Kinetic hydrate inhibitor performance of new copolymer poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine)s with TBAB

In oil and gas field, the application of kinetic hydrate inhibitors (KHIs) independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the combined use of KHIs and some synergists, which would enhance KHIs’ inhibitory effect on both hydrate nucleation and hydrate crystal growth. In this study, a novel kind of KHI copolymer poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine)s (HGs) is used in conjunction with TBAB to show its high performance on hydrate inhibition. The performance of HGs with different monomer ratios in structure II tetrahydrofuran (THF) hydrate is investigated using kinetic hydrate inhibitor evaluation apparatus by step-cooling method and isothermal cooling method. With the combined gas hydrate inhibitor at the concentration of 1.0 wt%, the induction time of 19 wt% THF solution could be prolonged to 8.5 h at a high subcooling of 6℃. Finally, the mechanism of HGs inhibiting the formation of gas hydrate is proposed.     

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.     

Accelerated nucleation of tetrahydrofuran(THF)hydrate in presence of ZIF-61

Clathrate hydrate can be used in energy gas storage and transportation,CO 2 capture and cool storage etc.However,these technologies are difficult to be used due to the low formation rate and long induction time of hydrate formation.In this paper,ZIF-61(zeolite imidazolate framework,ZIF) was first used in hydrate formation to stimulate hydrate nucleation.As an additive of clathrate hydrate,ZIF-61 promoted obviously the acceleration of tetrahydrofuran(THF) hydrate nucleation.It shortened the induction time of THF hydrate formation from 2-5 h to 0.3-1 h mainly due to the template function of ZIF-61 by which the nucleation of THF hydrate has been promoted.     

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.     

Chitosan as green kinetic inhibitors for gas hydrate formation

The kinetic inhibiting effect of a number of chitosans on hydrate formation was investigated using methane and methane/ethane gas mixtures.The results indicated that chitosan was a good kinetic inhibitor.The induction time of gas hydrate formation evidently increased with the degree of deacetylation(DD),however,when DD was higher than 80%,the effect of DD on the induction time was negligible.Moreover,it was found that the molecular weight(MW)of chitosan and the addition of polyethylene oxide(PEO)had little effect on the induction time.The optimal concentration of chitosan was found to be 0.6wt%.Finally,the mechanisms of the kinetic inhibitor on the hydrate formation were discussed.     

Hydrate phase equilibrium and structure for (methane + ethane + tetrahydrofuran + water) system

The separation of methane and ethane through forming hydrate is a possible choice in natural gas, oil processing, or ethylene producing. The hydrate formation conditions of five groups of (methane + ethane) binary gas mixtures in the presence of 0.06 mole fraction tetrahydrofuran (THF) in water were obtained at temperatures ranging from (277.7 to 288.2) K. In most cases, the presence of THF in water can lower the hydrate formation pressure of (methane + ethane) remarkably. However, when the composition of ethane is as high as 0.832, it is more difficult to form hydrate than without THF system. Phase equilibrium model for hydrates containing THF was developed based on a two-step hydrate formation mechanism. The structure of hydrates formed from (methane + ethane + THF + water) system was also determined by Raman spectroscopy. When THF concentration in initial aqueous solution was only 0.06 mole fraction, the coexistence of structure I hydrate dominated by ethane and structure II hydrate dominated by THF in the hydrate sample was clearly demonstrated by Raman spectroscopic data. On the contrary, only structure II hydrate existed in the hydrate sample formed from (methane + ethane + THF + water) system when THF concentration in initial aqueous solution was increased to 0.10 mole fraction. It indicated that higher THF concentration inhibited the formation of structure I hydrate dominated by ethane and therefore lowered the trapping of ethane in hydrate. It implies a very promising method to increase the separation efficiency of methane and ethane.     

Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching

In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.     

