Clay peptization and clay swelling inhibition in the presence of carbonic acid, bicarbonate and carbonate ions and calcium ions

Dmitriy A. Baranov, Sergey F. Vyaznikovtsev, Oksana G. Mamaeva
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Abstract

Relevance. The need to ensure the integrity of the wellbore, composed of clay rocks, and the stability of drilling fluid when drilling in conditions of carbon dioxide and bicarbonate aggression. Aim. To determine experimentally the effect of carbonic acid, bicarbonate and carbonate ions on clay depending on the presence of calcium ions in the dispersion medium. Objects. Water contaminated with carbonic acid, bicarbonate and carbonate ions with different equivalent concentrations of calcium ions. Methods. Inhibitory and peptizing properties of the objects of study in relation to the clay rock were studied by the method of clay swelling when it was in the water under study (on the Zhigacha-Yarov device); methods of chemical analysis (complexometric and acid-base titration) and potentiometry were used to control water composition and properties. Results. The peptizing and inhibiting properties of drilling fluid depend significantly on the form of carbonic acid present in the dispersion medium and the equivalent content of calcium ions (Ca2+). It was found that carbonic acid (H2CO3) contributes to clay inhibition (coagulation), bicarbonate ions (HCO3–) and carbonate ions (CO32–) – clay peptization. Calcium ions (Ca2+) do not have an inhibitory effect in the presence of carbonic acid (H2CO3) – hydrogen ions (H+) displace exchangeable cations from the interlayer space of clays and, due to their small diameter, independently inhibit clay swelling. In the presence of bicarbonate ions (HCO3–), calcium ions (Ca2+) also do not have an inhibitory effect – bicarbonate ions (HCO3–), being in a dispersion medium, draw calcium ions (Ca2+) from the clay surface, increasing the thickness of the electrical double layer. In the presence of carbonate ions (CO32–) the calcium ions (Ca2+) precipitate and effectively prevent clay peptization only in the presence of hydroxide ions (OH–). The authors proved experimentally that calcium ions (Ca2+) in the presence of hydroxide ions (OH–) have a better inhibitory ability than hydrogen ions (H+) of dissociated carbonic acid (H2CO3). A mechanism was proposed for inhibiting the swelling of clays by calcium ions (Ca2+) in the presence of hydroxide ions (OH-), based on the adsorption of the hydrated calcium ion (Ca2+) on a silica tetrahedral sheet due to the preliminary protonation of its oxygen atoms by water molecules. The conditions required for clay effective peptization are formulated: [CO32–]≥0; [OH–]>0, [Ca2+]=0, pH>11.5; for clay swelling inhibition: [CO32–]=0; [OH–]>0, [Ca2+]>0 and pH>11.5.
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碳酸、碳酸氢根、碳酸根离子和钙离子存在下的粘土胨化和粘土膨胀抑制作用
相关性。在二氧化碳和碳酸氢盐侵蚀条件下钻井时,需要确保由粘土岩组成的井筒的完整性和钻井液的稳定性。目的。通过实验确定碳酸、碳酸氢盐和碳酸根离子对粘土的影响,这取决于分散介质中是否存在钙离子。对象。被碳酸、碳酸氢根和碳酸根离子污染的水,其中钙离子的浓度不同。方法。通过粘土在所研究的水中膨胀的方法(Zhigacha-Yarov 装置),研究了研究对象与粘土岩的抑制和抑制特性;使用化学分析方法(络合滴定法和酸碱滴定法)和电位测定法来控制水的成分和特性。研究结果钻井液的酸化和抑制特性在很大程度上取决于分散介质中碳酸的形式和钙离子 (Ca2+) 的当量含量。研究发现,碳酸(H2CO3)对粘土有抑制(凝结)作用,碳酸氢根离子(HCO3-)和碳酸根离子(CO32-)对粘土有抑制作用。钙离子(Ca2+)在碳酸(H2CO3)存在的情况下没有抑制作用--氢离子(H+)从粘土的层间空间置换出可交换阳离子,由于其直径较小,可单独抑制粘土膨胀。在存在碳酸氢根离子 (HCO3-) 的情况下,钙离子 (Ca2+) 也不会产生抑制作用,因为碳酸氢根离子 (HCO3-) 处于分散介质中,会从粘土表面吸引钙离子 (Ca2+),从而增加电双层的厚度。在碳酸根离子(CO32-)存在的情况下,钙离子(Ca2+)沉淀,只有在氢氧根离子(OH-)存在的情况下才能有效防止粘土胨化。作者通过实验证明,存在氢氧根离子(OH-)的钙离子(Ca2+)比离解碳酸根离子(H2CO3)的氢离子(H+)具有更好的抑制能力。根据水合钙离子(Ca2+)由于其氧原子被水分子初步质子化而吸附在二氧化硅四面体薄片上,提出了钙离子(Ca2+)在氢氧根离子(OH-)存在下抑制粘土膨胀的机理。提出了粘土有效胨化所需的条件:[CO32-]≥0;[OH-]>0,[Ca2+]=0,pH>11.5;抑制粘土膨胀的条件:[CO32-]=0;[OH-]>0,[Ca2+]>0,pH>11.5。
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