Study on Rheology and Reaction Kinetics of Low Corrosion Self-Heating Gelling Fracturing Fluids
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摘要: 在稠油储层压裂改造过程中，压裂液进入裂缝后会降低储层温度，导致裂缝周围原油黏度增加，甚至会堵塞地层。针对此问题，以尿素、亚硝酸钠和氯化铵为生热材料，盐酸为催化剂，耐温耐盐共聚物FS-1为增稠剂，有机锆为交联剂，应用溶液共混法制备了一种低腐蚀自生热冻胶压裂液，评价了压裂液体系的生热产气性能、流变性和耐腐蚀性等性能，测试了反应产生气体组分，探究了不同因素对生热反应速率的影响规律，明确了其反应动力学参数。结果表明：自生热体系具有良好生热生气性能，当反应物浓度、酸性催化剂浓度和初始温度越大，峰值温度越高，生气量越大，到达峰值温度所需时间越短，但生气量随初始温度的增加而略有减少；体系中NH4Cl可大幅降低盐酸浓度，不仅降低了压裂液对压裂管线设备的腐蚀速率，而且有利于压裂液成胶，反应产生大量CO2和N2气体及热量；冻胶一定程度上弱化了生热剂的生热产气性能，60℃、170 s−1下剪切90 min，黏度保持在50 mPa·s以上；自生热冻胶压裂液反应级数m=2.67，n=1.69，活化能ΔE=49.54 kJ/mol，指前因子A=6.82 × 102，相比于自生热体系反应速度大幅下降，可通过反应动力学方程预测该体系反应过程参数并进行调控，为自生热压裂液优化设计提供依据。Abstract: In heavy oil reservoir fracturing, the fracturing fluid, after entering into the reservoir, causes the reservoir temperature to decrease and the viscosity of the crude oils around the fractures to increase to even block the pore throats of the formation. To deal with this problem, a low corrosion self-heating gelling fracturing fluid has been formulated through solution blending method using urea, sodium nitrite and ammonium chloride as heat generation materials, hydrochloric acid as catalyst, the high temperature salt-resistant copolymer FS-1 as viscosifier and organic zirconium as crosslinking agent. In laboratory experiment, the heat generation and gas production properties, rheology and corrosion resistant performance of the fracturing fluid were evaluated, the constituents of the gas produced were identified, the effects of different factors on the rate of heat generation reaction were investigated, and the kinetic parameters of the heat generation reaction were understood. It was found that the self-heating generation system has good heat generation and gas production properties. The higher the concentrations of the reactants, the concentration of the acid catalyst and the initial temperature, the higher the amount of gas produced, and the shorter the time required to reach the highest temperature; on the other hand, the amount of gas is slightly decreasing with an increase in the initial temperature. In the reactant system, the existence of ammonium chloride remarkably reduces the concentration of chloric acid, this not only reduces the rate of corrosion of the fracturing fluid to the pipes for fracturing, but also is beneficial to the gelling of the fracturing fluid. The reaction produces large amount of CO2 and N2 as well as heat. Gelling of the fracturing fluid to some extent weakens the heat generation and gas production properties of the heat generation agents. The gelling fracturing fluid, after shearing at 60℃ and 170 s-1 for 90 min, has viscosity of greater than 50 mPa·s. The reaction order m and n, the activation energy ΔE and the preexponential factor A of the reaction are 2.76, 1.69, 49.54 kJ/mol and 6.82 × 102, respectively. Compared with the self-heating system, the reaction rate of the self-heating gelling fracturing fluid system is greatly reduced. The process parameters of this reaction can be predicted using reaction kinetic equation and adjusted. This study has provided a base for the optimization and design of self-heating fracturing fluids.
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Key words:
- Low corrosion /
- In-situ heating /
- Gel fracturing fluid /
- Rheological properties /
- Reaction kinetics
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表 1 自生热压裂破胶液体系腐蚀性能对比
挂片编号 2 h腐蚀速率/（
g·m−2·h−1）4 h腐蚀速率/（
g·m−2·h−1）腐蚀
现象N-1 0.1653 0.1894 表面光滑，无点蚀或坑蚀 N-2 0.1734 0.1923 N-3 0.1721 0.1941 平均腐蚀速率/（g·m−2·h−1） 0.1703 0.1919 
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表 2 反应动力学参数
体系 反应级数m 反应级数n 活化能ΔE/（kJ·mol−1） 指前因子A 反应动力学方程 自生热体系 1.96 2.13 52.42 5.78× 107 $ \dfrac{{dC}}{{dt}} = - {\text{5}}{\text{.78 }} \times {\text{ }}{10^7}exp\left( { - 52.42/{\text{R}}T} \right){C_{{\text{H}} + }}^{1.96}{C_0}^{2.13} $ 自生热冻胶压裂液 2.67 1.69 49.54 6.82 × 102 $ \dfrac{{dC}}{{dt}} = - {\text{6}}.82 \times {10^2}exp\left( { - 49.54/{\text{R}}T} \right){C_{{\text{H}} + }}^{2.67}{C_0}^{1.69} $
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