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1.
In the present work, the three- and four-phase hydrate equilibria of (carbon dioxide (CO2) + tetrahydrofuran (THF) + water) system are measured by using Cailletet equipment in the temperature and pressure range of (272 to 292) K and (1.0 to 7.5) MPa, respectively, at different CO2 concentration. Throughout the study, the concentration of THF is kept constant at 5 mol% in the aqueous solution. In addition, the fluid phase transitions of LW–LV–V  LW–LV (bubble point) and LW–LV–V  LW–V (dew point) are determined when they are present in the ternary system. For comparison, the three-phase hydrate equilibria of binary (CO2 + H2O) are also measured. Experimental measurements show that the addition of THF as a hydrate promoter extends hydrate stability region by elevating the hydrate equilibrium temperature at a specified pressure. The three-phase equilibrium line H–LW–V is found to be independent of the overall concentration of CO2. Contradictory, at higher pressure, the phase equilibria of the systems are significantly influenced by the overall concentration of CO2 in the systems. A liquid–liquid phase split is observed at overall concentration of CO2 as low as 3 mol% at elevated pressure. The region is bounded by the bubble-points line (LW–LV–V  LW–LV), dew points line (LW–LV–V  LW + V) and the four-phase equilibrium line (H + LW + LV + V). At higher overall concentration of CO2 in the ternary system, experimental measurements show that pseudo-retrograde behaviour exists at pressure between (2.5 and 5) MPa at temperature of 290.8 K.  相似文献   

2.
《Fluid Phase Equilibria》2005,233(2):190-193
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.  相似文献   

3.
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–Lw–V) to two phases (Lw–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 + Lw + 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.  相似文献   

4.
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.  相似文献   

5.
A highly accurate P, V, T,x model is developed for aqueous chloride solutions of the binary systems, viz. (LiCl + H2O), (NaCl + H2O), (KCl + H2O), (MgCl2 + H2O), (CaCl2 + H2O), (SrCl2 + H2O), and (BaCl2 + H2O). The applied ranges of temperature, pressure, and concentrations for the systems (LiCl + H2O), (NaCl + H2O), (KCl + H2O), (MgCl2 + H2O), (CaCl2 + H2O), (SrCl2 + H2O), and (BaCl2 + H2O) are (273 K to 564 K, 0.1 MPa to 40 MPa, and 0 to 10 molal), (273 K to 573 K, 0.1 MPa to 100 MPa, and 0 to 6.0 molal), (273 K to 543 K, 0.1 MPa to 50 MPa, and 0 to 4.5 molal), (273 K to 543 K, 0.1 MPa to 40 MPa, and 0 to 3.0 molal), (273 K to 523 K, 0.1 MPa to 60 MPa, and 0 to 6.0 molal), (298 K to 473 K, 0.1 MPa to 2 MPa, and 0 to 2.0 molal) and (273 K to 473 K, 0.1 MPa to 20 MPa, and 0 to 1.6 molal), respectively. Comparison of the model with thousands of experimental data points concludes that the average deviation over the above T, P, m range is 0.020% to 0.066% in density (or volume) for these systems, which indicates high accuracy. From this model, various volumetric properties, such as the apparent molar volume at infinite dilution and isochores of fluid inclusions, can be calculated, thus having a wide range of geological applications, such as reservoir fluid flow simulation and fluid-inclusion study. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm and online calculations is made available on: www.geochem-model.org/models.htm  相似文献   

6.
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.  相似文献   

7.
《Fluid Phase Equilibria》2006,245(2):134-139
The vapor-hydrate equilibria were studied experimentally in detail for CH4 + C2H4 + tetrahydrofuran (THF) + water systems in the temperature range of 273.15–282.15 K, pressure range of 2.0–4.5 MPa, the initial gas–liquid volume ratio range of 45–170 standard volumes of gas per volume of liquid and THF concentration range of 4–12 mol%. The results demonstrated that, because of the presence of THF, ethylene was remarkably enriched in vapor phase instead of being enriched in hydrate phase for CH4 + C2H4 + water system. This conclusion is of industrial significance; it implies that it is feasible to enrich ethylene from gas mixture, e.g., various kinds of refinery gases or cracking gases in ethylene plant, by forming hydrate.  相似文献   

