BVR upgrading process with different hydrogen sources
(a): 410 ℃; (b): 420 ℃
图 4 不同氢源作用下BVR改质油的黏度和安定性等级随反应时间的变化
Figure 4 Properties of products from BVR upgrading process with different hydrogen sources versus reaction time
(a): υ50; (b): spot test rank
图 5 CO/H2-H2O对BVR热改质的可能作用分析
Figure 5 Possible influences of CO/H2-H2O on BVR upgrading
图 6 BVR临CO/H2-H2O改质生焦量随压力和含水量的变化
Figure 6 Coke yield as a function of pressure and water content during BVR upgrading with CO/H2-H2O
(a): pressure; (b): water content
表 1 油砂沥青掺稀原油及减压渣油的基本性质
Table 1 Main properties of BCO and BVR
Sample BCO BVR ρ420/(g·cm-3) 1.0078 1.0397 oAPI 8.4 4.2 υ80/(mm2·s-1) 814 45241 υ100/(mm2·s-1) 256 7878 wCCR/% 15.06 19.03 MW(VPO) 483 875 wS/% 5.44 6.27 wC/% 83.45 83 wH/% 10.42 10.02 wN/% 0.44 0.59 H/C (atomic ratio) 1.49 1.44 wNi/(μg·g-1) 38.8 62.5 wV/(μg·g-1) 133.5 230.1 
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表 2 相同生焦率条件下BVR改质油基本性质对比
Table 2 Main properties of products from BVR upgrading process with CO/H2-H2O and N2 at coke induction period
Thermal condition 410 ℃ 420 ℃ N2 CO/H2-H2O N2 CO/H2-H2O Coke induction period t/min 13 16.5 6.5 10.5 υ50/(mm2·s-1) 650 461 718 326 Relative viscosity reduction rate ηr/% - 29.1 - 54.6 oAPI 9.7 9.9 9.4 10.2 Spot test rank 1 1 1 1 Conversion of OSVR /% 31.77 33.41 29.82 34.26 note：${\eta _r} = \left| {\frac{{{v_{50}}({\rm{CO}}/{{\rm{H}}_2} - {{\rm{H}}_2}{\rm{O}}) - {v_{50}}({{\rm{N}}_2})}}{{{v_{50}}({{\rm{N}}_2})}}} \right| \times 100\% $
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表 3 不同氢源作用下BVR改质过程在生焦诱导期时的渣油转化率
Table 3 Conversion of BVR during upgrading process with different hydrogen sources at coke induction period
Hydrogen sources Temperature t/ ℃ Coke induction period t/min Conversion of OSVR x/% N2-H2O 410 14 31.73 420 7.5 30.37 CO-H2O 410 15 32.58 420 9 31.97 CO/H2-H2O 410 16.5 33.41 420 10.5 34.26 H2-H2O 410 18 34.13 420 12.5 35.86
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