超临界水稠油改质反应动力学研究

doi:10.11949/0438-1157.20250396

摘要/Abstract

摘要：

为探究超临界水注采中稠油原位转化的反应机制，通过反应釜实验探究了380~420℃时稠油在超临界水中改质产物的变化规律。结果表明，改质后减压渣油显著减少，各轻质组分含量增加；提高反应温度及延长反应时间能深化改质效果，但也使结焦加剧。基于实验结果，建立了6集总反应动力学模型，发现反应温度对反应平衡方向具有显著影响，380℃时轻质组分以及气体主要由减压渣油裂解产生，在更高温度下，减压瓦斯油与常压瓦斯油趋于向更轻质组分转化。结合动力学模型，通过油藏数值模拟研究了超临界水驱油的实际开采效果，结果表明在400℃以上时超临界水驱油效率较高，升温能提高采出油中轻质组分含量，但受流体传热传质影响，原位改质效果有一定限制。

关键词: 超临界水, 石油, 反应动力学, 原位改质, 数值模拟

Abstract:

In order to investigate the chemical reaction mechanisms of in-situ heavy oil upgrading during supercritical water flooding, batch reactor experiments were conducted to study the transformation of fraction distribution of upgraded heavy oil products in supercritical water at 380—420℃. The results showed that the vacuum residue content was significantly reduced after upgrading, while the content of various light components increased. Increasing the reaction temperature or extending the reaction time enhance the upgrading effect but also intensify coke formation. Based on the experimental results, a six-lumped kinetic model was established, revealing that reaction temperature has a significant impact on the reaction equilibrium. At 380℃, light fractions and gas are mainly produced from the cracking of vacuum residue, whereas at higher temperatures, vacuum gas oil and atmospheric gas oil sequentially tend to convert into lighter fractions. Integrating the kinetic model, reservoir numerical simulations were performed to evaluate the actual oil recovery performance of supercritical water flooding. The results indicate that at temperatures above 400℃, supercritical water flooding exhibits high efficiency of oil recovery. The content of light fractions in the produced oil increases with temperature. However, the effect of in-situ upgrading remains constrained due to the effects of fluid heat and mass transfer.

Key words: supercritical water, petroleum, reaction kinetics, in-situ upgrading, numerical simulation

中图分类号:

TQ 051

雷宇寰, 赵秋阳, 董宇, 张延龙, 郭烈锦. 超临界水稠油改质反应动力学研究[J]. 化工学报, 2025, 76(11): 5544-5553.

Yuhuan LEI, Qiuyang ZHAO, Yu DONG, Yanlong ZHANG, Liejin GUO. Kinetic study of heavy oil upgrading reaction in supercritical water[J]. CIESC Journal, 2025, 76(11): 5544-5553.

图/表 10

参考文献 41

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模型参数	参数值
模型截面积/cm²	12.57
模型长度/cm	43
网格块尺寸/cm	0.709×0.709×1.075
孔隙度/%	46.43
渗透率/mD	2330
岩石热导率/（J/(m∙d∙℃)）	1.496×10⁵
岩石热容/（J/(m³∙℃)）	2.607×10⁶
水相热导率/（J/(m∙d∙℃)）	5.35×10⁴
油相热导率/（J/(m∙d∙℃)）	1.15×10⁴
气相热导率/（J/(m∙d∙℃)）	1900
油藏初始温度/℃	150
油藏初始压力/MPa	7
注入温度/℃	380, 400, 420
生产井井底压力/MPa	25
注入速率/(ml/min)	3

模型参数	参数值
模型截面积/cm²	12.57
模型长度/cm	43
网格块尺寸/cm	0.709×0.709×1.075
孔隙度/%	46.43
渗透率/mD	2330
岩石热导率/（J/(m∙d∙℃)）	1.496×10⁵
岩石热容/（J/(m³∙℃)）	2.607×10⁶
水相热导率/（J/(m∙d∙℃)）	5.35×10⁴
油相热导率/（J/(m∙d∙℃)）	1.15×10⁴
气相热导率/（J/(m∙d∙℃)）	1900
油藏初始温度/℃	150
油藏初始压力/MPa	7
注入温度/℃	380, 400, 420
生产井井底压力/MPa	25
注入速率/(ml/min)	3

