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.     

Experimental investigation on the dissociation conditions of methane hydrate in the presence of imidazolium-based ionic liquids

In this work, the performance of nine ionic liquids (ILs) as thermodynamic hydrate inhibitors is investigated. The dissociation temperature is determined for methane gas hydrates using a high pressure micro deferential scanning calorimeter between (3.6 and 11.2) MPa. All the aqueous IL solutions are studied at a mass fraction of 0.10. The performance of the two best ILs is further investigated at various concentrations. Electrical conductivity and pH of these aqueous IL solutions (0.10 mass fraction) are also measured. The enthalpy of gas hydrate dissociation is calculated by the Clausius–Clapeyron equation. It is found that the ILs shift the methane hydrate (liquid + vapour) equilibrium curve (HLVE) to lower temperature and higher pressure. Our results indicate 1-(2-hydroxyethyl) 3-methylimidazolium chloride is the best among the ILs studied as a thermodynamic hydrate inhibitor. A statistical analysis reveals there is a moderate correlation between electrical conductivity and the efficiency of the IL as a gas hydrate inhibitor. The average enthalpies of methane hydrate dissociation in the presence of these ILs are found to be in the range of (57.0 to 59.1) kJ ⋅ mol⁻¹. There is no significant difference between the dissociation enthalpy of methane hydrate either in the presence or in absence of ILs.     

Thermodynamic stability of structure-H hydrates of methylcyclopentane and cyclooctane helped by methane

The four-phase equilibria were measured for the methylcyclopentane+methane+H₂O hydrate system (274.28–287.40 K, 1.75–9.34 MPa) and the cyclooctane+methane+H₂O hydrate system (274.08–288.57 K, 1.60–9.33 MPa). Each structure-H hydrate has the lower equilibrium pressure than the pure methane structure-I hydrate in the temperature range of the present work. The isothermal equilibrium pressures of both methylcyclopentane and cyclooctane hydrates are slightly higher than that of methylcyclohexane hydrate.     

Phase equilibrium measurements for semi-clathrate hydrates of the (CO2 + N2 + tetra-n-butylammonium bromide) aqueous solution system

The application of semi-clathrate hydrate formation technology for gas separation purposes has gained much attention in recent years. Consequently, there is a demand for experimental data for relevant semi-clathrate hydrate phase equilibria. In this work, semi-clathrate hydrate dissociation conditions for the system comprising mixtures of {CO₂ (0.151/0.399 mole fraction) + N₂ (0.849/0.601 mole fraction) + 0.05, 0.15, and 0.30 mass fraction tetra-n-butylammonium bromide (TBAB)} aqueous solutions have been measured and are reported. An experimental apparatus which was designed and built in-house was used for the measurements using the isochoric pressure-search method. The range of conditions for the measurements was from 277.1 K to 293.2 K for temperature and pressures up to 16.21 MPa. The phase equilibrium data measured demonstrate the high hydrate promotion effects of TBAB aqueous solutions.     

Experimental low temperature water content in gaseous methane,liquid ethane,and liquid propane in equilibrium with hydrate at cryogenic conditions

In low temperature gas processing, the presence of water can result in the formation of gas hydrate plugs. To avoid this problem, it is important to know the water solubility in natural gas components in equilibrium with gas hydrate. In this study experimental measurements of water content in gaseous methane in equilibrium with hydrate at 3.45 MPa (500 psia) and 6.90 MPa (1000 psia) and temperatures ranging from −3.2 °C (26.2 °F) to −80 °C (−112 °F) are presented. Similar measurements are presented for liquid ethane at 3.45 MPa (500 psia) and temperatures from −2.2 °C (28.0 °F) to −70 °C (−94 °F), and for liquid propane at 0.86 MPa (125 psia) and temperatures down to −60 °C (−76 °F), respectively.In measuring the water content, a Panametrics moisture sensor (calibrated to 1 ppb water content in nitrogen) has been used in flowing streams of the hydrocarbon-rich phases that are saturated with water. The results obtained with the Panametrics hygrometer show good agreement (normally better than ±4%) with previous measurements, which were obtained by a gas chromatographic technique for methane, ethane, and propane at temperatures ranging from −2.0 °C (28.4 °F) to −30 °C (−22 °F), which are within the hydrate region.     

