A solid-state NMR and X-ray powder diffraction investigation of the binding mechanism for self-healing cementitious materials design: The assessment of the reactivity of sodium silicate based systems

The identification of affordable healing agents for cement based materials, able to promote autonomous crack healing, is a challenge to improve the durability of building structures. In this study, a thorough investigation of the reactivity between a hydrated Portland cement and sodium silicate solutions, as healing agents, has been carried out.The goal is to quantitatively assess the chemical reactivity and actual binding capacity of sodium silicate. Mechanical recovery was evaluated by means of a healing agent strength test on hydrated cement treated with sodium silicate. XRPD and Solid-state NMR allowed the definition of reaction times, the involved species, and the nature and stability of the reaction products. Highlights show that sodium silicate reacts not only with Ca(OH)₂ (namely portlandite), but also with calcium aluminate phases (AFt, AFm, TAH) to extract calcium and/or aluminum ions, with the formation of crystalline/semi-crystalline C-S-H/C-A-S-H tobermorite phase.     

The downhole hydrocyclone separator for purifying natural gas hydrate:structure design,optimization, and performance

ABSTRACT

The exploitation efficiency of natural gas hydrate is highly affected by sand production. In this paper, hydrocyclone purification separator was designed. A combination of single factor with computational fluid dynamics (CFD) was used to optimize the structure parameters. The performance of optimized hydrocyclone was also investigated. It shows that the sand separation efficiency increases from 90.4% to 98.7%, and the natural gas hydrate separation efficiency increases from 89.5% to 97.8%. Furthermore, the cut size of sand and natural gas hydrate are as low as 3 and 2 µm, respectively, and separation efficiency remains above 80% under inlet parameters. It can provide some reference for the design and manufacture of the in situ purification separator for gas hydrate mixture slurry.     

CO2 sequestration in depleted methane hydrate deposits with excess water

The recent increase in atmospheric CO₂ concentration makes it necessary to investigate new ways to reduce CO₂ emissions. Simultaneously, natural gas hydrate mining technology is developing rapidly. The use of depleted methane hydrate (MH) deposits as potential sites for CO₂ storage is relatively safe and economical. This method can alleviate the shortage of hydrate displacement gas with CO₂. The purpose of this study was to investigate CO₂ hydrate formation characteristics during the seepage process—in reservoirs with excess water—and their effect on CO₂ storage. The experimental process can be divided into 5 parts: MH formation, water injection, MH dissociation, CO₂ hydrate formation, and CO₂ hydrate dissociation. Magnetic resonance imaging was employed to monitor the distribution of liquid water, and the effects of different parameters on the formation and dissociation of CO₂ hydrates were analyzed. It was found that a state of initial water saturation can effectively control hydrate saturation in artificial MH reservoirs for hydrate reservoirs with excess gas. In the process of CO₂ flow, initial water saturation was not the main controlling factor for CO₂ hydrate formation. Increasing the flow pressure and reducing the flow rate were beneficial for CO₂ hydrate formation. This study is of great significance for advancing the science of CO₂ geological storage in the form of deep‐sea hydrates.     

加氢裂化装置脱乙烷塔顶气水合物生成条件研究

加氢裂化装置脱乙烷塔顶回流管道在寒冷的冬季容易出现堵塞现象,发现该堵塞物为气体水合物.管道中一旦生成水合物,会减小流通面积,产生节流进而造成阀门、一些设备以及管道堵塞,严重影响管道的安全运行.采用Chen-Guo水合物理论模型对某厂加氢裂化装置脱乙烷塔顶气生成水合物的条件进行了计算,结果表明,根据该气体组成,在脱乙烷塔操作压力3.05 MPa下,操作温度低于37℃即可生成水合物.分析了多种抑制水合物堵塞管道的方法,指出添加水合物抑制剂的方法可行,但还需要考察添加水合物抑制剂对液化石油气产品质量的影响.     

Reactive molecular simulation on the ordered crystal and disordered glass of the calcium silicate hydrate gel

Modifying the properties of modern concrete highlights the decoding the molecular structure of C–S–H gel, which is the main binding phase in the cementitious materials. In this paper, the structural, dynamical and mechanical properties were investigated by using C–S–H glassy model and its crystal analog tobermorite 11 Å to represent the disordered and ordered molecular structure. By using reactive force field molecular simulation, the structural discrepancy for ordered and disordered phase was illustrated in respect of silicate chain skeletons, local structure of the calcium oxygen octahedrons and hydroxyl distribution. In the glassy model, the local structure of C–S–H gel, with defective silicate chains and distorted calcium sheet, is similar to the silicate glass phase of metallic ions. Furthermore, to predict the mechanical properties of the C–S–H gel and tobermorite, uniaxial tension testing by the reactive force field coupled with both the mechanical response and chemical response during the large tensile deformation process. During the tensile process, water molecules, attacking the Si–O and Ca–O bond, are detrimental to the cohesive force development in the C–S–H gel.     

