Tetrahydrofuran hydrate decomposition characteristics in porous media

Many tetrahydrofuran (THF) hydrate properties are similar to those of gas hydrates. In the present work THF hydrate dissociation in four types of porous media is studied. THF solution was cooled to 275.15 K with formation of the hydrate under ambient pressure, and then it dissociated under ambient conditions. THF hydrate dissociation experiments in each porous medium were conducted three times. Magnetic resonance imaging (MRI) was used to obtain images. Decomposition time, THF hydrate saturation and MRI mean intensity (MI) were measured and analyzed. The experimental results showed that the hydrate decomposition time in BZ-4 and BZ-3 was similar and longer than that in BZ-02. In each dissociation process, the hydrate decomposition time of the second and third cycles was shorter than that of the first cycle in BZ-4, BZ-3, and BZ-02. The relationship between THF hydrate saturation and time is almost linear.     

Methane hydrate dissociation above 0 °C and below 0 °C

The kinetic data of methane hydrate dissociation at various temperatures and pressures were measured in a sapphire cell apparatus by depressurizing method. When the temperature was higher than 0 °C, the experimental results showed that the hydrate dissociation rate was controlled by intrinsic dissociation reaction. When the temperature was lower than 0 °C, water generated from the hydrate dissociation would transform into ice rapidly at the surface of hydrate crystal. The released gas diffused from the hydrate and ice mixture to the bulk of gas phase. With the hydrate continuous dissociation, the boundary of ice–hydrate moved toward water/ice phase. The hydrate dissociation was controlled by gas diffusion, and the hydrate dissociation process was treated as a moving boundary problem. Corresponding kinetic models for hydrate dissociation were established and good agreements with experimental data were achieved.     

Formation process and fractal growth model of HCFC-141b refrigerant gas hydrate

The microscopic visualization experiment on the formation process of HCFC-141b refrigerant gas hydrate has been investigated, and the morphological photos of hydrate formation process have been obtained. The results show that gas hydrate originally nucleated on the interface of refrigerant HCFC-141b and water under the condition of supercooling, then the hydrate grows continually due to the inducement of formed nucleation and diffusion of refrigerant. The formation of gas hydrate presents an arboreous phenomenon. The fractal dimension of the hydrate formation morphology on different stages was calculated. The calculating results indicate that the initial stage of the hydrate formation belongs to fractal growth, and the dimension is about 1.52. Based on the fractal theory, an RIN-DLA (random inducement nucleation-diffusion limited aggregation) model for the HCFC-141b hydrate growth was developed. The hydrate growth process was simulated with the developed model, and the fractal dimension for the simulated     

Natural gas hydrate shell model in gas-slurry pipeline flow

A hydrate shell model coupled with one-dimensional two-fluid pipe flow model was established to study the flow characteristics of gas-hydrate slurry flow system. The hydrate shell model was developed with kinetic limitations and mass transfer limitations, and it was solved by Euler method. The analysis of influence factors was performed. It was found that the diffusion coefficient was a key parameter in hydrate forming process. Considering the hydrate kinetics model and the contacting area between gas and water, the hydrate shell model was more close to its practical situations.     

Experimental and modeling study on hydrate formation in wet activated carbon

The formation of methane hydrate in wet activated carbon was studied. The experimental results demonstrated that the formation of methane hydrate could be enhanced by immersing activated carbon in water. A maximum actual storage capacity of 212 standard volumes of gas per volume of water was achieved. The apparent storage capacity of the activated carbon + hydrate bed increased with the increasing of mass ratio of water to carbon until reaching a maximum, then decreased drastically as the bulk water phase emerged above the wet carbon bed. The highest apparent storage capacity achieved was 140 v/v. A hydrate formation mechanism in the wet activated carbon was proposed and a mathematical model was developed. It has been shown that the proposed model is adequate for describing the hydrate formation kinetics in wet activated carbon. The kinetic model and the measured kinetic data were used to determine the formation conditions of methane hydrate in wet carbon, which are in good agreement with literature values and demonstrate that hydrate formation in wet carbon requires lower temperature or higher pressure than in the free water system.     

Promoting effect of super absorbent polymer on hydrate formation

The effect of super absorbent polymer (SAP) on the formation of tetrahydrofuran (THF) hydrate was studied by the successional cooling method. It was found that THF solution samples with 0.004 wt% and 0.03 wt% of SAP formed THF hydrate completely during the same cooling process. The corresponding induction time was 16-29 min, 14-31 min, respectively, which was obviously shorter than that of THF solution samples without SAP (25-62 min). It indicated that SAP accelerated the formation of THF hydrate. At the same time, the pictures of hydrate formation with and without SAP had been compared. It was found that SAP did not change the morphology of the hydrate. Finally, the mechanism of SAP promoting effect on the formation of THF hydrate was suggested.     