8.
The paper reports the three-phase (gas + aqueous liquid + hydrate) equilibrium pressure (p) versus temperature (T) data for a (O3 + O2 + CO2 + H2O) system and, for comparison, corresponding data for a (O2 + CO2 + H2O) system for the first time. These data cover the temperature range from (272 to 279) K, corresponding to pressures up to 4 MPa, for each of the three different (O3 + O2)-to-CO2 or O2-to-CO2 mole ratios in the gas phase, which are approximately 1:9, 2:8, and 3:7, respectively. The mole fraction of ozone in the gas phase of the (O3 + O2 + CO2 + H2O) system was from ∼0.004 to ∼0.02. The modified pressure-search method, developed in our previous study [S. Muromachi, T. Nakajima, R. Ohmura, Y.H. Mori, Fluid Phase Equilib. 305 (2011) 145–151] for pT measurements in the presence of chemically unstable ozone, was applied, having been further modified for dealing with highly water-soluble CO2, for the (O3 + O2 + CO2 + H2O) system, while the conventional temperature-search method was used for the (O2 + CO2 + H2O) system. The measurement uncertainties (with 95% coverage) were ±0.11 K for T, ±6.0 kPa for p, and ±0.0015 for the mole fraction of each species in the gas phase. It was confirmed that, at a given CO2 fraction in the gas phase, p for the (O3 + O2 + CO2 + H2O) system was consistently lower than that for the (O2 + CO2 + H2O) system over the entire T range of the present measurements, indicating a preference of O3 to O2 in the uptake of guest-gas molecules into the cages of a structure I hydrate.  相似文献   

9.
《Fluid Phase Equilibria》2006,248(2):103-114
A thermodynamic model is presented to calculate N2 solubility in pure water (273–590 K and 1–600 bar) and aqueous NaCl solutions (273–400 K, 1–600 bar and 0–6 mol kg−1) with or close to experimental accuracy. This model is based on a semi-empirical equation used to calculate gas phase composition of the H2O–N2 system and a specific particle interaction theory for liquid phase. With the parameters evaluated from N2–H2O–NaCl system and using a simple approach, the model is extended to predict the N2 solubility in seawater accurately. Liquid phase density of N2–H2O–NaCl system at phase equilibrium and the homogenization pressure of fluid inclusions containing N2–H2O–NaCl can be calculated from this model. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm.  相似文献   

10.
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%.  相似文献   

11.
This study is focused on modelling the phase equilibrium behaviour of the reaction mixture (CO2 + methanol + DMC + H2O) at high pressure–temperature conditions using the Patel–Teja (PT) and Peng–Robinson–Stryjek–Vera (PRSV) equations of state along with the van der Waals One-Fluid (1PVDW) mixing rule. The optimum values of the binary interaction parameters (kij) were calculated from VLE data found in the literature, and then adjusted to a lineal temperature equation. As a result, the temperature-dependent model was applied to predict the fluid phase equilibria of the corresponding binary a ternary sub-systems and, later, successfully contrasted with experimental data. In addition, phase equilibrium data were experimentally measured at high pressure (8 MPa to 15 MPa) for the ternary system (CO2 + methanol + DMC), in order to confirm the ability of the model to predict the phase behaviour of the ternary system at high pressure–temperature. The agreement between the experimental data and the proposed model enables to predict the phase equilibrium behaviour of the mixture (CO2 + methanol + DMC + H2O), and thus, optimise the operation conditions in several reaction and separation processes.  相似文献   