促进天然气水合物形成的影响因素分析

天然气水合物(NGH)工业化生产中面临的主要问题是天然气水合物的合成速率较低。天然气水合物的生成反应为相间界面反应,任何影响气液相之间传质或传热的操作均可以增加天然气水合物的生成速率。结合影响天然气水合物形成的特点,从改善相平衡条件、增加气水接触面积和增加天然气的溶解度三方面介绍了促进天然气水合物形成的办法,并分析了各自的优缺点。     

乳化沥青对水化硅酸钙孔结构及微观形貌的影响

针对未掺乳化沥青的纯水化硅酸钙和用Na_2SiO_3·9H_2O,Ca(NO_3)_2·4H_2O,NaOH,去离子水及阴离子乳化沥青合成的水化硅酸钙,采用氮吸附-脱附试验、X射线衍射(XRD)和扫描电镜(SEM)等测试方法对比研究了乳化沥青对水化硅酸钙孔结构及微观形貌的影响,并运用FHH模型分析了其表面分形特征.结果表明:纯水化硅酸钙和掺杂乳化沥青的水化硅酸钙比表面积相差较小,且微孔分布几乎一致,说明掺杂乳化沥青后插层作用和"开孔"效应并未发生;乳化沥青可促进水化硅酸钙形成孔径较大的中孔,减少孔径较小的中孔,而对大孔及微孔的孔结构几乎没有影响;纯水化硅酸钙和掺杂乳化沥青的水化硅酸钙表面分形特征存在差异;沥青表面乳化剂中的—COOM基团与Ca键合可使水化硅酸钙胶束包裹在乳化沥青颗粒表面.     

Deep ocean bubble transport model coupled with multiple hydrate behavior characteristics

Submarine gas seepage is a widely observed process. In this study, a unified mechanistic model of bubble transport both inside and outside the gas hydrate stability zone (GHSZ) was developed. Multiple hydrate-related behaviors were considered, including hydrate nucleation, hydrate film lateral spread, hydrate shell dynamic growth, hydrate dissolution and decomposition, and collapse and fracture deformation of hydrate-coated bubbles. Using the proposed model, a series of simulation studies about bubble dissolution and rising fate were conducted. The results indicate that the formation of solid hydrates in the deep-sea environment can provide a fairly effective barrier for the dissolution and shrinkage of bubbles, and the deeper the initial release water depth, the smaller the critical size of the bubble required for arriving at the water surface. Furthermore, the majority of gases released from the seafloor would be absorbed by the shallow oceanic layer, but larger bubbles could still pass through the water column to the atmosphere.     

Effect of surface curvature and wettability on nucleation of methane hydrate

Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.     

不同季铵盐作用下的CO2水合物相平衡

CO₂气体水合物形成热力学性质是实施海水淡化、沼气纯化、碳捕集和封存、能源利用、天然气储存等技术的关键。采用恒容温度搜索法,在温度272.75~294.35 K,压力0.35~4.50 MPa的范围内,探究了四种季铵盐促进剂对CO₂气体水合物相平衡的影响。结果表明,相同条件下,季铵盐作用下CO₂水合物的相平衡温度由高到低分别为：四丁基氟化铵（TBAF）>四丁基溴化铵（TBAB）>四丁基氯化铵（TBAC）>苄基三乙基氯化铵（TEBAC）。基于Clausius-Clapeyron方程,计算了不同体系的相变潜热,探讨了其对水合物稳定性的影响。可以看出,水合物的相平衡压力对数与温度倒数呈线性关系,其中,TBAF、TBAB作用下的CO₂水合物相变潜热相接近且明显高于其他季铵盐,说明其促进效果最好,所对应的水合物生成条件也最为温和。利用Chen-Guo模型,结合PR状态方程和改进Joshi经验活度模型,分别计算了TBAF、TBAB、TBAC和TEBAC作用下CO₂水合物热力学相平衡数据,计算结果与实验数据吻合良好,最大平均相对误差为7.50%。