Experimental investigation of methane hydrate decomposition by depressurizing in porous media with 3-Dimension device

In order to simulate the behavior of gas hydrate formation and decomposition, a 3-Dimension experimental device was built, consisting of a high-pressure reactor with an inner diameter of 300 mm, effective height of 100 mm, and operation pressure of 16 MPa. Eight thermal resistances were mounted in the porous media at different depthes and radiuses to detect the temperature distribution during the hydrate formation/decomposition. To collect the pressure, temperature, and flux of gas production data, the Monitor and Control Generated System (MCGS) was used. Using this device, the formation and decomposition behavior of methane hydrate in the 20～40 mesh natural sand with salinity of 3.35 wt% was examined. It was found that the front of formation or decomposition of hydrate can be judged by the temperature distribution. The amount of hydrate formation can also be evaluated by the temperature change. During the hydrate decomposition process, the temperature curves indicated that the hydrate in the top and bottom of reactor dissociated earlier than in the inner. The hydrate decomposition front gradually moved from porous media surface to inner and kept a shape of column form, with different moving speed at different surface position. The proper decomposition pressure was also determined.     

Stabilization of methane hydrate by pressurization with He or N2 gas

The behavior of methane hydrate was investigated after it was pressurized with helium or nitrogen gas in a test system by monitoring the gas compositions. The results obtained indicate that even when the partial pressure of methane gas in such a system is lower than the equilibrium pressure at a certain temperature, the dissociation rate of methane hydrate is greatly depressed by pressurization with helium or nitrogen gas. This phenomenon is only observed when the total pressure of methane and helium (or nitrogen) gas in the system is greater than the equilibrium pressure required to stabilize methane hydrate with just methane gas. The following model has been proposed to explain the observed phenomenon: (1) Gas bubbles develop at the hydrate surface during hydrate dissociation, and there is a pressure balance between the methane gas inside the gas bubbles and the external pressurizing gas (methane and helium or nitrogen), as transmitted through the water film; as a result the methane gas in the gas bubbles stabilizes the hydrate surface covered with bubbles when the total gas pressure is greater than the equilibrium pressure of the methane hydrate at that temperature; this situation persists until the gas in the bubbles becomes sufficiently dilute in methane or until the surface becomes bubble-free. (2) In case of direct contact of methane hydrate with water, the water surrounding the hydrate is supersaturated with methane released upon hydrate dissociation; consequently, methane hydrate is stabilized when the hydrostatic pressure is above the equilibrium pressure of methane hydrate at a certain temperature, again until the dissolved gas at the surface becomes sufficiently dilute in methane. In essence, the phenomenon is due to the presence of a nonequilibrium state where there is a chemical potential gradient from the solid hydrate particles to the bulk solution that exists as long as solid hydrate remains.     

Fractal-like Kinetic Characteristics of Coalbed Methane Hydrate Dissociation at Normal Pressure

Surface modality of coalbed methane hydrate and fractal‐like kinetic characteristics of the hydrate dissociation at normal pressure have been studied by using fractal geometry theory. The results show that the surface modality of coalbed methane hydrate has fractal characteristic, and the dissociation kinetics of coalbed methane hydrate is fractal‐like. Moreover, a new kinetic model for coalbed methane hydrate dissociation was proposed, and its reliability was validated.     

CO2 capture from binary mixture via forming hydrate with the help of tetra-n-butyl ammonium bromide

Hydrate formation rate and separation effect on the capture of CO2 from binary mixture v/a forming hydrate with 5 wt% tetra-n-butyl ammonium bromide (TBAB) solution were studied.The results showed that the induction time was 5 min,and the hydrate formation process pressure of 7.30 MPa.The CO2 recovery was about 45% in the feed pressure range from 4.30 to 7.30 MPa.Under the feed pressure of 4.30 MPa,the maximum separation factor and CO2 concentration in hydrate phase were 7.3 and 38.2 tool%,respectively.The results demonstrated that TBAB accelerated hydrate formation and enriched CO2 in hydrate phase under the gentle condition.     

Characterization of non-stoichiometric hydration and the dehydration behavior of sitafloxacin hydrate

