The Performance of Set Aluminate Cement Modified by Micro Silica Compounded Sodium Hexametaphosphate under Condition of Shale Oil In-situ Conversion
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摘要: 低成熟度页岩油原位转化工况下极端高温会导致固井水泥石强度发生衰退。因此，研究了微硅复合六偏磷酸钠改性铝酸盐水泥在650 ℃处理前后的宏观性能及微观结构。结果表明，50 ℃下六偏磷酸钠能显著降低铝酸盐水泥石的渗透率，但对抗压强度提升不明显，微硅复合六偏磷酸钠改性铝酸盐水泥石的渗透率明显降低，同时抗压强度提升明显。650 ℃处理后，5.0%六偏磷酸钠改性铝酸盐水泥石的抗压强度最高，为47.19 MPa，而微硅复合六偏磷酸钠改性铝酸盐水泥石的抗压强度呈现降低趋势。铝酸盐水泥石在650 ℃处理前后水化产物发生明显转化，主要是C3AH6和AH3转化为C12A7和CA，其中，C3AH6和AH3主要在180～400 ℃期间发生热分解，同时水泥石由于晶型的转化导致孔隙增大。微硅促使铝酸盐水泥石在50 ℃环境下生成的C2ASH8，有助于改善水泥石的微观结构，但是，650 ℃处理后由于C2ASH8的分解同样会导致水泥石孔隙增大。Abstract: In the in-situ conversion of low purity shale oils, extremely high temperature will result in strength retrogression of the set cement. To solve this problem, study was conducted on the macro-properties and microstructures of an aluminate cement before and after aging 650 ℃. The aluminate cement is a cement modified by micro silica compounded sodium hexametaphosphate. It is found that at 50 ℃, sodium hexametaphosphate can significantly reduce the permeability of a set aluminate cement, and the compressive strength of the set cement is significantly increased. After treatment at 650 ℃, the aluminate cement modified with 5.0% sodium hexametaphosphate has the highest compressive strength, which is 47.19 MPa, while the aluminate cement modified with micro silica compounded sodium hexametaphosphate has strengths that are declining. The hydrational products of the aluminate cement before and after treatment at 650 ℃ have experienced significant changes, from C3AH6 and AH3 to C12A7 and CA, respectively. Among these products, C3AH6 and AH3 are thermally degraded in temperatures between 180 ℃ and 400 ℃, and because of the changes of the crystal form, the permeability of the set cement is increased. Micro silica accelerates the formation of C2ASH8 by the set cement at 50 ℃, and this is beneficial to the improvement of the microstructure of the set cement. Since C2ASH8 will degrade after treatment at 650 ℃, the sizes of the pores in the set cement will also increase.
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表 1 铝酸盐水泥及微硅的组分组成
% 物质 CaO Al2O3 SiO2 TiO2 铝酸盐水泥 47.14 39.13 4.61 4.58 微硅 0.38 0.31 83.06 物质 Fe2O3 K2O SO3 MgO 铝酸盐水泥 2.52 0.59 0.56 0.29 微硅 3.22 2.70 2.43 
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表 2 水泥浆配方
g 配方 CAC 微硅 定优胶 分散剂 六偏
磷酸钠降失
水剂消泡剂 水 0# 100 0 0.1 0.1 5.0 4 1 37.56 1# 95 5 0.1 0.2 5.0 4 1 35.55 2# 90 10 0.1 0.2 5.0 4 1 34.35
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表 3 水泥石水化产物类型及相对质量损失
T/ ℃ 物相 0#配方/% 1#配方/% 50 ℃ 650 ℃ 50 ℃ 650 ℃ 105～180 AH3-gel 0.53 0.28 1.11 0.28 180～220 AH3-gel、C2ASH8* 0.91 0.21 1.32 0.22 220～290 AH3 6.07 0.39 5.63 0.24 290～400 C3AH6 4.40 0.20 2.82 0.23 400～800 AH3 、 C3AH6 2.91 0.39 2.71 0.45 800～1000 C12A7 0.52 0.27 0.59 0.31
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表 4 不同类型水泥石的孔径分布对比
试样 处理
温度<10 nm/% 10～100 nm/% ˃100 nm/% 孔隙度/
%5.0%六偏磷
酸钠改性常温 0.48 7.45 18.98 26.92 650 ℃ 1.56 14.88 26.43 42.89 5.0%微硅复合六
偏磷酸钠改性常温 0.64 18.43 1.78 20.86 650 ℃ 1.97 20.00 20.44 42.40
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