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.     

二氧化碳水合物导热和热扩散特性

热导率和热扩散率是天然气水合物资源开采关键性基础热物性数据,采用反应釜内壁衬有氟塑料材料,低过冷度,让水合物在反应釜内逐层生成的合成方法,获得可直接用于导热测试的二氧化碳水合物样品。采用瞬变平面热源法原位测试了温度264.68～282.04 K、压力1.5～3 MPa二氧化碳水合物热导率、热扩散率,并测试了二氧化碳水合物在268.05 K、0.6 MPa左右发生自保护效应过程中热导率、热扩散率,获得了晶态下和自保护效应过程中的二氧化碳水合物热导率、热扩散率变化特性。测试结果将为天然气水合物资源的开发利用提供基础数据和理论依据。     

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.     

高黏原油和石英砂复配体系中水合物生成实验研究

在油井开采原油时,会产生伴生气,而在高压和低温环境中会生成天然气水合物,进而堵塞运输管道,因此研究油砂体系（含原油的体系）和纯石英砂体系（不含原油的体系）中水合物生成情况具有重要意义。在初始压力为4.00、6.00、8.00 MPa,石英砂粒径为20、30、60、80目,温度恒定的条件下,研究了油砂体系和纯石英砂体系中甲烷水合物的生成情况以及最终耗气量。结果表明,在初始压力相同的油砂体系中,石英砂粒径越小,水合物生成诱导期越短,水合物生成速率越大。研究石英砂粒径对水合物生成最终耗气量的影响发现,随着石英砂粒径的减小,耗气量先增加后减少,当石英砂粒径为60目时,耗气量达到最大,其值为0.19 mol。同时,对油砂体系和纯石英砂体系中水合物生成情况进行了对比。结果表明,由于两种体系中都存在SDS（十二烷基硫酸钠）溶液,因此水合物生成速率相差不大;在石英砂粒径相同的条件下,油砂体系中最终耗气量小于纯石英砂体系中的最终耗气量,这说明原油对水合物生成具有抑制作用。在油砂体系中,压力越大,越有利于水合物的生成。     

Improving the gas recovery and separation efficiency of a hydrate-based gas separation

Efficient gas recovery and separation in a hydrate-based system was investigated for a model gaseous mixture of R22 and nitrogen. The formed hydrate settled in the recovery vessel; excess water was recycled and the hydrate was subsequently decomposed by releasing pressure from the vessel. The gas uptake rate of R22 gas from the vapor phase and the gas recovery rate from the hydrate were determined from hydrate formation and decomposition, respectively. The gas recovery rate of R22 gas gradually increased with time. On the contrary, the nitrogen gas recovery rate was a maximum in the initial stage of hydrate decomposition. A high separation factor (S.F.) was achieved by first separating the N₂-rich gas generated during initial hydrate decomposition. An efficient hydrate-based gas separation and recovery process is proposed.     

水合三氯乙醛前体物的分子量分布和荧光特性

运用超滤分离技术将水合三氯乙醛前体物含量最高的夏季水样中溶解性有机物分为四个部分,采用三维激发发射矩阵荧光光谱对不同分子量有机物组分进行表征,并对20种氨基酸、牛血清白蛋白等模式化合物进行氯化试验,以找出水合三氯乙醛的主要前体物成分。结果表明MW＜1 kDa的水合三氯乙醛生成势含量最高,为24．81μg/L,其次为10 kDa＜MW＜0．45μm （17．49μg/L）、3 kDa＜MW＜10 kDa （8．16μg/L）和1 kDa＜MW＜3 kDa （5．50μg/L）,其中MW＜1 kDa和10 kDa＜MW＜0．45μm两部分有机物占水合三氯乙醛前体物含量的75．55％。三维激发发射矩阵荧光光谱结果表明水合三氯乙醛的主要前体物可能为类芳香性蛋白质和类微生物代谢产物等物质而非类富里酸和类腐殖酸。丙氨酸、天冬酰胺、天冬氨酸、半胱氨酸、组氨酸、苏氨酸、色氨酸、酪氨酸、牛血清白蛋白、鲱鱼精DNA等模式化合物是水合三氯乙醛主要前体物,其水合三氯乙醛生成量均大于30μg/mg C。     

多孔载体海绵对CH4-N2-O2瓦斯气体水合分离影响（英文）

The findings were presented from laboratory investigations on the hydrate formation and dissociation processes employed to recover methane from coal mine gas.The separation process of coal mine methane(CMM) was carried out at 273.15K under 4.00 MPa.The key process variables of gas formation rate,gas volume stored in hydrate and separation concentration were closely investigated in twelve THF-SDS-sponge-gas systems to verify the sponge effect in these hydrate-based separation processes.The gas volume stored in hydrate is calculated based on the measured gas pressure.The CH4 mole fraction in hydrate phase is measured by gas chromatography to confirm the separation efficiency.Through close examination of the overall results,it was clearly verified that sponges with volumes of 40,60 and 80 cm 3 significantly increase gas hydrate formation rate and the gas volume stored in hydrate,and have little effect on the CH4 mole fraction in hydrate phase.The present study provides references for the application of the kinetic effect of porous sponge media in hydrate-based technology.This will contribute to CMM utilization and to benefit for local and global environment.     

甲烷与冰快速形成天然气水合物的影响因素研究

设计了冰-气生成天然气水合物的实验装置,对由冰和甲烷反应生成天然气水合物的影响因素进行实验研究。结果表明,压力越高,温度越低,冰粒越小,越有利于水合物的生成,促进水合物快速形成的搅拌速度和促进剂浓度最佳值分别是800 r/min和800 mg/L。