Sitafloxacin (STFX) hydrate is a non-stoichiometric hydrate. The hydration state of STFX hydrate varies non-stoichiometrically depending on the relative humidity and temperature, though X-ray powder diffraction (XRPD) of STFX hydrate was not affected by storing at low and high relative humidities. The detailed properties of crystalline water of STFX hydrate were estimated in terms of hygroscopicity, thermal analysis combined with X-ray powder diffractometry, crystallography and density functional theory (DFT) calculation. STFX hydrate changed the water contents continuously and reversibly from an equivalent amount of dihydrate through that of sesquihydrate depending on the relative humidity at 25°C. Thermal analysis and X-ray powder diffraction (XRPD) simultaneous measurement also revealed that STFX hydrate dehydrated into a hydrated state equivalent to monohydrate by heating up to 100°C, whereas XRPD patterns were slightly affected. This indicated that the crystal structure of STFX hydrate was retained at the dehydration level of monohydrate. Single-crystal X-ray structural analysis showed that two STFX molecules and four water molecule sites were contained in an asymmetric unit. STFX molecules formed a channel structure where water molecules were included. At the partially dehydrated state, at least two of four water molecules were considered to be disordered in occupancy and/or coordinates. Insight into the crystal structure of STFX hydrate stored at low and high relative humidities and geometry of the hydrogen bond were helpful to estimate the origin of non-stoichiometric hydration of STFX hydrate.     

Pressurized laboratory experiments show no stable carbon isotope fractionation of methane during gas hydrate dissolution and dissociation

The stable carbon isotopic ratio of methane (δ(13)C-CH(4)) recovered from marine sediments containing gas hydrate is often used to infer the gas source and associated microbial processes. This is a powerful approach because of distinct isotopic fractionation patterns associated with methane production by biogenic and thermogenic pathways and microbial oxidation. However, isotope fractionations due to physical processes, such as hydrate dissolution, have not been fully evaluated. We have conducted experiments to determine if hydrate dissolution or dissociation (two distinct physical processes) results in isotopic fractionation. In a pressure chamber, hydrate was formed from a methane gas source at 2.5 MPa and 4 °C, well within the hydrate stability field. Following formation, the methane source was removed while maintaining the hydrate at the same pressure and temperature which stimulated hydrate dissolution. Over the duration of two dissolution experiments (each ~20-30 days), water and headspace samples were periodically collected and measured for methane concentrations and δ(13)C-CH(4) while the hydrate dissolved. For both experiments, the methane concentrations in the pressure chamber water and headspace increased over time, indicating that the hydrate was dissolving, but the δ(13)C-CH(4) values showed no significant trend and remained constant, within 0.5‰. This lack of isotope change over time indicates that there is no fractionation during hydrate dissolution. We also investigated previous findings that little isotopic fractionation occurs when the gas hydrate dissociates into gas bubbles and water due to the release of pressure. Over a 2.5 MPa pressure drop, the difference in the δ(13)C-CH(4) was <0.3‰. We have therefore confirmed that there is no isotope fractionation when the gas hydrate dissociates and demonstrated that there is no fractionation when the hydrate dissolves. Therefore, measured δ(13)C-CH(4) values near gas hydrates are not affected by physical processes, and can thus be interpreted to result from either the gas source or associated microbial processes.     

Time-resolved in situ neutron diffraction studies of gas hydrate: transformation of structure II (sII) to structure I (sI).

We report the in situ observation from diffraction data of the conversion of a gas hydrate with the structure II (sII) lattice to one with the structure I (sI) lattice. Initially, the in situ formation, dissociation, and reactivity of argon gas clathrate hydrate was investigated by time-of-flight neutron powder diffraction at temperatures ranging from 230 to 263 K and pressures up to 5000 psi (34.5 MPa). These samples were prepared from deuterated ice crystals and transformed to hydrate by pressurizing the system with argon gas. Complete transformation from D(2)O ice to sII Ar hydrate was observed as the sample temperature was slowly increased through the D(2)O ice melting point. The transformation of sII argon hydrate to sI hydrate was achieved by removing excess Ar gas and exposing the hydrate to liquid CO(2) by pressurizing the Ar hydrate with CO(2). Results suggest the sI hydrate formed from CO(2) exchange in argon sII hydrate is a mixed Ar/CO(2) hydrate. The proposed exchange mechanism is consistent with clathrate hydrate being an equilibrium system in which guest molecules are exchanging between encapsulated molecules in the solid hydrate and free molecules in the surrounding gas or liquid phase.     

热力学抑制剂作用下甲烷水合物分解过程的分子动力学模拟

采用正则系综(NVT)分子动力学方法模拟研究277.0 K、11.45 mol·L-1的热力学抑制剂乙二醇(EG)溶液作用下甲烷水合物分解微观过程. 模拟显示甲烷水合物的分解从甲烷水合物固体表面开始, 逐渐向内部推移, 固态水合物在分解过程中逐渐缩小, 直至消失. 固态水合物的分解从晶格扭曲变形开始, 之后笼形框架结构破裂, 最后形成笼形结构碎片. 同时已经分解的甲烷水合物在外层形成水膜, 包裹里层正在分解的甲烷水合物, 增大里层甲烷水合物分解传质阻力.     

