Preparation and Mechanism of HEDP-Intercalated Hydrotalcite Retarder
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摘要: 为解决现有缓凝剂在大温差条件下顶部强度发展缓慢的问题，通过离子交换法将羟基乙叉二磷酸（HEDP）插入水滑石层间，制备了羟基乙叉二磷酸插层水滑石Mg/Al-HEDP-LDH，并将其作为大温差缓凝剂，在水泥浆体系中进行了性能测试。研究结果表明，Mg/Al-HEDP-LDH的最佳制备工艺为pH值为4.5，晶化温度为150 ℃，晶化时间为6 h。Mg/Al-HEDP-LDH层间的HEDP会在水泥颗粒的水化过程中被释放出来起到缓凝的作用，加量在0.3%～0.7%的范围内均能呈现稳定的缓凝效果，且随着Mg/Al-HEDP-LDH加量的增加，稠化时间整体出现增加的现象。 Mg/Al-HEDP-LDH能提高水泥的早期强度，掺量为0.3%、0.5%、0.7%时，水泥石1、3、7、14 d的强度均高于纯水泥，尤其是其1～3 d强度提升明显，3 d强度达到最大值，相对于纯水泥提高了92.9%～103.6%。新型插层水滑石材料Mg/Al-HEDP-LDH在水泥浆体系中具有缓凝效果，能够促进水泥石的早期强度发展。Abstract: To address the problem of slow strength development of the top cement with retarders at large temperature differences, a 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) intercalated hydrotalcite Mg/Al-HEDP-LDH retarder was developed for use in large temperature difference environment. The retarder was prepared by intercalating HEDP in between the layers of hydrotalcite. Performance evaluation of the retarder in cement slurries shows that the optimal conditions for preparing Mg/Al-HEDP-LDH are as follows: pH = 4.5, crystallization temperature = 150 ℃, and crystallization time = 6 hours. The HEDP molecules between the layers of Mg/Al-HEDP-LDH is released during the hydration process of the cement particles to act as a retarder. At a concentration between 0.3% and 0.7%, Mg/Al-HEDP-LDH performs in a stable manner; with an increase of the concentration of Mg/Al-HEDP-LDH, the thickening time of the cement slurry increases. Mg/Al-HEDP-LDH increases the early strength of a cement slurry; at concentrations of 0.3%, 0.5% and 0.7%, the 1-day, 3-day, 7-day and 14-day strengths of the set cement are all higher than that of the blank cement slurry, especially the 1-day and the 3-day strengths, which increase significantly. The maximum 3-day strength is 92.9% – 103.6% higher than that of the blank cement slurry. The novel intercalated hydrotalcite Mg/Al-HEDP-LDH has retarding capacity in cement slurries, and can promote the development of the early strength of set cement.In summary, the novel intercalated hydrotalcite material Mg/Al-HEDP-LDH exhibits a retarding effect in cement slurry and can promote the development of the early strength of set cement.
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表 1 G级油井水泥主要化学成分及质量分数
化学
成分质量
分数/%化学
成分质量
分数/%化学
成分质量
分数/%Na2O 0.23 CaO 61.79 Fe2O3 4.15 Al2O3 3.37 SiO2 20.38 损失 2.61 MgO 1.95 K2O 0.45 其他 5.07 
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表 2 水泥浆配方
配方 G级
水泥/%水/
%HEDP/
%Mg/Al-
HEDP-LDH/
%G33S/
%SXY-2/
%消泡剂/
%C00 100 44 0 0 1 0.5 0.2 P03 100 44 0.3 0 1 0.5 0.2 P05 100 44 0.5 0 1 0.5 0.2 P07 100 44 0.7 0 1 0.5 0.2 P10 100 44 1.0 0 1 0.5 0.2 H03 100 44 0 0.3 1 0.5 0.2 H05 100 44 0 0.5 1 0.5 0.2 H07 100 44 0 0.7 1 0.5 0.2
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表 3 不同晶化条件下Mg/Al-HEDP-LDH 和Mg/Al-CO3-LDH的晶格参数
Mg/Al-HEDP-LDH d(003)/
nmd(006)/
nmd(009)/
nm2θ(003)/
（°）pH T/℃ t/h 3.5 130 8 0.77 0.39 0.26 11.39 140 7 0.78 0.39 0.26 11.29 150 6 0.78 0.39 0.26 12.86 4.0 130 8 0.89 0.44 0.25 9.80 140 7 0.92 0.46 0.27 9.81 150 6 0.90 0.45 0.26 9.75 4.5 130 8 1.24 0.62 0.41 7.08 140 7 1.20 0.60 0.40 7.34 150 6 1.18 0.59 0.39 7.43 Mg/Al-CO3-LDH 0.76 0.38 0.26 11.56
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表 4 Mg/Al-HEDP-LDH对油井水泥流动度及密度的影响
试样 ρ/（g·cm−3） 流动度/cm C00 1.91 24.5 H03 1.90 24.0 H05 1.90 24.0 H07 1.91 24.5
