Hybrid hydrate processes for CO2/H2 mixture purification: A techno-economic analysis

In this work, hydrate based separation technique was combined with membrane separation and amine-absorption separation technologies to design hybrid processes for separation of CO₂/H₂ mixture. Hybrid processes are designed in the presence of different types of hydrate promoters. The conceptual processes have been developed using Aspen HYSYS. Proposed processes were simulated at different flow rates for the feed stream. A comprehensive cost model was developed for economic analysis of novel processes proposed in this study. Based on the results from process simulation and equipment sizing, the amount of total energy consumption, fixed cost, variable cost, and total cost were calculated per unit weight of captured CO₂ for various flow rates of feed stream and in the presence of different hydrate promoters. Results showed that combination of hydrate formation separation technique with membrane separation technology results in a CO₂ capture process with lowest energy consumption and total cost per unit weight of captured CO₂. As split fraction and heat of hydrate formation increases, the share of hydrate formation section in total energy consumption increases. When TBAB is applied as hydrate promoter, due to its higher hydrate separation efficiency, more amount of CO₂ is captured in hydrate formation section and consequently the total cost for process decreases considerably. Hybrid hydrate-membrane process in the presence of TBAB as hydrate promoter with 29.47 US$/ton CO₂ total cost is the best scheme for hybrid hydrate CO₂ capture process. Total cost for this process is lower than total cost for single MDEA-based absorption process as the mature technology for CO₂ capture.     

A Finite Element Computational Method for Gas Hydrate. Part I: Theory

A finite element scheme is presented to model the dissociation of gas hydrates in porous media by hot water injection. We show a complete derivation of the finite element formulation, including the associated mass and energy conservation equations capable of performing transient analysis of both conductive and convective heat transfer for gas and liquid flow in porous media. The scheme also includes the latent heat effect to accommodate the change of phase due to melting of hydrate. In the companion paper, Part II, this method is successfully applied to hydrate reservoirs.     

Unusual kinetic inhibitor effects on gas hydrate formation

Gas hydrate formation experiments were conducted with a methane-ethane mixture at 273.7 or 273.9 K and 5100 kPa and using water droplets or water contained in cylindrical glass columns. The effect of kinetic inhibitors and the water/solid interface on the induction time for hydrate crystallization and on the hydrate growth and decomposition characteristics was studied. It was found that inhibitors GHI 101 and Luvicap EG delayed the onset of hydrate nucleation. While this inhibition effects has been reported previously some unusual behaviour was observed and reported for the first time. In particular, the water droplet containing GHI 101 or Luvicap EG was found to collapse prior to nucleation and spread out on the Teflon surface. Subsequently, hydrate was formed as a layer on the surface. Catastrophic growth and spreading of the hydrate crystals was also observed during hydrate formation in the glass columns in the presence of the kinetic inhibitor. Finally, when polyethylene oxide (PEO) was added into the kinetic inhibitor solution the memory effect on the induction time decreased dramatically.     

Kinetics of methane hydrate formation in aqueous electrolyte solutions

Experimental data on the kinetics of methane hydrate formation in aqueous electrolyte solutions are reported. The experiments were carried out in a semi-batch stirred tank reactor in three NaCl and two KCl solutions as well as in a solution containing a mixture of NaCl and KCl at three different nominal temperatures from 270 to 274 K and at pressures ranging from 3.78 to 7.08 MPa. The kinetic model developed by Englezos et al. (1987a) was adapted to predict the growth of hydrates. The model is based on the crystallisation theory coupled with the two-film theory for gas absorption in the liquid phase. The kinetic rate constant which appears in the model was that obtained earlier for methane hydrate formation in pure water. The effect of the electrolytes was taken into account through the computation of the three-phase equilibrium conditions and the corresponding fugacities. Overall, the model predictions match the experimental data very well with the largest prediction error being less than 10%.     