用分子动力学模拟天然气水合物的抑制效应

用分子动力学模拟方法确定了结构H型(SH)天然气水合物的稳定晶体生长面为(001), 系统研究了277 K时三种动力学抑制剂对此晶面的影响. 模拟显示抑制剂中的氧与表面水分子形成氢键, 从而破坏原有的稳定结构, 造成水合物笼型结构坍塌, 达到抑制水合物形成的效果. 比较三种不同动力学抑制剂对SH的抑制效果得出: PVCap＞PEO＞PVP. 在此基础上研究了PVCap对天然气水合物结构I型(SI), 结构II型(SII)和SH三种不同晶型的抑制效应. 模拟发现抑制效果的次序为: SH＞SI＞SII.     

天然气水合物浆体分解对其在垂直管中流动特性影响的研究

针对天然气水合物浆体开采提升过程中水合物分解的问题,采用Euler多相流模型以及Finite-Rate/Eddy-Dissipation模型对天然气水合物浆体垂直管输的固-液两相流动以及气-液-固三相流流动特性进行研究。结果表明,受天然气水合物分解产生的气体影响,天然气水合物颗粒的速度分布、体积浓度分布均随高度的变化呈现出波动-均匀-波动的规律;水合物分解对浆体管道运输具有减阻作用,并提出天然气水合物浆体分解工况下,其流动速度不应低于3m·s~(-1);通过对管道的阻力特性分析,拟合出水合物分解下的水力提升阻力损失与流速的关系式,为天然气水合物浆体管道的经济提升参数提供指导。     

Effect of temperature and pressure on the solubility of carbon dioxide in water in the presence of gas hydrate

The solubility of carbon dioxide in pure water in the presence of CO₂ gas hydrate has been measured at temperatures between 273 and 284 K and pressures ranging from 20 to 60 bar. It was found that the solubility decreases with decreasing temperature in the hydrate formation region. In the absence of gas hydrate, the gas solubility increases with decreasing temperature, but the hydrate formation process changes this trend. This confirms theoretical calculations as well as removes previously reported ambiguities. It was also observed that pressure was not a strong factor on the solubility.     

聚乙烯唑啉作用下甲烷水合物分解的分子动力学模拟

利用分子动力学模拟系统研究了不同质量浓度下(1.25%、2.50%、6.06%)聚乙烯唑啉(PEtO)对甲烷水合物的分解作用. 模拟体系为甲烷水合物2′2′2的超胞和聚合物对接体系. 模拟发现水分子间氢键构架的水合物笼型结构在PEtO的作用下出现扭曲, 最终导致水合物笼型结构完全坍塌. 通过氧原子径向分布函数、均方位移以及扩散系数比较不同浓度PEtO的作用, 证实在一定浓度范围内, PEtO的浓度越高, 其水合物分解作用越强. 此外, PEtO 具有一定的可生物降解性. PEtO 对水合物的作用为: PEtO 吸附在水合物表面, 其中的酰胺基(N―C＝O)与成笼的水分子形成氢键, 破坏邻近的笼形结构, 令水合物分解; PEtO不断分解表面的水合物, 直到水合物笼完全分解.     

A computer simulation of the mechanism of self-conservation of gas hydrates

Local density profiles and local component pressure profiles were obtained for two model systems containing methane hydrate and ice by molecular dynamics simulation. The ice matrix with methane hydrate clusters inserted into it was shown to be stable at normal pressure and even at a temperature higher than the temperature of methane hydrate dissociation. Calculations showed that the pressure in such a methane hydrate cluster inserted into ice was higher than in the ice phase. There were, however, no strong structure distortions because of the formation of a network of strong hydrogen bonds between the hydrate and ice phases.     

Hydrate film growth on the surface of a gas bubble suspended in water

The lateral film growth rate of CH4, C2H4, CO2, CH4 + C2H4, and CH4 + C3H8 hydrates in pure water were measured at four fixed temperatures of 273.4, 275.4, 277.4, and 279.4 K by means of suspending a single gas bubble in water. The results showed that the lateral growth rates of mixed-gas CH4 + C2H4 hydrate films were slower than that of pure gas (CH4 or C2H4) for the same driving force and that of mixed-gas CH4 + C3H8 hydrate film growth was the slowest. The dependence of the thickness of hydrate film on the driving force was investigated, and it was demonstrated that the thickness of hydrate film was inversely proportional to the driving force. It was found that the convective heat transfer control model reported in the literature could be used to formulate the lateral film growth rate v(f) with the driving force DeltaT perfectly for all systems after introduction of the assumption that the thickness of hydrate films is inversely proportional to the driving force DeltaT; i.e., v(f) = psiDeltaT(5/2) is correct and independent of the composition of gas and the type of hydrate. The thicknesses of different gas hydrate films were estimated, and it is demonstrated that the thicknesses of mixed-gas hydrate films were thicker than those of pure gases, which was qualitatively consistent with the experimental result.