Effect of antifreeze proteins on the nucleation, growth, and the memory effect during tetrahydrofuran clathrate hydrate formation

The inhibition activities of two antifreeze proteins (AFPs) on the formation of tetrahydrofuran (THF) clathrate hydrate have been tested. AFPs from fish (wfAFP) and insect (CfAFP) changed the morphology of growing THF hydrate crystals. Also, both AFPs showed higher activities in inhibiting the formation THF hydrate than a commercial kinetic inhibitor, poly(vinylpyrrolidone) (PVP). Strikingly, both AFPs also showed the ability to eliminate the "memory effect" in which the crystallization of hydrate occurs more quickly after the initial formation. This is the first report of molecules that can inhibit the memory effect. Since the homogeneous nucleation temperature for THF hydrate was measured to be 237 K, close to that observed for ice itself, the action of kinetic inhibitors must involve heterogeneous nucleation. On the basis of our results, we postulate a mechanism for heterogeneous nucleation, the memory effect and its elimination by antifreeze proteins.     

Molecular hydrogen storage in binary THF-H2 clathrate hydrates

The hydrogen storage capacity of binary THF-H(2) clathrate hydrate has been determined as a function of formation pressure, THF composition, and time. The amount of hydrogen stored in the stoichiometric hydrate increases with pressure and exhibits asymptotic (Langmuir) behavior to approximately 1.0 wt % H(2). This hydrogen concentration corresponds to one hydrogen molecule occupying each of the small 5(12) cavities and one THF molecule in each large 5(12)6(4) cavity in the hydrate framework. Contrary to previous reports, hydrogen storage was not increased upon decreasing the THF concentration below the stoichiometric 5.6 mol % solution to 0.5 mol %, at constant pressure, even after one week. This provides strong evidence that THF preferentially occupies the large 5(12)6(4) cavity over hydrogen, for the range of experimental conditions tested. The maximum amount of hydrogen stored in this binary hydrate was about 1.0 wt % at moderate pressure (<60 MPa) and is independent of the initial THF concentration over the range of conditions tested.     

Clustering structure of aqueous solution of kinetic inhibitor of gas hydrates

Poly-[N-vinylcaprolactam] (PVCAP) and its related compounds are specific polymeric compounds for inhibiting hydrate formation. To clarify the inhibition mechanism of these compounds on hydrate nucleation at the molecular level, we measured the mass spectra of clusters generated from the fragmentation of liquid droplets including N-methylcaprolactam (NMCAP; functional group of PVCAP). By comparing the mass spectra of clusters of the solutions--pure D2O, tetrahydrofuran (THF)-D2O, NMCAP-D2O, and THF-NMCAP-D2O--it was found that the interaction of NMCAP with D2O was much stronger than that of THF with D2O. The relative intensity ratio of D+(NMCAP)m(D2O)n clusters to all the clusters observed for the NMCAP-D2O (1:250) mixed solution was 0.45. On the other hand, the relative intensity ratio of D+(THF)1(D2O)n clusters to all the clusters observed for the THF-D2O (1:17) mixed solution was 0.15. In the case of the THF-NMCAP-D2O three-component mixed solution, the NMCAP-D2O interaction was more predominant than the THF-D2O interaction, even at a lower NMCAP concentration. NMCAP reduces free mobile water molecules around NMCAP, but THF does not. This correlates with the facts that THF forms its hydrate below the freezing point and that PVCAP works as an inhibitor of gas hydrates.     

5A分子筛粉末对四氢呋喃水合物的生成及分解过程的影响

在低于0 ℃和常压下, 将粉碎并筛分后的成型5A分子筛粉末加入四氢呋喃-水(二者质量比为19:81)体系中, 用显微镜观察5A分子筛粉末的存在对四氢呋喃水合物生成和分解过程的影响. 结果表明, 5A分子筛粉末能够促进四氢呋喃水合物的生成. 5A分子筛粉末存在下, 四氢呋喃水合物生成方式主要表现为两种, 脉状生成和块状生成; 同时5A分子筛粉末能够提高四氢呋喃水合物结晶所需要的温度, 降低四氢呋喃水合物的分解温度; 而且5A分子筛粉末粒径的大小及分布对四氢呋喃水合物生成及分解的特性也有很大影响.     

