Hydrogen wettability in carbonate reservoirs: Implication for underground hydrogen storage from geochemical perspective

Hydrogen has been considered as a promising renewable source to replace fossil fuels to meet energy demand and achieve net-zero carbon emission target. Underground hydrogen storage attracts more interest as it shows potential to store hydrogen at large-scale safely and economically. Meanwhile, wettability is one of the most important formation parameters which can affect hydrogen injection rate, reproduction efficiency and storage capacity. However, current knowledge is still very limited on how fluid-rock interactions affect formation wettability at in-situ conditions. In this study, we thus performed geochemical modelling to interpret our previous brine contact angle measurements of H₂-brine-calcite system. The calcite surface potential at various temperatures, pressures and salinities was calculated to predict disjoining pressure. Moreover, the surface species concentrations of calcite and organic stearic acid were estimated to characterize calcite-organic acid electrostatic attractions and thus hydrogen wettability. The results of the study showed that increasing temperature increases the disjoining pressure on calcite surface, which intensifies the repulsion force of H₂ against calcite and increases the hydrophilicity. Increasing salinity decreases the disjoining pressure, leading to more H₂-wet and contact angle increment. Besides, increasing stearic acid concentration remarkably strengthens the adhesion force between calcite and organic acid, which leads to more hydrophobic and H₂-wet. In general, the results from geochemical modelling are consistent with experimental observations that decreasing temperature and increasing salinity and organic acid concentration increase water contact angle. This work also demonstrates the importance of involving geochemical modelling on H₂ wettability assessment during underground hydrogen storage.     

Synthesis and Properties of New Cleavable Cationic Surfactants Containing Carbonate Groups

A novel series of cleavable alkyltrimethylammonium surfactants with different hydrocarbon chain lengths (C8–16) were synthesized. A carbonate break site inserted between the polar head and the hydrocarbon chain makes these compounds hydrolyzable. The reagents used are renewable, (bio)degradable, or reusable. The hydrolysis of these cleavable surfactants will lead to the generation of fatty alcohols and choline, which is an essential biological nutrient. The surface activities in aqueous solution of the synthesized carbonates fulfill the requirement of being good surfactants. In addition, the cleavable compounds containing n-decyl and n-dodecyl chains showed similar or higher antimicrobial activities when compared to a non-cleavable analog.     

Enhanced oil recovery from carbonate reservoirs by spontaneous imbibition of low salinity water

An experimental study was performed to investigate the impact of low salinity water on wettability alteration in carbonate core samples from southern Iranian reservoirs by spontaneous imbibition. In this paper, the effect of temperature, salinity, permeability and connate water were investigated by comparing the produced hydrocarbon curves. Contact angle measurements were taken to confirm the alteration of surface wettability of porous media. Oil recovery was enhanced by increasing the dilution ratio of sea water, and there existed an optimum dilution ratio at which the highest oil recovery was achieved. In addition, temperature had a very significant impact on oil recovery from carbonate rocks. Furthermore, oil recovery from a spontaneous imbibition process was directly proportional to the permeability of the core samples. The presence of connate water saturation inside the porous media facilitated oil production significantly. Also, the oil recovery from porous media was highly dependent on ion repulsion/attraction activity of the rock surface which directly impacts on the wettability conditions. Finally, the highest ion attraction percentage was measured for sodium while there was no significant change in pH for all experiments.     

Investigation of the ultimate particle size distribution of a carbonate sand

A series of ring shear tests were conducted to investigate the ultimate particle size distribution of a carbonate sand. The tests were carried out under different stress levels, on three types of specimens: 1) uniformly graded specimens made of dry natural sand 2) remoulded specimens of the crushed sand after first shearing to large strains 3) specimens made of natural sand grains but with the same grading as in (2). The first series of tests on type (1), carried out to very large strains, led to apparently stable gradings, distinct for each stress level. Only limited additional particle breakage could be induced by remoulding the specimens after shearing (type (2)) and subjecting them to more shearing. Tests on specimens created at the apparently stable gradings (type (3)) but from the intact sand particles however led to significantly greater breakage. For the three types a stable, fractal grading was achieved. Analyses of the soil particles’ shape showed that the aspect ratio, sphericity and circularity reach a steady value at large strains, in parallel to reaching a stable grading. The mobilized angle of shearing resistance however was not significantly different in the different types of samples, suggesting the final grading dominates the behaviour.     

