Application of nano-Fe3O4 catalyst in the viscosity reduction of heavy oil by hydrothermal cracking
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摘要: 通过高温热解法和低温双相回流法制备了四种不同尺寸的纳米Fe3O4催化剂，并将其应用于辽河油田稠油水热裂解降黏实验中。结果表明，制备过程中加入重烷基苯磺酸钠（HABS）表面活性剂能够有效提高Fe3O4催化剂在稠油水热裂解体系中的分散性，以高温热解法制备出的HABS修饰的9 nm Fe3O4催化剂降黏效果最佳。当稠油量为250 g时，按m（稠油）：m（催化剂）：m（油层水）质量比为100：0.3：30加入催化剂和油层水，加入0.75 g正作为己烷供氢体，在240℃下反应24 h，辽河油田稠油黏度从86200 mPa·s下降到2065 mPa·s，降黏率高达到97.6%。反应机理分析显示，纳米Fe3O4催化剂攻击稠油长链上键能最低C-S键，使其断键，重组分转化为轻组分。Abstract: Four nano-Fe3O4 catalysts with different particle sizes were prepared by high temperature pyrolysis and low temperature two-phase reflux method; their performance in the hydrothermal cracking and viscosity reduction of Liaohe oil-field heavy oil was investigated. The results indicate that the addition of sodium sulfonate (HABS) surfactant in the preparation process can effectively improve the dispersion of Fe3O4 catalyst in heavy oil for hydrothermal cracking; the HABS-modified 9 nm Fe3O4 catalyst prepared by high temperature pyrolysis exhibits the best viscosity reduction performance. In a reaction system with 250 g heavy oil and 0.75 g n-hexane as hydrogen donor, where the mass ratio of heavy oil:catalyst:reservoir water is 100:0.3:30, the viscosity of heavy oil can be reduced from 86200 to 2065 mPa·s after reaction at 240℃ for 24 h; the viscosity reduction rate is as high as 97.6%. Analysis on the reaction mechanism suggests that the nano-Fe3O4 catalyst attacks the C-S bond on the long-chain heavy oil, breaks the bond and converts the heavy component into light component.
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Key words:
- hydrothermal cracking /
- heavy oil /
- nano Fe3O4 /
- catalytic viscosity reduction /
- viscosity
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图 2 表面原子数占全部原子数的比例和粒子尺寸之间的关系
Figure 2 Relation between the ratio of surface atom number to total atom number and particle size of Fe3O4 materials
图 4 HABS修饰的纳米Fe3O4催化剂(9 nm)的TEM照片((a), (b)), 插图为纳米Fe3O4催化剂(9 nm)分散到正己烷
Figure 4 TEM images of HABS-modified nano-Fe3O4 catalyst (9 nm); the inset shows that nano-Fe3O4 catalyst (9 nm) is dispersed in n-hexane (inset)
图 5 纳米Fe3O4催化剂(9 nm)的FT-IR谱图
Figure 5 FT-IR spectrum of nanometer Fe3O4 catalyst (9 nm)
图 6 稠油经四种不同尺寸的Fe3O4催化剂改质后的黏度和降黏率
Figure 6 Viscosity and viscosity reduction rate of heavy oil after modification over four Fe3O4 catalysts of different particle sizes
图 7 催化剂用量对稠油水热裂解降黏的影响
Figure 7 Effect of catalyst amount on the viscosity reduction of heavy oil by hydrothermal cracking over 9 nm Fe3O4
图 8 反应温度对稠油水热裂解降黏的影响
Figure 8 Effect of reaction temperature on the viscosity reduction of heavy oil by hydrothermal cracking over 9 nm Fe3O4
图 9 反应时间对稠油水热裂解降黏的影响
Figure 9 Effect of reaction time on the viscosity reduction of heavy oil by hydrothermal cracking over 9 nm Fe3O4
图 10 水油质量比对稠油水热裂解降黏的影响
Figure 10 Effect of water-oil quality ratio on the viscosity reduction of heavy oil by hydrothermal cracking over 9 nm Fe3O4
图 11 气体产物气相色谱图
Figure 11 Gas chromatogram of gaseous products for the viscosity reduction of heavy oil by hydrothermal cracking over 9 nm Fe3O4
图 12 稠油水热裂解降黏机理
Figure 12 Viscosity reduction mechanism of heavy oil by hydrothermal cracking
表 1 稠油性质
Table 1 Properties of Liaohe oilfield heavy oil
Property Elemental analysis w/% Group analysis w/% ρ20/(g·cm-3) μ50/(mPa·s) C H S N O saturates aromatics resins asphaltenes 0.956 86200 85.16 11.72 0.66 1.64 0.82 25.2 28.3 39.6 6.9 ρ20, density at 20℃; μ50, viscosity at 50℃ 
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表 2 稠油四组分反应前后变化表
Table 2 Variance in the four-component composition of heavy oil during the viscosity reduction process
Saturates /% Aromatics /% Resins /% Asphaltenes /% Before reaction 25.2 28.3 39.6 6.9 After reaction(5 nm) 30.1 30.6 33.4 5.9 After reaction(9 nm) 33.2 32.2 29.3 5.3 After reaction(12 nm) 32.6 31.3 30.6 5.5 After reaction(16 nm) 32.1 31.1 31.2 5.6
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