Prediction of vapor-liquid-liquid-hydrate phase equilibrium for multicomponent systems containing tetrahydrofuran

Numbers of hydrate-based new techniques require the algorithm to be able to perform multiphase flash calculation where one phase is a gas hydrate phase.Tetrahydrofuran(THF)is frequently used as a thermodynamic promoter in the development of hydrate-based technique,which can reduce the hydrate formation pressure,especially when methane or hydrogen exists.However,it is a hard work to describe accurately the phase behavior of THF-water system due to their polarities.It has been proved that the water-in-oil(W/O)emulsion can raise the hydrate formation rate and improve the single stage separation efficiency,and furthermore prevent the hydrate from agglomeration to plug the facilities.The goal of this work is to present an extension of our previous work to the prediction of the vapor-liquid-liquid-hydrate equilibrium of such complex systems.These include ternary and quaternary mixtures with W/O emulsion containing THF.The proposed algorithm of four phase equilibrium calculation is very simple due to avoiding the complexity of simultaneous solution of the sophisticated equation group.The calculation results were found to be in satisfactory agreement with the experimental data.     

Assessment of hydrate kinetic inhibitors with visual observations

The hydrate inhibition effect of three kinetic inhibitors (inhibex 301, 501, and 713) was assessed from (CH₄ + C₂H₆ + C₃H₈) gas mixture + brine systems using a high pressure sapphire cell. The onset time of hydrate formation was determined by visual observation method and pressure drop profile method, respectively. The experimental results demonstrated that the onset time was able to be determined by the visual observation method all the time while the pressure drop profile method failed to detect the onset time clearly and correctly at lower temperatures. In some cases, the initial appearance of hydrate crystals cannot induce a clear break in the pressure–time relationship curve. The onset time measured by the visual observation method is usually shorter than or at least the same as that determined by the pressure drop profile method. The inhibiting effect on the growth of hydrate crystals can be shown by the difference of the onset time obtained by the two methods. The maximum tolerated subcooling of each inhibitor was also investigated based on the onset time. It was found that inhibex 301 behaves as the best inhibitor that can tolerate the maximum subcooling of 8.3 K at 0.5 wt% and 10.6 K at 1.0 wt%, respectively. The maximum subcooling for inhibex 501 is 6.8 K at 0.5 wt% and 6.6 K at 1.0 wt%, respectively. Inhibex 713 has relatively poor inhibiting effect among the three inhibitors with the maximum subcooling of less than 3.5 K at 0.5 wt% and 5.1 K at 1.0 wt%, respectively.     

NMR/MRI study of clathrate hydrate mechanisms

Clathrate hydrates are of great importance in many aspects. However, hydrate formation and dissociation mechanisms, essential to all hydrate applications, are still not well understood due to the limitations of experimental techniques capable of providing dynamic and structural information on a molecular level. NMR has been shown to be a powerful tool to noninvasively measure molecular level dynamic information. In this work, we measured nuclear magnetic resonance (NMR) spin lattice relaxation times (T1's) of tetrahydrofuran (THF) in liquid deuterium oxide (D2O) during THF hydrate formation and dissociation. At the same time, we also used magnetic resonance imaging (MRI) to monitor hydrate formation and dissociation patterns. The results showed that solid hydrate significantly influences coexisting fluid structure. Molecular evidence of residual structure was identified. Hydrate formation and dissociation mechanisms were proposed based on the NMR/MRI observations.     

Heat capacity of tetrahydrofuran clathrate hydrate and of its components, and the clathrate formation from supercooled melt

We report a thermodynamic study of the formation of tetrahydrofuran clathrate hydrate by explosive crystallization of water-deficient, near stoichiometric, and water-rich solutions, as well as of the heat capacity, C(p), of (i) supercooled tetrahydrofuran-H2O solutions and of the clathrate hydrate, (ii) tetrathydrofuran (THF) liquid, and (iii) supercooled water and the ice formed on its explosive crystallization. In explosive freezing of supercooled solutions at a temperature below 257 K, THF clathrate hydrate formed first. The nucleation temperature depends on the cooling rate, and excess water freezes on further cooling. The clathrate hydrate melts reversibly at 277 K and C(p) increases by 770 J/mol K on melting. The enthalpy of melting is 99.5 kJ/mol and entropy is 358 J/mol K. Molar C(p) of the empty host lattice is less than that of the ice, which is inconsistent with the known lower phonon frequency of H2O in the clathrate lattice. Analysis shows that C(p) of THF and ice are not additive in the clathrate. C(p) of the supercooled THF-H2O solutions is the same as that of water at 247 K, but less at lower temperatures and more at higher temperatures. The difference tends to become constant at 283 K. The results are discussed in terms of the hydrogen-bonding changes between THF and H2O.     