流量替代渗透率评价破碎性储层工作流体伤害程度

若地层岩石整体强度偏低,在力学环境改变后岩石易破碎成不规则破裂体,则储存油气资源的此类破碎地层被称为破碎性储层。由于破碎性储层在纵向上存在着较强的非均质性,通过测试单个柱塞岩样在工作流体伤害前后的渗透率变化难以体现工作流体对储层的整体伤害程度。为此,利用达西定律先从理论上探讨用流量替代渗透率定量表征储层伤害程度的可行性,再开展单层开采、双层及三层并采的流量测试实验,评价工作流体对单层、多层储层的整体伤害程度,并将流量损害率与渗透率损害率进行对比以求证流量替代渗透率的可行性。研究结果表明:①单层开采时,流量损害率与渗透率损害率基本一致,渗透率损害率是流量损害率的一种特殊形式;②双层及三层并采时,单层各自稳定流量损害率与渗透率损害率接近,且流量损害率可以定量表征并采储层的整体伤害程度,而渗透率损害率则无法定量表证;③稳定流量损害率较累积流量损害率更接近渗透率损害率。结论认为,测定稳定流量可以替代测定渗透率评价工作流体对破碎性储层的伤害程度,从而为优选工程技术与评价工作流体的适应性提供了方法依据。     

PLA-g-GMA的制备及其对PLA/PPC共混体系性能的影响

采用双螺杆挤出机将甲基丙烯酸缩水甘油酯(GMA)接枝到聚乳酸(PLA)上,而后将接枝产物(PLA-g-GMA)与聚乳酸(PLA)、聚碳酸亚丙酯(PPC)反应性共混,考察了接枝物中GMA加入量变化对PLA/PPC/PLA-g-GMA共混体系的力学性能、热稳定性能的影响,并对共混体系的断裂机理进行了研究。结果表明,PLA-g-GMA的引入能够在一定程度上改善PLA与PPC的相容性。随着接枝物中GMA加入量的增加,共混物的冲击强度、断裂伸长率及拉伸强度均呈现出先升高后降低的趋势,并在接枝物中GMA加入量为3%时达到最大值。扫描电镜结果显示,PLA-g-GMA引入后共混物的韧性断裂特征越发显著,其冲击断裂方式由脆性断裂过渡为韧性断裂。热失重分析结果显示,加入PLA-g-GMA后共混物的起始分解温度和完全分解温度均有一定程度的提高。     

Performance of LiNi1/3Co1/3Mn1/3O2 prepared from spent lithium-ion batteries by a carbonate co-precipitation method

Spherical LiNi_1/3Co_1/3Mn_1/3O₂ cathode particles were resynthesized by a carbonate co-precipitation method using spent lithium-ion batteries (LIBs) as a raw material. The physical characteristics of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, the (Ni_1/3Co_1/3Mn_1/3)₃O₄ intermediate, and the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material were investigated by laser particle-size analysis, scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), thermogravimetry–differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), inductively coupled plasma–atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ was studied by continuous charge–discharge cycling and cyclic voltammetry. The results indicate that the regenerated Ni_1/3Co_1/3Mn_1/3CO₃ precursor comprises uniform spherical particles with a narrow particle-size distribution. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ comprises spherical particles similar to those of the Ni_1/3Co_1/3Mn_1/3CO₃ precursor, but with a narrower particle-size distribution. Moreover, it has a well-ordered layered structure and a low degree of cation mixing. The regenerated LiNi_1/3Co_1/3Mn_1/3O₂ shows an initial discharge capacity of 163.5 mA h g^?1 at 0.1 C, between 2.7 and 4.3 V; the discharge capacity at 1 C is 135.1 mA h g^?1, and the capacity retention ratio is 94.1% after 50 cycles. Even at the high rate of 5 C, LiNi_1/3Co_1/3Mn_1/3O₂ delivers the high capacity of 112.6 mA h g^?1. These results demonstrate that the electrochemical performance of the regenerated LiNi_1/3Co_1/3Mn_1/3O₂ is comparable to that of a cathode synthesized from fresh materials by carbonate co-precipitation.     

碳羟磷灰石对废水中铅离子吸附研究

利用废弃蛋壳制备碳羟磷灰石（简称CHAP），并用作去除废水中Pb^2＋的吸附剂。考查了pH值、吸附时间、温度、吸附剂用量以及Pb^2＋初始浓度等因素对吸附效果的影响。结果表明：0．6g／L的CHAP对750mg／L的Pb^2＋的去除率高达99．9％，吸附容量达到1243．75mg／g。CHAP对Pb^2＋吸附的吸附等温线均符合Freundlich和Langmuir两种模式，从Freundlich方程中的常数1／n=0．0184可知，该吸附反应为吸热自发反应，且反应速率快。     

湖北双河硒矿地质特征及成因浅析

本文介绍了双河硒矿地质特征、分布规律;阐述了成矿与碳酸盐台地海盆浅部沼泽(主要为藻沼)环境中局部出现的黑色炭质硅质岩相有关;矿质来源与火山活动有关;探讨了成矿机制;提出了该硒矿属于沉积-成岩-表生层控成因。     

碳酸镧直接电解制备金属镧试验工艺研究

本试验重点研究了碳酸镧电解制取金属镧的工艺条件。通过将碳酸镧直接加入电解炉后,研究熔盐组成、电解温度、原料钐质量对电效的影响因素及碳酸镧回收利用对产品质量的影响。