Phase behaviour of heavy petroleum fractions in pure propane and n-butane and with methanol as co-solvent

This work reports phase equilibrium experimental results for heavy petroleum fractions in pure propane and n-butane as primary solvents and using methanol as co-solvent. Three kinds of oils were investigated from Marlim petroleum: a relatively light fraction coming from the first distillation of crude petroleum at atmospheric pressure (GOP – heavy gas oil of petroleum), the residue of such distillation (RAT) and the crude petroleum sample. Phase equilibrium measurements were performed in a high-pressure, variable-volume view cell, following the static synthetic method, over the temperature range of 323 K to 393 K, pressures up to 10 MPa and overall compositions of heavy component varying from 1 wt% to 40 wt%. Transition pressures for low methanol and oil concentrations were very close for GOP, RAT, and crude Marlim when using propane as the primary solvent. Close to propane critical temperature, two and three-phase transitions were observed for GOP and Marlim when methanol was increased. When n-butane was used as primary solvent, all transitions observed were of (vapour + liquid) type with transition pressure values smaller than those obtained for propane.     

Inhibition effect of 1-ethyl-3-methylimidazolium chloride on methane hydrate equilibrium

The dissociation conditions of methane hydrate in the presence of 0.1, 0.2, 0.3 and 0.4 mass fraction of 1-ethyl-3-methylimidazolium chloride (abbreviated by EMIM-Cl hereafter) were experimentally determined. A high pressure micro-differential scanning calorimeter equipped with a motorized pump was applied to measure the dissociation temperature of the (hydrate + liquid water + vapor) three-phase equilibrium under a constant pressure process with a pressure ranging from (5.0 to 35.0) MPa. The addition of EMIM-Cl would inhibit the methane hydrate formation. The most significant inhibition effect was observed at 0.4 mass fraction of EMIM-Cl in aqueous solution to lower the dissociation temperature by 12.82 K at 20.00 MPa in comparison to that of the (methane + water) system. The Peng–Robinson–Stryjek–Vera equation of state incorporated with COSMO-SAC activity coefficient model and the first order modified Huron–Vidal mixing rule were applied to evaluate the fugacity of vapor and liquid phase. A modified van der Waals and Platteeuw model with an explicit pressure dependence of the Langmuir adsorption constant was applied to determine the fugacity of hydrate phase. The predictive thermodynamic model successfully describes the tendency of phase behavior of methane hydrate in the presence of EMIM-Cl in the range from 0.1 to 0.4 mass fraction with absolute average relative deviation in predicted temperature of 0.70%.     

Hydrate structural transition depending on the composition of methane + cyclopropane mixed gas hydrate

The methane + cyclopropane mixed gas hydrate system has been investigated at 291.1 K by means of gas chromatography and Raman spectroscopy. Both of pure guest species generate the structure-I hydrate in the present conditions. Isothermal phase equilibria exhibit discontinuity around the equilibrium cyclopropane composition (water-free) in the gas phase of 0.20. The Raman shifts have changed bordering at the point. These results reveal that the methane + cyclopropane mixed gas hydrate generates the structure-II crystal in the methane rich region, while the structure-I crystal is generated in the cyclopropane rich region.     

A thermodynamic study of the (difluoromethane + water) system

A study of the (difluoromethane + water) system was conducted at temperatures between (255 and 298) K, and pressures from (0.06 to 1.30) MPa. The solubility of difluoromethane in liquid water was measured from (280 to 298) K, at pressures up to the hydrate formation pressure. The (p, T) behavior of the (liquid + hydrate + vapor) three-phase equilibrium was measured from (274 to 292) K. The (p, T) behavior of the (ice + hydrate + vapor) three-phase equilibrium was measured from (257 to 273) K. Solubility-corrected enthalpies of dissociation were determined at the lower quadruple point (Q1) using the Clapeyron equation. The de Forcrand method was used to determine the hydration number of the hydrate at Q1. The results show that not all of the cages in the SI hydrate structure are filled.     