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表 5 Mg/Al-HEDP-LDH对水泥浆流变性的影响
Mg/Al-HEDP-LDH/
%φ3/φ6/φ100/φ200/φ300/φ600 n K/
（Pa·sn）0 16/20/55/87/106/194 0.596 1.316 0.5 16/22/60/92/115/204 0.573 1.649 0.7 18/24/64/95/120/209 0.554 1.937
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表 6 Mg/Al-CO3-LDH以及Mg/Al-TA-LDH对水泥浆稠化时间的影响
配方 Mg/Al-CO3-LDH/% Mg/Al-HEDP-LDH/% T/
℃p/
MPa稠化
时间/minC00 0 0 90 45 140 H03 0 0.3 90 45 381 H05 0 0.5 90 45 251 H07 0 0.7 90 45 >600
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表 7 不同配方水泥石抗压强度
配方 养护
温度/℃不同养护时间（d）的抗压强度/MPa 1 3 7 14 C00 90 17.76 20.04 25.98 27.50 P03 90 0 16.40 18.29 22.46 P05 90 0 16.86 16.83 19.70 P07 90 0 17.47 22.20 28.34 P10 90 0 9.42 12.33 15.20 H03 90 28.92 40.81 39.42 32.36 H05 90 32.84 38.66 34.82 35.16 H07 90 34.66 36.04 34.26 31.68
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表 8 Mg/Al-HEDP-LDH对不同顶底温差条件养护不同时间水泥石抗压强度的影响
预制
温度/℃p/MPa（60 ℃） p/MPa（90 ℃） 24 h 48 h 72 h 24 h 48 h 72 h 120 10.86 14.35 16.48 13.54 17.04 17.42 140 7.95 11.66 16.35 12.12 15.26 17.20 160 7.90 10.60 15.86 10.16 14.28 17.08 180 6.24 10.36 15.48 8.24 12.38 16.98
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表 9 90 ℃不同配方水泥石养护3 d的EDS能谱元素分析
元素 区域A 区域B 原子分数/% 质量分数/% 原子分数/% 质量分数/% C 8.47 15.94 9.03 15.78 O 40.98 22.10 30.29 15.16 Al 5.60 5.09 6.72 5.67 Si 9.50 8.99 11.39 10.01 Ca 47.88 35.45 43.57 53.38 元素 区域C 区域D 原子分数/% 质量分数/% 原子分数/% 质量分数/% C 1.54 3.48 2.02 0.85 O 57.85 37.32 62.16 42.01 Al 1.90 2.06 1.36 1.55 Si 11.15 12.63 11.62 13.78 Ca 27.55 44.52 24.00 40.64
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[1] Wu X Z, Wan F L, Chen Z, et al. Drilling and completion technologies for deep carbonate rocks in the Sichuan basin: practices and prospects[J]. Natural Gas Industry B, 2020, 7(5): 547-556. doi: 10.1016/j.ngib.2020.09.012 [2] 郑明贵, 李期. 中国2020-2030年石油资源需求情景预测[J]. 地球科学进展, 2020, 35(3): 286-296.Zheng Minggui, Li Qi. Scenario prediction of China's oil resource demand in 2020-2030[J]. Advances in Earth Science, 2020, 35(3): 286-296. [3] Zhang D W. Development prospect of natural gas industry in the Sichuan basin in the next decade[J]. Natural Gas Industry B, 2022, 9(2): 119-131. doi: 10.1016/j.ngib.2021.08.025 [4] 黄福喜, 汪少勇, 李明鹏, 等. 中国石油深层、超深层油气勘探进展与启示[J]. 天然气工业, 2024, 44(1): 86-96. doi: 10.3787/j.issn.1000-0976.2024.01.008Huang Fuxi, Wang Shaoyong, Li Mingpeng, et al. Progress and implications of deep and ultra-deep oil and gas exploration in PetroChina[J]. Natural Gas Industry, 2024, 44(1): 86-96. doi: 10.3787/j.issn.1000-0976.2024.01.008 [5] 张超鹏, 陈立超, 张典坤, 等. 深层非常规油气固井材料发展现状及趋势浅析[J]. 世界石油工业, 2023, 30(6): 96-105. doi: 10.20114/j.issn.1006-0030.20231024001Zhang Chaopeng, Chen Lichao, Zhang Diankun, et al. Analysis on development status and trend of new cementing materials for deep unconventional oil and gas[J]. World Petroleum Industry, 2023, 30(6): 96-105. doi: 10.20114/j.issn.1006-0030.20231024001 [6] 贾承造, 王祖纲, 姜林, 等. 中国页岩油勘探开发研究进展与科学技术问题[J]. 