Preparation and Application of a Salt- and Shear-Resistant Thickening Agent
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摘要: 针对常规耐盐稠剂化耐盐能力有限，耐高速剪切能力差，无法满足气田水回用需求等问题，以丙烯酰胺（AM）、对苯乙烯磺酸钠（SSS）、N,N-二乙基丙烯酰胺（DEAM）、烷基二甲基烯丙基氯化铵（CnDMAAC）为聚合单体，通过乳液聚合制备出聚合物稠化剂ASCM，并通过正交实验优化了聚合条件。ASCM耐盐能力达到85 000 mg/L，耐Ca2+、Mg2+能力达到6000 mg/L，在标准盐水中的黏度保持率在80%左右，经2000 s−1高速剪切后，黏度恢复率达90%。气田水配制的1.6%ASCM，在120℃、170 s−1下剪切90 min后黏度在50 mPa·s左右，静态悬砂2 h无沉降，30～120 min可控破胶，破胶液表面张力25～27 mN/m，残渣含量小于200 mg/L，岩心伤害小于25%。开展气田水、返排液回用9井次，累计回用气田水、返排液1.43×104 m3，施工参数、改造效果与清水配制的一致，综合成本节约20%以上。ASCM具有耐剪切、高悬砂、低伤害、低摩阻的特点，满足气田水、返排液等复杂水质规模化回用的需求。Abstract: Conventional salt-resistant thickening agents cannot satisfy the requirement of recycling gas-field waters because of their limited salt resistance and poor high-speed shearing resistance. In this study a polymer thickening agent ASCM was developed to deal with this problem. ASCM is synthesized by emulsion polymerization with these monomers: acrylamide (AM), sodium p-styrenesulfonate (SSS), N,N-diethylacrylamide (DEAM), alkyldimethylally ammonium chloride (CnDMAAC). The synthesis conditions were optimized through orthogonal experiments. ASCM has salt tolerance of 85 000 mg/L and Ca2+ and Mg2+ tolerance of 6 000 mg/L. In standard salt water ASCM has viscosity retention rate of about 80%. After shearing at 2 000 s−1, 90% of the viscosity can be restored. A 1.6%ASCM solution formulated with a gas field water had viscosity of about 50 mPa·s after shearing at 120℃ and 170 s−1 for 90 min. After statically suspending for 2 h, no settlement of sand was found. The gel of the ASCM solution can be broken under control in 30-120 min. The solution after gel breaking had surface tension of 25-27 mN/m, residue content of less than 200 mg/L, and core damage of less than 25%. ASCM fracturing fluid formulated with gas field waters and flowback liquids was used for 9 well times, the accumulated volume of the reused gas field waters and flowback liquids reached 1.43 × 104 m3, the operation parameters and stimulation effects of the fracturing fluid formulated with ASCM were the same with those of the fracturing fluids formulated with fresh water, and the comprehensive cost was saved by more than 20%. ASCM has the characteristics of good shear resistance, high suspending capacity, low formation damage and low friction, satisfying the needs of large-scale reuse of waters with complex water quality, such as gas field waters and flowback fluids.
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Key words:
- Salt resistant /
- Shear resistant /
- Thickening agent /
- Gas field water /
- Fracturing fluid
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表 1 优化后的ASCM稠化剂聚合物条件
聚合物单体物质的量比
AM∶SSS∶DEAM∶CnDMAAC乳化剂/% 油水体积比 引发剂/% T/℃ 聚合单体质量浓度/% 8∶0.5∶1∶0.15 7 1∶1～1∶1.2 0.2～0.25 40～50 30 
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表 2 ASCM在不同水质中的溶解增黏性能
水质类型 加量/% 起黏时间/s η/mPa·s 黏度保持率/% 清水 1.0 20～25 90 1.2 20 114 1.4 20 139 标准盐水 1.0 30 72 80.0 1.2 25～30 93 81.6 1.4 25 111 79.9 气田水 1.0 30～40 69 76.7 1.2 30 90 78.9 1.4 30 109 78.4 注：标准盐水配方[26]：2.0% KCl+5.5% NaCl+0.45% MgCl2+0.55%CaCl2。气田水矿化度35 000 mg/L，Ca2+、Mg2+含量5700 mg/L，Cl−1含量18 300 mg/L。
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表 3 ASCM压裂液破胶实验情况
配方 破胶剂/
%t/
minη/
mPa·s残渣量/
mg·L−1表面张力/
mN·m−1清水+1.2%ASCM 0.01～0.02 40～100 2.3 159 25.1 返排液+1.4%ASCM 0.01～0.03 30～120 2.5 174 25.9 气田水+1.6%ASCM 0.01～0.04 30～120 2.7 191 26.5
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表 4 不同水质配制ASCM压裂液破胶液的对岩心损害情况
配方 K0/mD Kd/mD 损害率/% 清水+1.2%ASCM 3.04 2.51 17.4 返排液+1.4%ASCM 2.80 2.26 19.3 气田水+1.6%ASCM 3.95 3.05 22.8
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表 5 S59-16-XXH2井现场返排液及气田水水质指标
指标 pH Ca2+/
mg·L−1Mg2+/
mg·L−1悬浮物/
mg·L−1Cl−/
mg·L−1矿化度/
mg·L−1返排液 7 601 77 43 91 00 17 600 气田水 7 5 700 129 26 18 300 35 000
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表 6 S59-16-XXH2井气田水动态回用方案及优化配方
混合比例/% 矿化度/（mg·L−1） 配方 η/mPa·s 气田水 35 000 （1.5%～1.6%）ASCM+（0.02%～0.04%）破胶剂 120～132 返排液 16 700 （1.3%～1.4%）ASCM+（0.02%～0.03%）破胶剂 108～120 （30%～50%）气田水 11 000～18 000 （1.2%～1.4%）ASCM+（0.01%～0.02%）破胶剂 100～130 （50%～70%）气田水 18 000～25 000 （1.4%～1.5%）ASCM+（0.02%～0.03%）破胶剂 110～130
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