Tuning methane content in gas hydrates via thermodynamic modeling and molecular dynamics simulation

Storage and transportation of natural gas as gas hydrate (“gas-to-solids technology”) is a promising alternative to the established liquefied natural gas (LNG) or compressed natural gas (CNG) technologies. Gas hydrates offer a relatively high gas storage capacity and mild temperature and pressure conditions for formation. Simulations based on the van der Waals–Platteeuw model and molecular dynamics (MD) are employed in this study to relate the methane gas content/occupancy in different hydrate systems with the hydrate stability conditions including temperature, pressure, and secondary clathrate stabilizing guests. Methane is chosen as a model system for natural gas. It was found that the addition of about 1% propane suffices to increase the structure II (sII) methane hydrate stability without excessively compromising methane storage capacity in hydrate. When tetrahydrofuran (THF) is used as the stabilizing agent in sII hydrate at concentration between 1% and 3%, a reasonably high methane content in hydrate can be maintained (∼85–100, v/v) without dealing with pressures more than 5 MPa and close to room temperature.     

Experimental study of hydrogen sulfide hydrate formation: Induction time in the presence and absence of kinetic inhibitor

In this paper, the effect of adding different concentrations of kinetic inhibitors on the induction time of hydrogen sulfide hydrate formation in a reactor equipped with automatic adjustable temperature controller is studied. A novel method namely “sudden cooling” is used for performing the relevant measurements, in which the induction time of H₂S hydrate in the presence/absence of PVP and L-tyrosine with different concentrations (100, 500, and 1000 ppm) is determined. As a result, PVP with the concentration of 1000 ppm in aqueous solution is detected as a more suitable material for increasing the induction time of H₂S hydrate formation among the investigated kinetic hydrate inhibitors.     

Formation of periodic layered pattern of tetrahydrofuran clathrate hydrates in porous media

Directional growth of tetrahydrofuran (THF) clathrate hydrates was studied in a mixture of glass beads and a stoichiometric THF-water solution. Results showed that disseminated pore space type hydrates formed in a mixture containing 50-microm beads. However, a pure hydrate layer formed pushing the beads in a mixture containing 2-microm beads (frost heaving of hydrates). As the growth proceeded, new layers were formed repeatedly, leading to the eventual formation of a periodic layered pattern. It was found that as the growth rate increased, both the thickness of a hydrate layer and the interval between the neighboring layers decreased according to power laws. The effects of the applied temperature gradient and the weight ratio of the solution and glass beads were also systematically studied. Further, the possibility of applying our model experiments to the formation of natural methane hydrates was discussed.     

The specific surface area of methane hydrate formed in different conditions and manners

The specific surface area of methane hydrates, formed both in the presence and absence of sodium dodecyl sulfate (SDS) and processed in different manners (stirring, compacting, holding the hydrates at the formation conditions for different periods of time, cooling the hydrates for different periods of time before depressurizing them), was measured under atmospheric pressure and temperatures below ice point. It was found that the specific surface area of hydrate increased with the decreasing temperature. The methane hydrate in the presence of SDS was shown to be of bigger specific surface areas than pure methane hydrates. The experimental results further demonstrated that the manners of forming and processing hydrates affected the specific surface area of hydrate samples. Stirring or compacting made the hydrate become finer and led to a bigger specific surface area. Supported by the National natural Science Foundation of China (Grant Nos.20490207, 2076145, uo633003), Program for New Century Excellent Talents in University and National The National High Technology Research and Development Program of China Project.     

Investigation on Gas Storage in Methane Hydrate

The effect of additives (anionic surfactant sodium dodecyl sulfate (SDS), nonionic surfactantalkyl polysaccharide glycoside (APG), and liquid hydrocarbon cyclopentane (CP)) on hydrate inductiontime and formation rate, and storage capacity was studied in this work. Micelle surfactant solutions werefound to reduce hydrate induction time, increase methane hydrate formation rate and improve methanestorage capacity in hydrates. In the presence of surfactant, hydrate could form quickly in a quiescentsystem and the energy costs of hydrate formation were reduced. The critical micelle concentrations of SDS and APG water solutions were found to be 300x 10-6 and 500x 10-6 for methane hydrate formation systemrespectively. The effect of anionic surfactant (SDS) on methane storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduced hydrate induction time and improved hydrateformation rate, but could not improve methane storage in hydrates.