反应路径	反应速率常数k_ij /min^-1			指前因子A/min^-1	活化能E/(J/mol)	决定系数R²
反应路径	380℃	400℃	420℃	指前因子A/min^-1	活化能E/(J/mol)	决定系数R²
K₁₂	1.86×10^-3	2.45×10^-3	3.33×10^-3	2.67×10³⁶	5.48×10⁴	0.9973
K₂₁	5.64×10^-4	2.57×10^-3	6.12×10^-3	1.65×10³³	2.25×10⁵	0.9810
K₂₃	1.33×10^-3	2.25×10^-3	5.65×10^-3	1.08×10²⁰	1.35×10⁵	0.9692
K₃₂	7.03×10^-4	3.76×10^-3	9.15×10^-3	4.90×10¹⁸	2.42×10⁵	0.9750
K₃₄	1.43×10^-3	2.43×10^-3	4.01×10^-3	1.82×10¹⁶	9.69×10⁴	1.0000
K₄₃	4.91×10^-3	1.13×10^-2	5.19×10^-2	2.11×10¹⁵	2.21×10⁵	0.9663
K₁₅	2.37×10^-4	3.38×10^-4	4.73×10^-4	6.10×10¹⁴	6.52×10⁴	1.0000
K₄₅	4.21×10^-3	1.31×10^-2	8.41×10^-2	1.10×10¹⁴	2.81×10⁵	0.9760
K₄₂	2.63×10^-4	2.96×10^-3	3.51×10^-2	8.45×10⁷	4.60×10⁵	0.9995
K₄₁	4.27×10^-3	8.57×10^-3	3.84×10^-2	6.42×10⁵	2.06×10⁵	0.9503
K₃₁	1.76×10^-5	2.52×10^-4	4.22×10^-3	8.03×10⁴	5.15×10⁵	0.9988
K₁₃	1.02×10^-3	2.33×10^-3	3.24×10^-3	4.45×10¹	1.10×10⁵	0.9502
K₄₆	2.14×10^-2	5.19×10^-2	3.27×10^-1	3.89×10¹	2.55×10⁵	0.9535

反应路径	反应速率常数k_ij /min^-1			指前因子A/min^-1	活化能E/(J/mol)	决定系数R²
反应路径	380℃	400℃	420℃	指前因子A/min^-1	活化能E/(J/mol)	决定系数R²
K₁₂	1.86×10^-3	2.45×10^-3	3.33×10^-3	2.67×10³⁶	5.48×10⁴	0.9973
K₂₁	5.64×10^-4	2.57×10^-3	6.12×10^-3	1.65×10³³	2.25×10⁵	0.9810
K₂₃	1.33×10^-3	2.25×10^-3	5.65×10^-3	1.08×10²⁰	1.35×10⁵	0.9692
K₃₂	7.03×10^-4	3.76×10^-3	9.15×10^-3	4.90×10¹⁸	2.42×10⁵	0.9750
K₃₄	1.43×10^-3	2.43×10^-3	4.01×10^-3	1.82×10¹⁶	9.69×10⁴	1.0000
K₄₃	4.91×10^-3	1.13×10^-2	5.19×10^-2	2.11×10¹⁵	2.21×10⁵	0.9663
K₁₅	2.37×10^-4	3.38×10^-4	4.73×10^-4	6.10×10¹⁴	6.52×10⁴	1.0000
K₄₅	4.21×10^-3	1.31×10^-2	8.41×10^-2	1.10×10¹⁴	2.81×10⁵	0.9760
K₄₂	2.63×10^-4	2.96×10^-3	3.51×10^-2	8.45×10⁷	4.60×10⁵	0.9995
K₄₁	4.27×10^-3	8.57×10^-3	3.84×10^-2	6.42×10⁵	2.06×10⁵	0.9503
K₃₁	1.76×10^-5	2.52×10^-4	4.22×10^-3	8.03×10⁴	5.15×10⁵	0.9988
K₁₃	1.02×10^-3	2.33×10^-3	3.24×10^-3	4.45×10¹	1.10×10⁵	0.9502
K₄₆	2.14×10^-2	5.19×10^-2	3.27×10^-1	3.89×10¹	2.55×10⁵	0.9535

产油参数	实验值	模拟值	误差/%
采收率/%	93.43	94.98	1.55
产物质量分数/%
石脑油	1.76	1.65	0.11
常压瓦斯油	13.35	12.32	1.03
减压瓦斯油	24.82	25.44	0.62
减压渣油	60.07	60.59	0.52