A Low Temperature Early Strength Gel Material Based on Reconstruction of Hydrate Layer Frame
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摘要: 针对于天然气水合物能源试采过程中出砂导致试采作业被迫终止的问题，在水合物第2次试采工作经验和层内加固、防砂理论的基础上，进行了水合物层骨架重构的低温早强胶凝材料体系构建研究。该研究对比了嘉华G级、超细水泥和早强水泥的低温早期强度和长期长度、粒径分布，基于满足层内加固骨架重构孔隙尺寸，进行了低温早强胶凝材料组分设计，以水泥浆流动度、早强性及成本为目标，尽可能提高固结体的早期强度，为后续增渗提供更多强度下降空间。通过研究超细油井水泥与嘉华G级水泥的配比、早强剂优选及加量优化，构建出了低温早强胶凝材料体系，该体系在15 ℃水浴下24 h抗压强度可达到12.86 MPa，具有良好的流动性、稠化时间和失水可控性，相较于文献的低温早强水泥浆体系具有更好的增渗高强特性。该研究为后续研究水合物层内骨架重构高渗透、高强度的工作液体系奠定了材料基础。Abstract: In the trial production of natural gas hydrate resources, sand production often forces the operation to terminate. A study, aimed at the construction of low temperature early strength gel materials through reconstruction of hydrate layer frames, is conducted based on the experiences gained in the second trail production of hydrate resources and the theory of intralayer reinforcement and sand control. In the study, the low temperature early strength, the long-term length and the particle size distribution of three kinds of cement, which are Jiahua class G, ultra-fine cement and early strength cement, are compared. Based on satisfying the requirements of reconstructing pore sizes through intralayer reinforcement of frames, the components of the low temperature early strength gel materials are designed. The early strength of the solidification body is increased to a degree that is as high as possible taking into account the fluidity of the cement slurry, the early strength and the cost as the main design targets, thereby leaving more space for the strength decline in subsequent permeability improvement. By studying the ratio of the ultra-fine oil well cement to the Jiahua class G cement, optimizing the early strength agents and their concentrations, a low temperature early strength gel system is developed. The low temperature early strength gel system has 24 h compressive strength in 15 ℃ water bath of 12.86 MPa, good fluidity and controllable thickening time and filtration rate. Compared with other low temperature early strength cement slurries introduced in relevant literatures, this cement slurry has better permeability enhancement and high strength characteristics. This study has laid the material foundation for subsequent researches on frame reconstructing high permeability high strength working fluid systems within hydrate layers.
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Key words:
- Hydrate layer /
- Frame reconstruction /
- Low temperature early strength /
- Gel material
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表 1 水泥材料的化学组成 %
水泥 SiO2 Al2O3 Fe2O3 CaO MgO K2O SO3 嘉华G级水泥 22.70 3.39 4.81 65.6 0.90 0.37 1.21 超细水泥 20.36 8.57 3.19 58.59 5.12 0.59 2.03 早强水泥 0.45 77.23 0.47 18.25 0.43 0.67 2.98 
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表 2 嘉华G级水泥不同养护时间的抗压强度
常用胶凝材料 加量/
%分散剂/
%t养护/
d水固比 p/
MPa嘉华G级水泥 100 0 1 0.44 8.66 100 0 3 0.44 21.49 100 0 7 0.44 31.52 超细水泥 100 0.25 1 0.50 13.75 100 0.25 3 0.50 23.29 100 0.25 7 0.50 31.84 早强水泥 100 0 1 0.44 20.09 100 0 3 0.44 25.31 100 0 7 0.44 28.22
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表 3 3种水泥粒径及比表面积对比
水泥 粒径/μm 比表面积/
m2·g−1最大 10%
以上50%
以上90%
以上平均 嘉华G级水泥 ≥64 ≤5.98 ≤18.31 ≤40.38 21.18 0.171 超细油井水泥 ≤35 ≤2.354 ≤7.19 ≤15.52 8.435 0.505 早强水泥 ≥103 ≤3.534 ≤19.73 ≤64.44 27.57 0.297
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表 4 超细油井水泥和嘉华G级水泥复配体系的抗压强度
超细油井
水泥/%嘉华G级
水泥/%流动度/
cmp1 d/
MPap3 d/
MPa90 10 14.5 12.44 12.54 80 20 15.8 9.71 12.91 70 30 18.3 9.50 13.48 60 40 20.5 9.12 14.37 50 50 23.1 7.37 13.44
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表 5 不同类型早强剂对固结体1d抗压强度的影响
早强剂 加量/% p1 d/MPa 无 0 9.12 氯化钙 0.50 12.13 三乙醇胺 0.05 11.73 有机曼尼希 0.03 7.86 氯化锂 1.00 12.86 硫酸钠 2.00 11.27
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表 6 早强剂加量对固结体1 d抗压强度的影响
早强剂 不同加量（%）下的1 d抗压强度/MPa 0 0.25 0.50 0.75 1.00 1.25 1.50 氯化锂 9.12 10.55 11.78 11.81 12.86 12.52 12.14 氯化钙 9.12 10.93 11.43 10.34 10.07 11.34 10.90
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表 7 早强胶凝材料体系的抗压强度与渗透性的关系
增渗剂 p1 d/
MPa1 d渗透率/
10−3 μm27 d渗透率/
10−3 μm20 12.86 1.64 0.008 15%煤油+0.13%复合乳化剂 5.16 13.96 7.820 15%煤油+0.25%复合乳化剂 4.95 23.96 12.130 15%煤油+0.50%复合乳化剂 4.06 24.62 12.230
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表 8 文献早强胶凝材料体系的抗压强度与渗透性的关系
增渗剂 p1 d/
MPa1 d渗透率/
10−3 μm27 d渗透率/
10−3 μm20 6.20 0.96 0.004 15%煤油+0.13%复合乳化剂 3.65 8.27 4.820 15%煤油+0.25%复合乳化剂 2.95 13.23 7.680 15%煤油+0.50%复合乳化剂 1.06 9.560
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