随着二氧化碳埋存、二氧化碳驱油以及超深井、稠油热采井的开发，对固井水泥石 的耐腐蚀和耐高温性能要求不断提高，常规波特兰水泥（即硅酸盐水泥）无法满足现场 需要。地质聚合物火山灰材料来源广泛，不污染环境，同时还具有传统水泥所没有的高 强度、耐高温、耐腐蚀等优异性能而日益被人关注，在建筑欧亿·体育（中国）有限公司已经有初步的应用，但 在油井固井中研究较少，因此研究耐高温固井地质聚合物固结体系有着种大的意义。 本文利用偏高岭土、粉煤灰、矿渣等火山灰材料，通过对地质聚合物激发材料的优 选和对各种矿物的配比对固结体系抗压强度的影响进行研究，初步研发了一种高强度、 耐高温、耐腐蚀的地质聚合物固结体系，并对影响此体系凝结时间的各个因素和与此种 体系相适应的缓凝剂进行了探索，同时测试了该体系的流变性能和降失水性能，为高温 固井施工的安全实施提供了保障。 通过实验研究，优选的碱外掺料为氢氧化钠和硅酸钠，硅酸钠加量为 40%-60%， 氢氧化钠加量为 4%-6%，水灰比为 0.7。在低于 140℃温度的高温井下，优选的地质聚 合物矿物组分为：偏高岭土占地质聚合物材料的 60%，矿渣和粉煤灰各占 20%；在高于 140℃温度的高温井下，只采用偏高岭土来合成地质聚合物。 本报告对地质聚合物的耐久性实验发现地质聚合物在高温 220℃条件下养护一个月 强度仍能保持 20MPa 以上，对地质聚合物的耐腐蚀性能研究发现在 CO 2 腐蚀条件下养 护 15 天强度基本保持稳定。本文测试了不同因素对地质聚合物凝结时间的影响，并对 缓凝剂进行了探索，优选出缓凝效果最好的缓凝剂为氯化钡，加量为 5%，测得的凝结 时间能达到 4 个小时，但稠化性能不好且对强度影响较大，不利于其应用。优选的分散 剂为 syjz-1，加量为 2%，地质聚合物 30 分钟的失水量为 32mL，可满足固井施工的要 求。 关键词：地质聚合物，偏高岭土，碱激发材料，抗压强度，凝结时间，耐 CO 2 腐蚀ii Feasibility Study of Geopolymer Based Metakaolin Applied to High Temperature Cementing Liu Yang（Oil& Gas Well Engineering) Directed by Professor Bu Yuhuan Abstract As the development of carbon dioxide storage, carbon dioxide drive and ultra deep well, and heavy oil thermal recovery well, the requirements of the high temperature resistant and corrosion resistant properties of well cementing cement constantly improve. Normal Portland cement cannot meet the needs of the field. Geopolymer material has extensive sources, don’t pollute the environment, but also has the high strength traditional cement don’t have, high temperature resistance, corrosion resistance and other excellent performance and is increasingly concerned by people. Geopolymer have preliminary application in the construction industry, but less research in oil well cementing, so the research of high temperature cementing geopolymer consolidation system has a big significance. This paper use metakaolin, fly ash, slag, such as volcanic ash material, through the optimization of geopolymer excitation material and ratio of various mineral on consolidation system to study the influence of compressive strength, preliminary developed a geopolymer consolidation of high temperature resistance and corrosion resistance system. This paper also carried on the exploration of all the factors affecting the setting time and retarder adapted to the system, and tested the rheological properties and filtration properties of the system, which provided a guarantee for the safety construction of high temperature well cementing. Through experimental research, the optimal activator are sodium hydroxide and sodium silicate. The amount of sodium silicate is 40% to 60%, the amount of sodium hydroxide is 4% to 6%, water cement ratio is 0.7. Under the temperature below 140 ℃, the optimization of geopolymer mineral group is divided into:metakaolin accounted for 60% of geopolymer, eachiii of fly ash and slag accounted for 20%; Under the temperature higher than 140 ℃, only use metakaolin to make geopolymer. This thesis durability experiment of geopolymer found that the strength of geopolymer still can maintain more than 20 MPa under the condition of high temperature 220 ℃ curing a month. Corrosion resistance research of geopolymer found that the strength remained stable under the condition of CO 2 corrosion curing 15 days. This paper tests the influence of different factors on the geopolymer setting time and has carried on the exploration to retarder. This paper selected the retarder is barium chloride, plus the amount of 5%, the setting time can reach four hours, But bad thickening performance and bad impact on the strength, is not conducive to its application Selected the dispersant is syjz-1, plus the amount of 2%, geopolymer’s water loss is 32 mLin 30 minutes, can meet the requirements of cementing. Key words: Geopolymer, Metakaolin, Alkali-active materials, Compressive strength, Setting time, Corrosion resistance of CO 2iv 目 录 第一章 绪 论........................................................................................................................1 1.1 研究的目的及意义...................................................................................................... 1 1.2 地质聚合物的研究现状.............................................................................................. 2 1.2.1 地质聚合物的特点............................................................................................ 2 1.2.2 地质聚合物的国内外发展进程........................................................................ 3 1.2.3 地质聚合物水化硬化机理调研........................................................................ 5 1.2.4 地质聚合物目前存在的问题............................................................................ 5 1.3 报告的研究目标、研究内容和技术路线.................................................................. 6 1.3.1 研究目标............................................................................................................ 6 1.3.2 研究内容............................................................................................................ 6 1.3.3 技术路线............................................................................................................ 7 第二章 地质聚合物固结体系激发材料优选........................................................................8 2.1 实验装置及实验方法.................................................................................................. 8 2.2 激发材料种类和加量的优选.................................................................................... 10 2.2.1 硫酸钠的激发特性.......................................................................................... 10 2.2.2 氢氧化钙的激发特性...................................................................................... 11 2.2.3 氢氧化钠的激发特性...................................................................................... 12 2.2.4 硅酸钠的激发特性.......................................................................................... 13 2.3 激发材料的复配对地质聚合物固结性能的研究.................................................... 14 2.3.1 硅酸钠和氢氧化钠复配的激发特性研究...................................................... 14 2.3.2 硫酸钠和氢氧化钠复配的激发特性研究...................................................... 15 2.4 高温下硅酸钠和氢氧化钠复配的激发效果研究.................................................... 16 2.5 本章小结.................................................................................................................... 16 第三章 偏高岭土基地质聚合物组分优化研究..................................................................17 3.1 矿渣和粉煤灰对偏高岭土地质聚合物性能影响研究............................................ 17 3.1.1 粉煤灰加量对地质聚合物的性能影响.......................................................... 17v 3.1.2 矿渣加量对地质聚合物的性能影响.............................................................. 20 3.1.3 粉煤灰和矿渣的复掺对偏高岭土地质聚合物性能的影响.......................... 23 3.2 水灰比对地质聚合物性能影响研究........................................................................ 25 3.2.1 水灰比对地质聚合物抗压强度影响.............................................................. 25 3.2.2 水灰比对地质聚合物流变性能的影响.......................................................... 2