H_2-THF水合物形成过程研究

利用定容恒温法研究了H2-5.56 mol%THF-水在2℃,不同压力下的水合物形成特性,比较2种不同的氢气水合物形成方法:1)氢气-THF水溶液体系;2)氢气-THF水合物颗粒体系,考察形成过程,并计算储氢量。实验结果表明,在上述条件下,不同的方法氢气水合物的形成速率不同,第2种方法下氢气水合物的形成速率相对较快,且储氢量也高,约为质量分数0.33%,2种体系下的储氢量均随着压力的增高而增加。最后对2个体系下的氢气水合物的形成机理进行分析。     

深海甲烷激光拉曼光谱原位探测器的研究

为了对深海痕量甲烷进行原位实时检测,研制出一种甲烷激光拉曼光谱探测器。介绍了拉曼散射的量子机理和拉曼光谱的特性,对合成甲烷水体进行了拉曼光谱测试,确定了水中甲烷的拉曼振动光谱范围在2 904~2 917 cm-1之间,且水分子的振动谱峰与甲烷的振动谱峰不重叠。利用这一特点可以设计甲烷激光拉曼光谱探测器,能原位、快速地分析和检测出海水中痕量甲烷组分,并通过耐压光纤将检测数据进行实时的远程传输,具有高灵敏度,适应4 000m深海高压低温环境作业的特点。     

深海天然气及其水合物开发模式与钻采技术探讨

中国南海的石油天然气资源十分丰富,但其大多数都埋藏于深水区,油气勘探开发工作面临着许多难题和挑战。历经多年的探索与实践,我国海洋油气钻探工程已经实现了从浅水（水深300 m以内）到超深水（水深超过1 500 m）的跨越,并在南海发现了丰富的天然气与海域天然气水合物（以下简称水合物）资源,亟待进行安全高效开发,因而对相应的天然气及其水合物高效开发模式与技术支撑体系提出了迫切的需求。为此,针对深海天然气及其水合物安全高效开发的重大课题,提出了适用于常规天然气的“水平井或复杂结构井浮式钻完井+水下钻采系统+浮式生产、集输与浮式液化天然气生产储卸装置（FLNG）处理系统+船运外输”的开发模式及其技术支撑体系,以及适用于非常规天然气——海域天然气水合物的“水平井或复杂结构井浮式钻完井+水合物原位分解开采+水下或浮式生产与集输处理系统+管道或船运外输”的开发模式及其技术支撑体系;论述了大位移井、“U”形井等先进井型的开发模式及其适用的海洋地质环境,并给出了“U”形井的连通控制模型;此外,还介绍了与深水钻井力学和设计控制技术相关的研究进展。结论认为,建立先进适用的工程模式及其技术支撑体系,寻求实现“地质—工程—市场”一体化的解决方案,同时加强相关的信息化与智能化建设,是深海天然气及其水合物安全高效开发的关键之所在。     

溶剂结构对PVP分子链尺寸的影响

以H2O/THF/PVP体系为研究对象,采用稀溶液粘度法研究了PVP在混合溶剂中的粘度行为,为PVP在H2O/THF混合溶剂体系中尺寸增大提出了新的解释,分析了包合结构存在的可能性。     

Dielectric Properties of Na<Subscript>0.7</Subscript>CoO<Subscript>2</Subscript> and of the Superconducting Na<Subscript>0.3</Subscript>CoO<Subscript>2</Subscript>·1.3H<Subscript>2</Subscript>O

We present dielectric properties of ceramic anhydrous Na_0.7CoO₂ and the superconducting Na_0.3CoO₂·1.3H₂O materials. The presence of water which induces superconductivity also may increase the dielectric constant (ε) of the hydrated material. This is consistent with the predicted relationship between the highε and the enhancement ofT _c in highT _c superconductors. The anhydrous sample is porous and the transport is due to some percolation via the pores. The porosity is much higher for the hydrated material and the transport is ionic inside bulk water.     

Evaluation of natural gas hydrates as a future methane source

In recent years, attention has been given to obtaining methane gas from natural gas hydrates (NGHs) sediment; but its production, economics, and safety are still far away from being commercially viable for many years, and so more research is needed. NGHs are nonstoichiometric crystalline solid compounds that form from mixtures of water molecules and light weight natural gases such as methane, ethane, propane, and carbon dioxide. They are formed in specific thermodynamic conditions, low temperatures (5–15°C) and high pressures (2–3 MPa), and are found in (a) onshore polar regions beneath permafrost and (b) offshore deep-sea sediments. Methane, NG, is the cleanest fossil fuel and its huge amounts in NGHs have carbon quantities more than double of all fossil fuels. The methods that have been proposed for NG extraction from NGHs include: (a) depressurization, (b) thermal stimulation, and (c) chemical inhibitor injections. The authors review the potential of methane gas from NGHs as an unconventional source of future energy. The formation of NGHs as well as extraction of methane from NGHs coupled with technical and environmental challenges are also addressed.