Kinetic and thermodynamic behaviour of CF4 clathrate hydrates

This study presents experimental kinetic and thermodynamic data for CF₄ clathrate hydrates. Experimental measurements were undertaken in a high pressure equilibrium cell with a 40 cm³ inner volume. The measurements of experimental hydrate dissociation conditions were performed in the temperature range of (273.8 to 278.3) K and pressures ranging from (4.55 to 11.57) MPa. A thermodynamic model based on van der Waals and Platteeuw (vdW–P) solid solution theory was used for prediction and comparison of hydrate dissociation conditions and the Langmuir constant parameters for CF₄ based on Parrish and Prausnitz equation are reported. For the kinetics, the effect of initial pressure and temperature on the induction time, CF₄ hydrate formation rate, the apparent rate constant of reaction, storage capacity, and water to hydrate conversion during the hydrate formation were studied. Kinetic experiments were performed at initial temperatures of (275.3, 276.1 and 276.6) K and initial pressures of (7.08, 7.92, 9.11, 11.47 and 11.83) MPa. Results show that increasing the initial pressure at constant temperature decreases the induction time, while CF₄ hydrate formation rate, the apparent rate constant of reaction, storage capacity, and water to hydrate conversion increase. The same trends are observed with a decrease in the initial temperature at constant pressure.     

Hydrate phase equilibrium in the system of (carbon dioxide + 2,2-dimethylbutane + water) at temperatures below freezing point of water

The four-phase equilibrium conditions of (vapor + liquid + hydrate + ice) were measured in the system of (CO₂ + 2,2-dimethylbutane + water). The measurements were performed within the temperature range (254.2 to 270.2) K and pressure range (0.490 to 0.847) MPa using an isochoric method. Phase equilibrium conditions of hydrate formed in this study were measured to be at higher temperatures and lower pressures than those of structure I CO₂ simple hydrate. The largest difference in the equilibrium pressures of structure I CO₂ hydrate and the hydrate formed in the present study was 0.057 MPa at T = 258.3 K. On the basis of the four-phase equilibrium data obtained, the quintuple point for the (ice + structure I hydrate + structure H hydrate + liquid + vapor) was also determined to be T = 266.4 K and 0.864 MPa. The results indicate that structure H hydrate formed with CO₂ and 2,2-dimethylbutane is stable exclusively at the temperatures below the quintuple temperature.     

Isothermal (vapour + liquid) equilibrium for binary mixtures of polyethylene glycol mono-4-nonylphenyl ether (PEGNPE) with methanol,ethanol, or 2-propanol

Saturated pressures of three binary systems of oligomeric polyethylene glycol mono-4-nonylphenyl ether (PEGNPE) with methanol, ethanol, and 2-propanol have been measured by using an autoclave (vapour + liquid) equilibrium (VLE) apparatus at temperatures ranging from (340 to 455) K and the oligomer content ranging from 0.100 to 0.400 in mole fraction. With a given feed composition, equilibrium pressures were measured at various temperatures to obtain VLE data. The experimental data were fitted to the Antoine equation and also correlated with activity coefficient models, the NRTL and the UNIQUAC. The correlation results showed good agreement between the calculated values and the experimental data. In general, the NRTL model yielded better results. Additionally, the solvent activities were evaluated from the experimental results and were compared with those from the NRTL and the UNIQUAC models.     

