低温低水化热固井水泥浆体系研究
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摘要
深水海域地区的天然气水合物资源丰富,加快天然气水合物开采是世界各国能源发展的重要规划,我国中长期科学和技术发展规划中将天然气水合物开发技术作为前沿技术单独提出。但由于天然气水合物仅在低温高压条件下稳定存在,如何避免固井时天然气水合物层失稳的安全开采对固井提出了新要求,而我国在天然气水合物固井技术研究方面还很薄弱。本研究是为适应深水水合物层固井要求而进行的前沿性应用基础研究。针对天然气水合物固井面临的低温、天然气水合物失稳、浅层水-气流动等问题,论文开展了低水化热水泥外掺料、对水泥浆水化热影响小的促凝剂、低水化热水泥的吸热剂、降失水剂、防气窜剂等研究。
依据硅酸盐水化机理、胶凝材料的微集料效应、形态效应以及火山灰反应等原理,通过在G级油井水泥中引入具有低水化热性能的胶凝材料稀释水泥体系中具有高水化热的熟料成分,从而达到降低水泥体系整体水化热的目的。在水泥熟料的水化机理和低水化热胶凝材料水化及活化理论指导下,优选了用于深水水合物层固井的低水化热胶凝材料,评价分析了低水化热胶凝材料对水泥水化热、水泥浆稠化时间、流变性及水泥石强度等性能的影响,得出了单独加入低水化热胶凝材料的水泥组成配方。两种或两种以上胶凝材料同时加入水泥可获得性能上的优势互补。因此,将优选的低水化热胶凝材料(矿渣、粉煤灰)同时加入水泥,形成的低水化热水泥配方LHC-3:矿渣、粉煤灰各15%、胜维G级水泥70%,其浆体生成的纤维状放射型C-S-H凝胶数目最多,更大限度的填充和密实了水泥石微空隙,增强了水泥石强度,且LHC-3水泥体系的浆体温度比G级水泥原浆的温度低12℃。
LHC-3水泥配方虽然性能具有更大的优势,但其水泥石强度尚无法完全满足深水水合物层固井要求,论文研究探讨了LHC-3体系中低水化热胶凝材料潜在活性激发问题及体系水泥石强度改善情况。单独使用或复合使用碱性激活剂、硫酸盐激活剂、有机激活剂都可不同程度的激发低水化热胶凝材料的潜在活性,并具有一定的促凝早强作用,有利于水泥石获得较高的早期强度。但它们发热量大,不利于水合物的稳定。优选的(1.0%CaO+1.5%Na_2SO_4+0.03%TEA)无机有机复合激活剂在激发水泥活性的同时,还可兼顾水泥石强度的改善和降低水泥水化热之间的平衡。
深水低温环境导致施工水泥浆凝固缓慢,延长了建井周期。依据曼尼希反应原理,将含有羟基官能团的胺类进行氨甲基化对称反应制备了四羟基有机曼尼希碱促凝剂DWGZ-1。该促凝剂加量小,质量百分含量仅为0-0.05%,而传统促凝剂加量在1.0-3.0%之间;对低水化热水泥体系促凝早强效果明显且能使水泥浆成直角稠化(传统促凝剂做不到);对水泥浆体系水化热影响小,加入该促凝剂水泥浆温度变化与不加的基本相同,而传统促凝剂可使水泥浆温度多升高20℃左右。因此,DWGZ-1促凝剂与同类产品比较,可更好地适应深水低温固井要求。
依据无机盐类的结晶水合物在失去结晶水时会吸收环境热量的原理,以乙基纤维素作为囊壁材料,KAl(SO_4)_2·12H_2O或CaSO_4·2H_2O结晶水合物作为囊芯材料,利用微胶囊包裹技术对带结晶水的无机盐类物质实施微胶囊包裹,成功研制了低水化热水泥吸热剂DWGCX。该剂吸收热量具有温度选择性,吸收温度高于60℃的环境热量,可使水泥浆的温度保持在60℃左右,既不影响水泥浆正常水化升温,又可避免深部地热对水合物的影响。
针对深水水合物层固井的特殊性和低温低水化热固井水泥的适应性,开发研究了低水化热固井水泥浆体系配套外加剂。成膜型低水化热水泥降失水剂DWGJ-2低温下具有较好的降失水性能,并对低温下的水泥浆稠化时间影响较小。防气窜剂DWGJR的胶乳微颗粒和成膜性能使其具有良好的防气窜性能还能强化降失水剂的降失水效果,改善水泥石渗透率,提高水泥石的抗腐蚀能力。
形成的低温低水化热固井水泥浆体系DWGC很好的控制了浆体水化放热,具有良好的流动性能,稠化时间可调,静胶凝强度过渡时间短,可以减少水-气窜发生的几率;在配套外加剂的作用下,水泥石强度和耐腐蚀性得到改善,为深水水合物层固井技术的基础性研究打下了一定的基础。
Resources of gas hydrate are rich in deep sea region. Speeding up the exploitation of gas hydrates are important energy development planning around the world. The development technology of natural gas hydrate as cutting-edge technology is separately advanced in China's medium and long-term development plan of science and technology. Stability existence of gas hydrate is only at a certain scope. How to avoid instability when cementing the gas hydrate layer and safe exploitation of natural gas hydrate resources are a new request of cementing. Our country in natural gas hydrate layer cementing technology research is still a zero. In order to meet the development strategy of China's oil and gas resources, basic research of cutting-edge applications, this is carried out in this study. Gas hydrate cementing is faced with the low temperature, instability of gas hydrates, shallow water-gas flow problem. Thesis is the first to conduct research about the low hydration heat of cement system, the small heat-affected cement accelerator, the low hydration heat cement endothermic agent, fluid loss agent, anti-gas channeling agent, etc.
