超高强度凝胶氧化破胶降解动力学研究

贾虎; 李仲国; 聂一凡; 李志杰; 余维初

doi:10.11911/syztjs.2025019

超高强度凝胶氧化破胶降解动力学研究

1.
油气藏地质及开发工程全国重点实验室（西南石油大学），四川成都 610500
2.
中国石油塔里木油田分公司，新疆库尔勒 841000
3.
长江大学化学与环境工程学院，湖北荆州 434023

基金项目: 四川省自然科学基金重点项目“基于机器学习分子设计的分离膜增稠CO₂无水控水压裂液体系构筑”（编号：2025ZNSFSC0029），霍英东教育基金会第十七届高等院校青年教师基金项目“离子液体纳米复合凝胶的构筑及堵水堵漏机理研究”（编号：171043）联合资助。

详细信息

作者简介:
贾虎（1983—），男，湖北武汉人，2006年毕业于长江大学石油工程专业，2012年获西南石油大学油气田开发工程专业博士学位，教授，主要从事油气田化学、储集层保护与改造、提高油气采收率等方面的研究工作。E-mail：tiger-jia@163.com

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出版历程
- 收稿日期: 2024-05-03
- 修回日期: 2025-03-10
- 网络出版日期: 2025-03-25

Degradation kinetics of ultra-high strength gel with oxidative gel breakage

1.
National Key Laboratory of Oil and Gas Reservoir Geology and Exploitation(Southwest Petroleum University), Chengdu, Sichuan, 610500, China
2.
PetroChina Tarim Oilfield Company, Korla, Xinjiang, 841000, China
3.
College of Chemistry & Environmental Engineering, Yangtze University, Jingzhou, Hubei, 434023, China

摘要

摘要:
为明确单体聚合类凝胶在暂堵作业结束后的氧化破胶降解机理，开展了凝胶氧化破胶降解动力学研究。运用Horowitz-Metzger、Coats-Redfern和Flynn-Wall-Ozawa模型，计算得到超高强度凝胶（USGel）降解动力学参数，对比分析得到适合USGel的降解动力学模型；结合扫描电镜、傅里叶红外光谱分析等实验，揭示了破胶剂破碎降解USGel的机理，并得到低、中、高温修正后的降解预测模型。研究结果表明，该模型适用于预测USGel中高温降解时间；根据凝胶降解机理，破胶剂逐步消耗USGel酰胺基团的氨基（—NH₂）和羧酸基团的羟基（—OH）等化学键，聚合物分子链逐步断裂，最终USGel破碎变成液体。研究结果为改进油气井暂堵破胶技术提供了理论依据。
- 降解动力学 /
- 降解预测 /
- 降解机理 /
- 氧化破胶 /
- 凝胶
Abstract:
(Aim) In order to clarify the mechanism of oxidative gel degradation of monomer-polymerised gels at the end of temporary plugging operations, a kinetic study on the oxidative gel degradation of gels was carried out. (Methods) Using the Horowitz-Metzger, Coats-Redfern and Flynn-Wall-Ozawa models, the degradation kinetic parameters of ultra-high-strength gel (USGel) were calculated, and the degradation kinetic model suitable for USGel was obtained by comparative analysis; combining with the scanning electron microscope, Fourier infrared spectroscopy analysis and other experiments, the mechanism of the degradation of USGel by breaking of gel breakers was revealed, were obtained by using Semenov's equation to obtain the modified degradation prediction model for low, medium, and high temperatures, which was suitable for predicting the time of degradation at medium and high temperatures of USGel by analysing the experimental data; and the degradation mechanism was clarified, the The gel-breaker gradually consumes the chemical bonds such as amino group (-NH₂) and hydroxyl group (-OH) of amide group and carboxylic acid group in USGel, and the polymer molecular chain is gradually broken, and finally USGel is broken into liquid. (Conclusion) The results of the study provide a theoretical basis for the improvement of the temporary plugging and breaking technology of oil and gas wells.
- degradation kinetics /
- degradation prediction /
- degradation mechanism /
- oxidative gel-breaking /
- gel

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图 1 不同质量分数活化剂的USGel非等温降解DSC曲线

Figure 1. DSC curves for non-isothermal degradation of USGel with different activator concentrations

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图 2 不同质量分数氧化剂的USGel非等温降解DSC曲线