12.
In the present work, experimental data on the equilibrium conditions of mixed CO2 and THF hydrates in aqueous electrolyte solutions are reported. Seven different electrolytes (metal halides) were used in this work namely sodium chloride (NaCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), potassium bromide (KBr), sodium fluoride (NaF), potassium chloride (KCl), and sodium bromide (NaBr). All equilibrium data were measured by using Cailletet apparatus. Throughout this work, the overall concentration of CO2 and THF were kept constant at (0.04 and 0.05) mol fraction, respectively, while the concentration of electrolytes were varied. The experimental temperature ranged from (275 to 305) K and pressure up 7.10 MPa had been applied. From the experimental results, it is concluded that THF, which is soluble in water is able to suppress the salt inhibiting effect in the range studied. In all quaternary systems studied, a four-phase hydrate equilibrium line was observed where hydrate (H), liquid water (LW), liquid organic (LV), and vapour (V) exist simultaneously at specific pressure and temperature. The formation of this four-phase equilibrium line is mainly due to a liquid–liquid phase split of (water + THF) mixture when pressurized with CO2 and the split is enhanced by the salting-out effect of the electrolytes in the quaternary system. The strength of hydrate inhibition effect among the electrolytes was compared. The results shows the hydrate inhibiting effect of the metal halides is increasing in the order NaF < KBr < NaCl < NaBr < CaCl2 < MgCl2. Among the cations studied, the strength of hydrate inhibition increases in the following order: K+ < Na+ < Ca2+ < Mg2+. Meanwhile, the strength of hydrate inhibition among the halogen anion studied decreases in the following order: Br? > Cl? > F?. Based on the results, it is suggested that the probability of formation and the strength of ionic–hydrogen bond between an ion and water molecule and the effects of this bond on the ambient water network are the major factors that contribute to hydrate inhibition by electrolytes.  相似文献   

13.
The solubility of the binary system (LiNO3 + H2O) from T = 273.15 K to T = 333.15 K and solubility isotherms of the ternary system (LiCl + LiNO3 + H2O) were elaborately measured at T = 273.15 K and T = 323.15 K. These solubility data, as well as water activities in the binary systems from the literature, were treated by an empirically modified BET model. The isotherms of the ternary system (LiCl + LiNO3 + H2O) were reproduced and a complete phase diagram of the ternary system in the temperature range from 273.15 K to 323.15 K predicted. It is shown that the solubility data for the binary system (LiNO3 + H2O) measured in this work are slightly different from the literature data. Simulated results showed that the saturated salt solution of (2.8LiCl + LiNO3) is in equilibrium with the stable solid phase LiNO3(s) over the temperature range from 283.15 K to 323.15 K, other than the solid phases LiNO3 · 3H2O(s) and LiClH2O(s) as reported by Iyoki et al. [S. Iwasaki, Y. Kuriyama. T. Uemura, J. Chem. Eng. Data 38 (1993) 396–398].  相似文献   

14.
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.  相似文献   

15.
The bromide minerals solubility in the mixed system (m1NaBr + m2MgBr2)(aq) have been investigated at T = 323.15 K by the physico-chemical analysis method. The equilibrium crystallization of NaBr·2H2O(cr), NaBr(cr), and MgBr2·6H2O(cr) has been established. The solubility-measurements results obtained have been combined with all other experimental equilibrium solubility data available in literature at T = (273.15 and 298.15) K to construct a chemical model that calculates (solid + liquid) equilibria in the mixed system (m1NaBr + m2MgBr2)(aq). The solubility modeling approach based on fundamental Pitzer specific interaction equations is employed. The model gives a very good agreement with bromide salts equilibrium solubility data. Temperature extrapolation of the mixed system model provides reasonable mineral solubility at high temperature (up to 100 °C). This model expands the previously published temperature variable sodium–potassium–bromide and potassium–magnesium–bromide models by evaluating sodium–magnesium mixing parameters. The resulting model for quaternary system (Na + K + Mg + Br + H2O) is validated by comparing solubility predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solution models due to data insufficiencies at high temperature are discussed.  相似文献   

16.
We describe a new apparatus suitable for measurements of the phase behaviour and phase properties of fluid mixtures under conditions of high-pressure. We propose a synthetic method for the determination of gas solubility, and present results for the system (CO2 + H2O). In addition, we report new measurements of the hydrate equilibrium curves in aqueous systems containing either pure carbon dioxide or mixed gases including CO2. For hydrates formed in the (CO2 + H2O) system, we find an enthalpy of dissociation of 77 kJ · mol?1. This value was unchanged by the addition of mass fraction 0.043 of NaCl to the water. Compared with pure CO2, mixtures of CO2 with air exhibited markedly different dissociation pressures at given temperature, but were characterised by the same enthalpy of dissociation. However, two mixtures containing either nitrogen or methane and hydrogen both exhibited a higher enthalpy of dissociation, 106 kJ · mol?1, consistent with these systems forming structure II hydrates.  相似文献   