Based on the mechanism of hydration of Portland, micro-aggregate effect, morphological effect and pozzolanic reaction, the low heat performance foreign admixtures are introduced into the class G oil well cement in order to dilute the high hydration heat compositions of cement clinker, thus reducing the overall hydration heat of the cement system. Under the guidance of hydration mechanism of the cement clinker and activation theory of the low hydration heat materials, the thesis has optimized low hydration materials for deep water hydrate layer cementing, has evaluated hydration heat of materials with low hydration heat, cement slurry thickening time, rheology and strength of cement stone, etc. And a cement formulation of separately adding low hydration materials has been acquired.
Two or more cementitious materials added into cement at the same time are available to the complementary performance advantages. Therefore, the low hydration heat preferred materials (slag, fly ash) simultaneously are added into cement, then forms an low hydration heat of cement formulation LHC-3: slag, fly ash of 15%, Shengwei class G cement 70%. Its fibrous actinomorphic generated C-S-H gel has the largest number, it can maximumly fill and compact the cement micro-gap, enhance the strength of cement paste, furthermore its strength is equivalent with slag - cement system. And the hydration heat of LHC-3 cement system is lower, Cement slurry temperature only rises 11℃than the initial temperature, in contrast G class increased by 23℃than the initial temperature of cement. Therefore, LHC-3 achieves a better optimization of performance advantages in cement strength and hydration heat of cement slurry.
Although LHC-3 has a greater advantage of performance cement, its cement strength can not fully meet the requirements of deep water hydrate layer cementing. The dissertation has researched how to excite the potential activity of the low hydration heat materials and how to improve the cement strength. The separate use or the compositional use of alkaline activator, sulphate activator, organic activators can inordinately excite the potential activity of the low hydration heat materials, and they has early strength acceleration to make cement stone acquire higher early strength. But they their hydration heat are so high not conducive to the stability of hydrate.
Deepwater low temperature causes the slow solidification of construction cement, and it can extend construction cycle of oil and gas well. In accordance with Mannich reaction principle, amine with Hydroxyl functional group has aminomethylation and generate the Mannich alkali accelerator DWGZ-1. The accelerator has a small dosage(0-0.05%), while the traditional accelerator is used between 1.0- 3.0% dosage; it has a strong accelerating effect for cement system of low hydration heat and makes cement slurry right-angle thickening(The traditional accelerator does not). DWGZ-1 has a small hydration heat impact on the cement slurry system. Therefore, DWGZ-1 has unparalleled advantages with similar accelerators, and it can better meet the requirements of deep water hydrate layer cementing.
Based on the principles which the inorganic salts with crystal water will absorb environmental heat when hydrate is losing its crystal water, with ethyl cellulose as the wall material and KAl(SO_4)_2·12H_O or CaSO_4·2H_2O as capsule-core, The use of microencapsulation technology has packaged the inorganic salts with crystal water, and successfully prepare the cement endothermic agent DWGCX of a low heat hydration. Absorption heat of the agent has a temperature selection, it can absorb heat of the Environment which the temperature is higher than 60℃. It will enable the slurry to maintain the temperature at around 60℃, without affecting the normal hydration of cement slurry, also avoiding the deep geothermal impact on the hydrate.
In connection with particularity of deepwater hydrate layer cementing and adaptability of low temperature and low hydration heat cement, matched additive system of low temperature and low hydration heat has been researched and developed. Under low temperature Filmformed fluid loss agent DWGJ-2 has good low temperature performance and reducing fluid loss performance, and it does not affect the thickening time of cement slurry. The latex micro- particles and film-forming properties of anti-gas channeling agent DWGJR make it have good anti-gas channeling performance. It can strengthen the reducing fluid loss performance of fluid loss agent, it can improve cement penetration, and it can improve the corrosion resistance of cement.