Isothermal phase equilibria for the (HFC-32 + HFC-134a) mixed-gas hydrate system

Isothermal phase equilibria (pressure-composition relations in hydrate, gas, and aqueous phases) in the {difluoromethane (HFC-32) + 1,1,1,2-tetrafluoroethane (HFC-134a)} mixed-gas hydrate system were measured at the temperatures 274.15 K, 279.15 K, and 283.15 K. The heterogeneous azeotropic-like behaviour derived from the structural phase transition of (HFC-32 + HFC-134a) mixed-gas hydrates appears over the whole temperature range of the present study. In addition to the heterogeneous azeotropic-like behaviour, the isothermal phase equilibrium curves of the (HFC-32 + HFC-134a) mixed-gas hydrate system exhibit the negative homogeneous azeotropic-like behaviour at temperatures 279.15 K and 283.15 K. The negative azeotropic-like behaviour, which becomes more remarkable at higher temperatures, results in the lower equilibrium pressure of (HFC-32 + HFC-134a) mixed-gas hydrates than those of both simple HFC-32 and HFC-134a hydrates. Although the HFC-134a molecule forms the simple structure-II hydrate at the temperatures, the present findings reveal that HFC-134a molecules occupy a part of the large cages of the structure-I mixed-gas hydrate.     

Isothermal phase equilibria for the (xenon + cyclopropane) mixed-gas hydrate system

Isothermal three-phase equilibria of gas, aqueous, and hydrate phases for the {xenon (Xe) + cyclopropane (c-C₃H₆)} mixed-gas hydrate system were measured at two different temperatures (279.15 and 289.15) K. The structural phase transitions from structure-I to structure-II and back to structure-I, depending on the mole fraction of guest mixtures, occur in the (Xe + c-C₃H₆) mixed-gas hydrate system. The isothermal pressure–composition relations have two local pressure minima. The most important characteristic in the (Xe + c-C₃H₆) mixed-gas hydrate system is that the equilibrium pressure–composition relations exhibit the complex phase behavior involving two structural phase transitions and two homogeneous negative azeotropes. One of two structural phase transitions exhibits the heterogeneous azeotropic-like behavior.     

Solubility of carbon dioxide,methane, and ethane in 1-butanol and saturated liquid densities and viscosities

A designed pressure–volume–temperature (PVT) apparatus has been used to measure the (vapor + liquid) equilibrium properties of three binary mixtures (methane +, ethane +, and carbon dioxide + 1-butanol) at two temperatures (303 and 323) K and at the pressures up to 6 MPa. The solubility of the compressed gases in 1-butanol and the saturated liquid densities and viscosities were measured. In addition, the density and viscosity of pure 1-butanol were measured at two temperatures (303 and 323) K and at the pressures up to 10 MPa. The experimental results show that the solubility of the gases in 1-butanol increases with pressure and decreases with temperature. The dissolution of gases in 1-butanol causes a decline in the viscosity of liquid phase. The saturated liquid density follows a decreasing trend with the solubility of methane and ethane. However, the dissolution of carbon dioxide in 1-butanol leads to an increase in the density of liquid phase. The experimental data are well correlated with Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR) equations of state (EOSs). SRK EOS was slightly superior for correlating the saturated liquid densities.     

Solubility of methane and carbon dioxide in ethylene glycol at pressures up to 14 MPa and temperatures ranging from (303 to 423) K

This work reports solubility data of methane and carbon dioxide in ethylene glycol and the Henry’s law constant of each solute in the studied solvent at saturation pressure. The measurements were performed at (303, 323, 373, 398, and 423.15) K and pressures up to 6.3 MPa for mixtures containing carbon dioxide and pressures up to 13.7 MPa for mixtures containing methane. The experiments were performed in an autoclave type phase equilibrium apparatus using the total pressure method (synthetic method). All investigated systems show an increase of gas solubility with the increase of pressure. A decrease of carbon dioxide solubility with the increase of temperature and an increase of methane solubility with the increase of temperature was observed. From the variation of solubility with temperature, the partial molar enthalpy, and entropy change are calculated.     