Figure 2. DSC curves for non-isothermal degradation of USGel with different oxidant concentrations

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图 3 不同升温速率下的USGel非等温降解的DSC曲线

Figure 3. DSC curves for non-isothermal degradation of USGel at different heating rates

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图 4 不同升温速率下的USGel转化率曲线

Figure 4. USGel conversion curve at different heating rates

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图 5 Horowitz-Metzger模型不同升温速率下 $\color[RGB]{34,86,159}{\ln\left({\ln}\left(\dfrac{{1}}{{1-}{\alpha}}\right)\right)}$ 与θ的关系

Figure 5. The relationship between $\color[RGB]{34,86,159}{\ln\left({\ln}\left(\dfrac{{1}}{{1-\alpha}}\right)\right)}$ and θ=T−T_S under different heating rates in Horowitz-Metzger model

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图 6 Coats-Redfern模型不同升温速率下 $\color[RGB]{34,86,159}{\ln\left({\ln}\left(\frac{{1}}{{1-}{\alpha}}\right){/}{{T}}^{{2}}\right)}$ 与T⁻¹的关系

Figure 6. Relationship between $\color[RGB]{34,86,159}{\ln\left({\ln}\left(\frac{{1}}{{1-}{\alpha}}\right){/}{{T}}^{{2}}\right)}$ and T⁻¹ under different warming rates in Coats-Redfern model

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图 7 Flynn-Wall-Ozawa模型不同转化率α下lgβ与T⁻¹的关系

Figure 7. Relationship between lgβ andT⁻¹ under different conversions α of Flynn-Wall-Ozawa model

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图 8 低温USGel转化率拟合曲线

Figure 8. Low temperature USGel conversion fitting curve

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图 9 中温USGel转化率拟合曲线

Figure 9. Fitting curve of USGel conversion at medium temperature

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图 10 高温USGel转化率拟合曲线

Figure 10. High temperature USGel conversion fitting curve

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图 11 温度105 ℃下USGel质量保留率

Figure 11. USGel quality retention at 105 ℃

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图 12 105 ℃下破胶不同时间USGel微观结构变化

Figure 12. The change of USGel microstructure at different time of breaking at 105 ℃

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图 13 不同样品红外光谱图

Figure 13. Infrared spectra of different samples

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表 1 Horowitz-Metzger模型降解动力学参数

Table 1 Degradation kinetics parameters of Horowitz-Metzger model

β/(K·min⁻¹)	E/(kJ·mol⁻¹)	T_S/K	斜率	截距	lnA	决定系数
2	66.696	358.41	0.062 45	0.005 68	20.31	0.994
4	67.288	383.15	0.055 13	-0.035 40	19.69	0.992
6	60.021	396.33	0.045 93	-0.009 04	16.92	0.999
8	53.871	404.15	0.039 67	-0.003 04	14.82	0.999

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表 2 Coats-Redfern模型降解动力学参数

Table 2 Degradation kinetics parameters of Coats-Redfern model

β/(K·min⁻¹)	E/(kJ·mol⁻¹)	n	斜率	截距	lnA	决定系数
2	54.882	1	−6 601.19	6.652	16.26	0.995
4	25.031	1	−3 010.73	−5.122	4.66	0.972
6	23.954	1	−2 881.14	−6.05	4.13	0.973
8	21.210	1	−2 551.08	−7.428	2.87	0.952

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表 3 Flynn-Wall-Ozawa模型降解动力学参数

Table 3 Degradation kinetics parameters of Flynn-Wall-Ozawa model

α，%	E/(kJ·mol⁻¹)	斜率	截距	lnA	决定系数
10	24.22	−2 912.62	9.36	6.58	0.988
20	17.63	−2 120.00	6.64	5.21	0.977
30	17.14	−2 061.44	6.30	5.18	0.961
40	16.80	−2 020.85	6.08	5.14	0.968
50	16.26	−1 955.15	5.82	5.11	0.982
60	15.79	−1 899.18	5.60	5.05	0.992
70	15.06	−1 811.72	5.31	5.01	0.996
80	14.34	−1 724.87	5.02	4.96	0.994
90	13.47	−1 620.38	4.69	4.97	0.994

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超高强度凝胶氧化破胶降解动力学研究

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Degradation kinetics of ultra-high strength gel with oxidative gel breakage

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