The low temperature and low hydration heat cement slurry system DWGC can better control exothermic hydration heat of the slurry, have good flow properties. Its thickening time can adjust according to cementing requirement. Its transition time of static gel strength is short and the probability of gas or water channeling occurrence will be decreased. Under the effects of the matched additives, cement strength and corrosion resistance got improved, it will help extend the life of oil wells. DWGC system can well adapt to the requirements of deep water hydrate layer cementing.
依据硅酸盐水化机理、胶凝材料的微集料效应、形态效应以及火山灰反应等原理,通过在G级油井水泥中引入具有低水化热性能的胶凝材料稀释水泥体系中具有高水化热的熟料成分,从而达到降低水泥体系整体水化热的目的。在水泥熟料的水化机理和低水化热胶凝材料水化及活化理论指导下,优选了用于深水水合物层固井的低水化热胶凝材料,评价分析了低水化热胶凝材料对水泥水化热、水泥浆稠化时间、流变性及水泥石强度等性能的影响,得出了单独加入低水化热胶凝材料的水泥组成配方。两种或两种以上胶凝材料同时加入水泥可获得性能上的优势互补。因此,将优选的低水化热胶凝材料(矿渣、粉煤灰)同时加入水泥,形成的低水化热水泥配方LHC-3:矿渣、粉煤灰各15%、胜维G级水泥70%,其浆体生成的纤维状放射型C-S-H凝胶数目最多,更大限度的填充和密实了水泥石微空隙,增强了水泥石强度,且LHC-3水泥体系的浆体温度比G级水泥原浆的温度低12℃。
LHC-3水泥配方虽然性能具有更大的优势,但其水泥石强度尚无法完全满足深水水合物层固井要求,论文研究探讨了LHC-3体系中低水化热胶凝材料潜在活性激发问题及体系水泥石强度改善情况。单独使用或复合使用碱性激活剂、硫酸盐激活剂、有机激活剂都可不同程度的激发低水化热胶凝材料的潜在活性,并具有一定的促凝早强作用,有利于水泥石获得较高的早期强度。但它们发热量大,不利于水合物的稳定。优选的(1.0%CaO+1.5%Na_2SO_4+0.03%TEA)无机有机复合激活剂在激发水泥活性的同时,还可兼顾水泥石强度的改善和降低水泥水化热之间的平衡。
深水低温环境导致施工水泥浆凝固缓慢,延长了建井周期。依据曼尼希反应原理,将含有羟基官能团的胺类进行氨甲基化对称反应制备了四羟基有机曼尼希碱促凝剂DWGZ-1。该促凝剂加量小,质量百分含量仅为0-0.05%,而传统促凝剂加量在1.0-3.0%之间;对低水化热水泥体系促凝早强效果明显且能使水泥浆成直角稠化(传统促凝剂做不到);对水泥浆体系水化热影响小,加入该促凝剂水泥浆温度变化与不加的基本相同,而传统促凝剂可使水泥浆温度多升高20℃左右。因此,DWGZ-1促凝剂与同类产品比较,可更好地适应深水低温固井要求。
依据无机盐类的结晶水合物在失去结晶水时会吸收环境热量的原理,以乙基纤维素作为囊壁材料,KAl(SO_4)_2·12H_2O或CaSO_4·2H_2O结晶水合物作为囊芯材料,利用微胶囊包裹技术对带结晶水的无机盐类物质实施微胶囊包裹,成功研制了低水化热水泥吸热剂DWGCX。该剂吸收热量具有温度选择性,吸收温度高于60℃的环境热量,可使水泥浆的温度保持在60℃左右,既不影响水泥浆正常水化升温,又可避免深部地热对水合物的影响。
针对深水水合物层固井的特殊性和低温低水化热固井水泥的适应性,开发研究了低水化热固井水泥浆体系配套外加剂。成膜型低水化热水泥降失水剂DWGJ-2低温下具有较好的降失水性能,并对低温下的水泥浆稠化时间影响较小。防气窜剂DWGJR的胶乳微颗粒和成膜性能使其具有良好的防气窜性能还能强化降失水剂的降失水效果,改善水泥石渗透率,提高水泥石的抗腐蚀能力。
形成的低温低水化热固井水泥浆体系DWGC很好的控制了浆体水化放热,具有良好的流动性能,稠化时间可调,静胶凝强度过渡时间短,可以减少水-气窜发生的几率;在配套外加剂的作用下,水泥石强度和耐腐蚀性得到改善,为深水水合物层固井技术的基础性研究打下了一定的基础。
Resources of gas hydrate are rich in deep sea region. Speeding up the exploitation of gas hydrates are important energy development planning around the world. The development technology of natural gas hydrate as cutting-edge technology is separately advanced in China's medium and long-term development plan of science and technology. Stability existence of gas hydrate is only at a certain scope. How to avoid instability when cementing the gas hydrate layer and safe exploitation of natural gas hydrate resources are a new request of cementing. Our country in natural gas hydrate layer cementing technology research is still a zero. In order to meet the development strategy of China's oil and gas resources, basic research of cutting-edge applications, this is carried out in this study. Gas hydrate cementing is faced with the low temperature, instability of gas hydrates, shallow water-gas flow problem. Thesis is the first to conduct research about the low hydration heat of cement system, the small heat-affected cement accelerator, the low hydration heat cement endothermic agent, fluid loss agent, anti-gas channeling agent, etc.