Phase equilibria for H2 + CO2 + H2O system containing gas hydrates

Isothermal phase equilibrium (pressure–composition in the gas phase) for the ternary system of H₂ + CO₂ + H₂O has been investigated in the presence of gas hydrate phase. Three-phase equilibrium pressure increases with the H₂ composition of gas phase. The Raman spectra suggest that H₂ is not enclathrated in the hydrate-cages and behaves only like the diluent gas toward the formation of CO₂ hydrate. This fact is also supported by the thermodynamic analysis using Soave–Redlich–Kwong equation of state.     

Spherical resonator for vapor-phase speed of sound and measurements of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane (RE347mcc) and trans-1,3,3,3-tetrafluoropropene [R1234ze(E)]

We describe an apparatus to measure the speed of sound of gas samples at temperatures from (265 to 500) K with pressures up to 10 MPa. The speed of sound was determined from the frequency of the three lowest-order radial resonance modes for the gas in a spherical cavity machined from type 321 stainless steel for corrosion resistance. The spherical resonator was contained in an isothermal copper block that was maintained at the temperature of interest by a multilayer thermostat with vacuum insulation. The dimensions of the spherical cavity were characterized as a function of temperature and pressure though calibration measurements with high-purity argon. The performance of the apparatus was demonstrated with measurements of high-purity methane and ethane. Measurements of the sound speed of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane (RE347mcc) are reported at temperatures from (325 to 500) K with pressures up to 1.6 MPa. Measurements on trans-1,3,3,3-tetrafluoropropene (R1234ze(E)) are reported at temperatures from (280 to 420) K with pressures up to 2.8 MPa. The average relative combined expanded uncertainties of the measured sound speed for RE347mcc and R1234ze(E) are (0.029 and 0.041)%, respectively.     

Hydrate phase equilibrium for the (hydrogen + tert-butylamine + water) system

The three-phase equilibrium conditions of ternary (hydrogen + tert-butylamine + water) system were first measured under high-pressure in a “full view” sapphire cell. The tert-butylamine–hydrogen binary hydrate phase transition points were obtained through determining the points of intersection of three phases (H–L_w–V) to two phases (L_w–V) experimentally. Measurements were made using an isochoric method. Firstly, (tetrahydrofuran + hydrogen) binary hydrate phase equilibrium data were determined with this method and compared with the corresponding experimental data reported in the literatures and the acceptable agreements demonstrated the reliability of the experimental method used in this work. The experimental investigation on (tert-butylamine + hydrogen) binary hydrate phase equilibrium was then carried out within the temperature range of (268.4 to 274.7) K and in the pressure range of (9.54 to 29.95) MPa at (0.0556, 0.0886, 0.0975, and 0.13) mole fraction of tert-butylamine. The three-phase equilibrium curve (H + L_w + V) was found to be dependent on the concentration of tert-butylamine solution. Dissociation experimental results showed that tert-butylamine as a hydrate former shifted hydrate stability region to lower pressure and higher temperature.     

Phase equilibrium measurements and the tuning behavior of new sII clathrate hydrates

We suggest two types of new amine-type sII formers: pyrrolidine and piperidine. These guest compounds fail to form clathrate hydrate structures with host water, but instead have to combine with light gaseous guest molecules (methane) for enclathration. First, two binary clathrate hydrates of (pyrrolidine + methane) and (piperidine + methane) were synthesized at various amine concentrations. ¹³C NMR and Raman analysis were done to identify the clathrate hydrate structure and guest distribution over sII-S and sII-L cages. XRD was also used to find the exact structure and corresponding cell parameters. At a dilute pyrrolidine concentration of less than 5.56 mol%, the tuning phenomenon is observed such that methane molecules surprisingly occupy sII-L cages. At the critical guest concentration of about 0.1 mol%, the cage occupancy ratio reaches the maximum of approximately 0.5. At very dilute guest concentration below 0.1 mol%, the methane molecules fail to occupy large cages on account of their rarefied distribution in the network. Direct-release experiments were performed to determine the actual guest compositions in the clathrate hydrate phases. Finally, we measured the clathrate hydrate phase equilibria of (pyrrolidine + methane) and (piperidine + methane).