A Cement Slurry for Large Temperature Difference in Wells of Ten Thousand Meter Depth
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摘要: 针对超深井长封固固井中，顶部底部水泥浆温差大，顶部低温段水泥浆超缓凝、水泥石强度发展缓慢的问题，采用水溶液聚合法制备了一种MgAl-EDTA-LDH（EDTA插层型水滑石）大温差早强剂，并配套形成了一套大温差水泥浆体系。实验结果表明，该大温差早强剂具有一定的缓凝效果，当其加量为2.0%，复配4.0%缓凝剂时，在240 ℃下其稠化时间可达509 min。该水泥浆在60 ℃养护1 d和30 ℃下养护6 d的抗压强度均大于7 MPa，最大温差为210 ℃。大温差早强剂在不影响水泥浆稠化可调性的前提下，有利于低温段水泥浆柱的强度发展，耐热温度达300 ℃以上，适用于大温差固井需求。Abstract: In cementing operation in ultradeep wells with long cementing sections, there is a large difference between the temperature at the top of the cement slurry and that at the bottom of the cement slurry. The low temperature at the top of the cement slurry retards the development of the strength of the set cement. To solve this problem, an early strength additive named EDTA-LDH (EDTA intercalated hydrotalcite) was developed through water solution polymerization. A cement slurry for working at big temperature difference conditions was formulated with EDTA-LDH. Laboratory experimental results show that this early strength additive has retarding effect to some extent; at a concentration of 2.0% EDTA-LDH and 4.0% retarder, a cement slurry has thickening time of 509 min at 240 ℃. After aging at 60 ℃ for 1 d or at 30 ℃ for 6 d, the cement slurry has compressive strengths of both greater than 7 MPa, and experiences maximum temperature difference of 210 ℃. The use of EDTA-LDH is beneficial to the development of the strength of the cement slurry column in low temperature without affecting the adjustability of the thickening time of the cement slurry. This early strength additive can work normally at temperatures above 300 ℃, and is suitable for cementing wells with large temperature differences.
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表 1 大温差早强剂与外加剂配伍性评价
配方 分散剂 降失水剂 缓凝剂 实验条件 t稠化/min 1-1# DRS-1S G33S GH-9L 140 ℃×70 MPa×70 min 293 1-2# USZ DRF-3L GH-8L 160 ℃×80 MPa×80 min 393 1-3# USZ G33S GH-8L 180 ℃×90 MPa×90 min 275 1-4# DRS-1S DRF-3L GH-9L 205 ℃×130 MPa×70 min 438 1-5# USZ G33S GH-9L 215 ℃×130 MPa×110 min 506 1-6# ZF-1 ZJ-5 ZH-6 240 ℃×110 MPa×130 min 441 注：水泥浆基础配方为100%水泥+30%石英砂+5%微硅+(0～2%)大温差早强剂+(0.4%～0.6%)分散剂+(1.5%～2.0%)降失水剂+(2%～4%)缓凝剂+1.5%高温悬浮稳定剂+H2O(W/S=0.44)。 
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表 2 大温差水泥浆综合性能评价
配方 缓凝剂
ZH-6/%大温差
早强剂/%流动度/
cmFL/
mLΔρ/
g·cm−3n K/
Pa·sn2-1# 3.0 0 24.0 37 0.01 0.84 0.61 2-2# 3.0 0.1 24.0 39 0.01 0.83 0.67 2-3# 3.0 0.5 24.0 36 0.01 0.86 0.64 2-4# 3.0 1.0 23.5 43 0.01 0.84 0.63 2-5# 3.0 2.0 23.0 40 0.02 0.87 0.67 注：水泥浆基础配方为100%水泥+30%石英砂+5%微硅+0.4%分散剂ZF-1+2%降失水剂ZJ-5 +1.5%高温悬浮稳定剂BH-ZW-1+H2O(W/S=0.44)。
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表 3 大温差水泥浆性能评价实验
配方 实验条件 ZH-6/
%大温差
早强剂/%t稠化/
min3-1# 120 ℃×60 MPa×60 min 1.5 0.3 308 3-2# 140 ℃×70 MPa×70 min 1.6 0.6 319 3-3# 160 ℃×80 MPa×80 min 1.8 0.8 364 3-4# 180 ℃×90 MPa×90 min 2.5 1.2 444 3-5# 205 ℃×130 MPa×70 min 3.0 1.5 438 3-6# 215 ℃×130 MPa×110 min 3.5 1.8 442 3-7# 240 ℃×110 MPa×130 min 4.0 2.0 509 注：水泥浆基础配方：100%水泥+30%石英砂+5%微硅+0.4%分散剂ZF-1 +2%降失水剂ZJ-5+1.5%高温悬浮稳定剂BH-ZW-1+H2O(W/S=0.44)。
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表 4 大温差水泥浆体系抗压强度测试结果
配方 静止温度下
p24 h /MPa不同温差不同养护时间的水泥石抗压强度/MPa 返高温度90 ℃ 返高温度60 ℃ 返高温度30 ℃ 1 d 2 d 3 d 1 d 2 d 3 d 6 d 3-1# 26.59 19.23 21.98 22.31 18.54 19.66 20.13 15.21 3-2# 25.13 15.62 17.34 19.74 11.03 13.28 15.45 12.65 3-3# 23.87 13.58 15.27 16.88 10.67 11.34 14.86 10.54 3-4# 21.03 12.15 14.07 16.91 9.64 10.91 12.74 8.75 3-5# 19.89 12.37 14.51 14.82 10.89 11.36 13.64 9.01 3-6# 20.46 11.87 13.98 14.75 11.37 13.84 14.21 8.69 3-7# 17.73 9.12 10.12 11.05 7.59 8.97 9.61 7.35
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