Based on the mechanism of hydration of Portland, micro-aggregate effect, morphological effect and pozzolanic reaction, the low heat performance foreign admixtures are introduced into the class G oil well cement in order to dilute the high hydration heat compositions of cement clinker, thus reducing the overall hydration heat of the cement system. Under the guidance of hydration mechanism of the cement clinker and activation theory of the low hydration heat materials, the thesis has optimized low hydration materials for deep water hydrate layer cementing, has evaluated hydration heat of materials with low hydration heat, cement slurry thickening time, rheology and strength of cement stone, etc. And a cement formulation of separately adding low hydration materials has been acquired.
Two or more cementitious materials added into cement at the same time are available to the complementary performance advantages. Therefore, the low hydration heat preferred materials (slag, fly ash) simultaneously are added into cement, then forms an low hydration heat of cement formulation LHC-3: slag, fly ash of 15%, Shengwei class G cement 70%. Its fibrous actinomorphic generated C-S-H gel has the largest number, it can maximumly fill and compact the cement micro-gap, enhance the strength of cement paste, furthermore its strength is equivalent with slag - cement system. And the hydration heat of LHC-3 cement system is lower, Cement slurry temperature only rises 11℃than the initial temperature, in contrast G class increased by 23℃than the initial temperature of cement. Therefore, LHC-3 achieves a better optimization of performance advantages in cement strength and hydration heat of cement slurry.
Although LHC-3 has a greater advantage of performance cement, its cement strength can not fully meet the requirements of deep water hydrate layer cementing. The dissertation has researched how to excite the potential activity of the low hydration heat materials and how to improve the cement strength. The separate use or the compositional use of alkaline activator, sulphate activator, organic activators can inordinately excite the potential activity of the low hydration heat materials, and they has early strength acceleration to make cement stone acquire higher early strength. But they their hydration heat are so high not conducive to the stability of hydrate.
Deepwater low temperature causes the slow solidification of construction cement, and it can extend construction cycle of oil and gas well. In accordance with Mannich reaction principle, amine with Hydroxyl functional group has aminomethylation and generate the Mannich alkali accelerator DWGZ-1. The accelerator has a small dosage(0-0.05%), while the traditional accelerator is used between 1.0- 3.0% dosage; it has a strong accelerating effect for cement system of low hydration heat and makes cement slurry right-angle thickening(The traditional accelerator does not). DWGZ-1 has a small hydration heat impact on the cement slurry system. Therefore, DWGZ-1 has unparalleled advantages with similar accelerators, and it can better meet the requirements of deep water hydrate layer cementing.
Based on the principles which the inorganic salts with crystal water will absorb environmental heat when hydrate is losing its crystal water, with ethyl cellulose as the wall material and KAl(SO_4)_2·12H_O or CaSO_4·2H_2O as capsule-core, The use of microencapsulation technology has packaged the inorganic salts with crystal water, and successfully prepare the cement endothermic agent DWGCX of a low heat hydration. Absorption heat of the agent has a temperature selection, it can absorb heat of the Environment which the temperature is higher than 60℃. It will enable the slurry to maintain the temperature at around 60℃, without affecting the normal hydration of cement slurry, also avoiding the deep geothermal impact on the hydrate.
In connection with particularity of deepwater hydrate layer cementing and adaptability of low temperature and low hydration heat cement, matched additive system of low temperature and low hydration heat has been researched and developed. Under low temperature Filmformed fluid loss agent DWGJ-2 has good low temperature performance and reducing fluid loss performance, and it does not affect the thickening time of cement slurry. The latex micro- particles and film-forming properties of anti-gas channeling agent DWGJR make it have good anti-gas channeling performance. It can strengthen the reducing fluid loss performance of fluid loss agent, it can improve cement penetration, and it can improve the corrosion resistance of cement.
The low temperature and low hydration heat cement slurry system DWGC can better control exothermic hydration heat of the slurry, have good flow properties. Its thickening time can adjust according to cementing requirement. Its transition time of static gel strength is short and the probability of gas or water channeling occurrence will be decreased. Under the effects of the matched additives, cement strength and corrosion resistance got improved, it will help extend the life of oil wells. DWGC system can well adapt to the requirements of deep water hydrate layer cementing.
引文
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