17.
The thermal properties of {tetra-n-butylammonium bromide + tetra-n-butylammonium chloride (TBAB + TBAC)} mixed semiclathrate hydrates prepared from aqueous solutions were investigated by dissociation temperature measurements and differential scanning calorimetry (DSC). The maximum dissociation temperature of the mixed hydrate crystals at 0.1 MPa is 288.5 K for xTBAB = 0.2 {mole fraction of TBAB to (TBAB + TBAC)}, which is higher than that of the pure hydrates {T = (285.5 and 288.2) K for TBAB and TBAC hydrates, respectively}. In addition, the dissociation enthalpies of the mixed hydrates are higher than those of the pure hydrates {(5.55 ± 0.06) kJ  mol−1 H2O for pure TBAB hydrate and (5.30 ± 0.05) kJ  mol−1 H2O for pure TBAC hydrate}, with a maximum of (5.95 ± 0.12) kJ  mol−1 H2O recorded at approximately xTBAB = 0.4. It was therefore suggested that the crystal distortion in (TBAB + TBAC) mixed hydrates, caused by replacing water molecules by both bromide and chloride anions, was smaller than that observed for each pure hydrate. Consequently, the hydration numbers in the mixed hydrates were hypothesized to be slightly higher than those of the pure hydrates.  相似文献   

18.
Water activities in the ternary system (CaCl2 + SrCl2 + H2O) and its sub-binary system (CaCl2 + H2O) at T = 298.15 K have been elaborately measured by an isopiestic method. The data of the measured water activity were used to justify the reliability of solubility isotherms reported in the literature by correlating them with a thermodynamic Pitzer–Simonson–Clegg (PSC) model. The model parameters for representing the thermodynamic properties of the (CaCl2 + H2O) system from (0 to 11) mol  kg−1 at T = 298.15 K were determined, and the experimental water activity data in the ternary system were compared with those predicted by the parameters determined in the binary systems. Their agreement indicates that the PSC model parameters can reliably represent the properties of the ternary system. Under the assumption that the equilibrium solid phases are the pure solid phases (SrCl2  6H2O and CaCl2  6H2O)(s) or the ideal solid solution consisting of CaCl2  6H2O(s) and SrCl2  6H2O(s), the solubility isotherms were predicted and compared with experimental data from the literature. It was found that the predicted solubility isotherm agrees with experimental data over the entire concentration range at T = 298.15 K under the second assumption described above; however, it does not under the first assumption. The modeling results reveal that the solid phase in equilibrium with the aqueous solution in the ternary system is an ideal solid solution consisting of SrCl2  6H2O(s) and CaCl2  6H2O(s). Based on the theoretical calculation, the possibility of the co-saturated points between SrCl2  6H2O(s) and the solid solution (CaCl2  6H2O + SrCl2  6H2O)(s) and between CaCl2  6H2O(s) and the solid solution (CaCl2  6H2O + SrCl2  6H2O)(s), which were reported by experimental researchers, has been discussed, and the Lippann diagram of this system has been presented.  相似文献   

19.
《Supramolecular Science》1998,5(3-4):267-273
Interaction of a molecule with micropore walls strongly depends on the micropore width. Molecules confined in the micropore tend to form an intermolecular structure inherent to each molecule/pore system in order to lower the whole molecular energy. Supercritical NO is adsorbed in micropores of zolite or activated carbon fiber in the form of a dimer at 303 K. The NO dimerization varies with the micropore width. CCl4 molecules only in pore of pore width =1.0 nm at 303 K form a plastic crystalline structure which is observed at 246–250 K in the bulk phase. H2O molecules are associated with each other to form an ordered assembly in carbon micropores at 303 K; the smaller the pore width, the more ordered the assembly structure. The presence of preadsorbed H2O noticeably enhances adsorption of supercritical CH4 in carbon micropores at 303 K due to methane nanohydrate formation, which has an optimum pore width of 1 nm.  相似文献   

20.
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.  相似文献   

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