世界石油工业, 2024, 31(4): 1-11.Jia Chengzhao, Wang Zugang, Jiang Lin, et al. Progress and key scientific and technological problems of shale oil exploration and development in China[J]. World Petroleum Industry, 2024, 31(4): 1-11 [7] Wang X R, Sun B J, Liu S J, et al. A coupled model of temperature and pressure based on hydration kinetics during well cementing in deep water[J]. Petroleum Exploration and Development, 2020, 47(4): 867-876. doi: 10.1016/S1876-3804(20)60102-1 [8] Qin J K, Pang X Y, Santra A, et al. Various admixtures to mitigate the long-term strength retrogression of Portland cement cured under high pressure and high temperature conditions[J]. Journal of Rock Mechanics and Geotechnical Engineering, 2023, 15(1): 191-203. doi: 10.1016/j.jrmge.2022.02.005 [9] Guo S L, Bu Y H, Liu H J, et al. The abnormal phenomenon of class G oil well cement endangering the cementing security in the presence of retarder[J]. Construction and Building Materials, 2014, 54: 118-122. doi: 10.1016/j.conbuildmat.2013.12.057 [10] 孙欣, 曾林. AMPS聚合物类油井水泥缓凝剂研究进展[J]. 青岛科技大学学报(自然科学版), 2015, 36(S2): 1-3.Sun Xin, Zeng Lin. Research progress on AMPS polymer oil well cement retarder[J]. Journal of Qingdao University of Science and Technology (Natural Science Edition), 2015, 36(S2): 1-3. [11] 谢云媚, 张晔, 马勇, 等. 基于AMPS的早强型缓凝剂的合成及性能[J]. 钻井液与完井液, 2025, 42(3): 379-385. doi: 10.12358/j.issn.1001-5620.2025.03.014Xie Yunmei, Zhang Ye, Ma Yong, et al. Synthesis and properties of an early-strength retarder based on AMPS[J]. Drilling Fluid & Completion Fluid, 2025, 42(3): 379-385. doi: 10.12358/j.issn.1001-5620.2025.03.014 [12] 邹亦玮, 代丹, 王义昕, 等. 有机膦酸盐缓凝剂异常增稠油井水泥浆作用机理[J]. 钻井液与完井液, 2025, 42(1): 110-116. doi: 10.12358/j.issn.1001-5620.2025.01.012Zou Yiwei, Dai Dan, Wang Yixin, et al. Mechanisms of organic phosphonate retarders to abnormally thicken oil well cement[J]. Drilling Fluid & Completion Fluid, 2025, 42(1): 110-116. doi: 10.12358/j.issn.1001-5620.2025.01.012 [13] 林鑫, 刘硕琼, 夏修建, 等. 环氧磷酸缓凝剂研发及抗220 ℃常规密度水泥浆综合性能[J]. 钻井液与完井液, 2024, 41(2): 215-219. doi: 10.12358/j.issn.1001-5620.2024.02.011Lin Xin, Liu Shuoqiong, Xia Xiujian, et al. Development of an epoxy phosphate retarder and a high temperature cement slurry resistant to 220 ℃[J]. Drilling Fluid & Completion Fluid, 2024, 41(2): 215-219. doi: 10.12358/j.issn.1001-5620.2024.02.011 [14] 凌勇, 于倩倩, 马如然, 等. 固井用高温缓凝剂的研究与应用[J]. 钻井液与完井液, 2023, 40(2): 209-215.Ling Yong, Yu Qianqian, Ma Ruran, et al. Study and application of a high temperature retarding agent for well cementing[J]. Drilling Fluid & Completion Fluid, 2023, 40(2): 209-215. [15] Wu W C, Yu X R, Hu A B, et al. Amphoteric retarder for long-standing cementing: preparation, properties and working mechanism[J]. Geoenergy Science and Engineering, 2023, 223: 211524. doi: 10.1016/j.geoen.2023.211524 [16] Ma L, Qiang Y J, Zhao W J. Designing novel organic inhibitor loaded MgAl-LDHs nanocontainer for enhanced corrosion resistance[J]. Chemical Engineering Journal, 2021, 408: 127367. doi: 10.1016/j.cej.2020.127367 [17] Kubissa W, Jaskulski R, Grzelak M. Torrent air permeability and sorptivity of concrete made with the use of air entraining agent and citric acid as setting retardant[J]. Construction and Building Materials, 2021, 268: 121703. doi: 10.1016/j.conbuildmat.2020.121703 [18] Pan Y N, Du J L, Chen J, et al. Interlayer intercalation of Li/Al-LDHs responsible for high-efficiency Boron extraction[J]. Desalination, 2022, 539: 115966. doi: 10.1016/j.desal.2022.115966 [19] Lin Y J, Li D Q, Evans D G, et al. Modulating effect of Mg–Al–CO3 layered double hydroxides on the thermal stability of PVC resin[J]. Polymer Degradation and Stability, 2005, 88(2): 286-293. doi: 10.1016/j.polymdegradstab.2004.11.007 [20] Costa R, Cardoso T, Degen M, et al. Influence of retarder admixtures on the hydration, rheology, and compressive strength of white portland cements under different temperatures[J]. Cement, 2023, 11: 100057. doi: 10.1016/j.cement.2023.100057 [21] Jagtap A, Wagle P G, Jagtiani E, et al. Layered double hydroxides (LDHs) for coating applications[J]. Journal of Coatings Technology and Research, 2022, 19(4): 1009-1032. doi: 10.1007/s11998-022-00624-y [22] Shu X, Ran Q P, Liu J P, et al. Tailoring the solution conformation of polycarboxylate superplasticizer toward the improvement of dispersing performance in cement paste[J]. Construction and Building Materials, 2016, 116: 289-298. doi: 10.1016/j.conbuildmat.2016.04.127 [23] Kumar S, Bera A, Shah S N. Potential applications of nanomaterials in oil and gas well cementing: current status, challenges and prospects[J]. Journal of Petroleum Science and Engineering, 2022, 213: 110395. doi: 10.1016/j.petrol.2022.110395 [24] Cao L, Guo J T, Tian J H, et al. Preparation of Ca/Al-layered double hydroxide and the influence of their structure on early strength of cement[J]. Construction and Building Materials, 2018, 184: 203-214. doi: 10.1016/j.conbuildmat.2018.06.186 [25] 王萌. 水滑石及蒙脱土基超分子双电层纳米材料的制备、表征及应用研究[D]. 北京: 北京化工大学, 2017.Wang Meng. Preparation, characterization, and application of supramolecular double layer nanomaterials based on hydrotalcite and montmorillonite[D]. Beijing: Beijing University of Chemical Technology, 2017. [26] 罗润泽. 水滑石/碳纳米管对水泥砂浆性能影响研究[D]. 衡阳: 南华大学, 2021.Luo Runze. Study on the influence of hydrotalcite/carbon nanotubes on the properties of cement mortar[D]. Hengyang: University of South China, 2021. [27] 贾慧, 金鑫, 魏浩光, 等. 碳纳米管羧基功能化及其对水泥石的影响[J]. 钻井液与完井液, 2024, 41(5): 640-645. doi: 10.12358/j.issn.1001-5620.2024.05.011Jia Hui, Jin Xin, Wei Haoguang, et al. Carboxyl functionalized carbon nanotube and its effects on set cement[J]. Drilling Fluid & Completion Fluid, 2024, 41(5): 640-645. doi: 10.12358/j.issn.1001-5620.2024.05.011 [28] Fakoya M F, Shah S N. Emergence of nanotechnology in the oil and gas industry: emphasis on the application of silica nanoparticles[J]. Petroleum, 2017, 3(4): 391-405. doi: 10.1016/j.petlm.2017.03.001 [29] Liu Y, Liu M Y, Li H, et al. Hydration kinetics of portland cement shifting from silicate to aluminate dominance based on multi-mineral reactions and interactions[J]. Materials & Design, 2023, 233: 112228. doi: 10.1016/j.matdes.2023.112228 [30] Li P P, Hu M M, Liu M, et al. Thixotropic and hydration effects of Mg/Al-layered double hydroxide and sodium montmorillonite composite dispersion on oil well cement paste[J]. Cement and Concrete Composites, 2022, 134: 104785. doi: 10.1016/j.cemconcomp.2022.104785 [31] 张春龙, 王铎, 郝亮亮, 等. 改性纳米SiO2@AEPM聚合物耐温缓凝剂制备及性能评价[J]. 化学工程师, 2023, 37(6): 104-108, 103.Zhang Chunlong, Wang Duo, Hao Liangliang, et al. Preparation and performance evaluation of modified nano-SiO2@AEPM polymeric temperature-resistant retarder[J]. Chemical Engineer, 2023, 37(6): 104-108,103. [32] Xu S L, Chen Z R, Zhang B W, et al. Facile preparation of pure CaAl-layered double hydroxides and their application as a hardening accelerator in concrete[J]. Chemical Engineering Journal, 2009, 155(3): 881-885. doi: 10.1016/j.cej.2009.08.003 [33] Li H Y, Liu Y, Yang K, et al. Effects of synthetic CSH-tartaric acid nanocomposites on the properties of ordinary Portland cement[J]. Cement and Concrete Composites, 2022, 129: 104466. doi: 10.1016/j.cemconcomp.2022.104466 -
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