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Thermodynamics of LNG
(2020)
Densities of eight gravimetrically prepared ternary and quaternary gas mixtures consisting of methane, ethane, propane, and partially nitrogen were investigated along the four isotherms of –250, –230, –210, and –190 °F at pressures of 350, 500, 650, and 1000 psig using a cryogenic single-sinker densimeter. The experimental densities were compared to densities calculated by various models, namely the EOS-LNG fundamental Helmholtz equation of state, the COSTALD correlation, the Lee-Kessler-Plöcker equation of state, and the Peng-Robinson equation of state. The best performance was shown by the EOS-LNG equation of state which is capable of predicting the liquid densities within the specified uncertainty of the model of 0.05 %. The other models, however, showed significant differences that disqualify for calculation within the p,T-region investigated of the gas mixtures.
Continuing our study on (CO2 + O2) mixtures, this work reports new experimental (p, rho, T) data for two oxygen-rich mixtures with mole fractions x(O2) = (0.50 and 0.75) mol·mol−1, in the temperature range T = (250–375) K and pressure range p = (0.5–20) MPa, using a single-sinker densimeter. Experimental density data were compared to two well-established equation-of-state models: EOS-CG and GERG-2008. In the p, T-range investigated, the EOS-CG gave a better reproduction for the equimolar mixture (x(O2) = 0.5), whereas the GERG-2008 performed significantly better for the oxygen-rich mixture (x(O2) = 0.75). The EOS-CG generally overestimates the density, while the GERG-2008 underestimates it. This complete set of new experimental data, together with previous measurements, is used to calculate the virial coefficients B(T, x) and C(T, x), as well as the second interaction virial coefficient B12(T) for the (CO2+ O2) system.
Solubility data of carbon dioxide (CO2) in the ionic liquid 1-ethyl-3-methylimidazolium methanesulfonate [EMIM][CH3SO3] at T= (273.15 to 413.15) K and pressures up to p= 5.0 MPa are reported. The solubility measurements were carried out using an isochoric method which operates in decrements of ΔT = 20 K within the investigated temperature range and at selected four different pressure steps ranging froma pressure p of around 5.0 MPa down to around 0.4 MPa. The solubility of CO2 in the ionic liquid monotonously decreases with increasing temperatures at a constant pressure. Within the p,T-range investigated, CO2 displayed a solubility in [EMIM] [CH3SO3] from a mole fraction x= 0.0160 mol·mol−1 and a corresponding molality m = 0.0791 mol·kg−1 at T = 413.15 K and p =0.432 MPa up to x = 0.4049 mol·mol−1 and m = 3.2982 mol·kg−1 at T = 293.15 K and p = 4.577 MPa. Henry's law constant was calculated from the solubility data reported here, and literature data were reviewed for comparison. Additionally, thermodynamic state properties that can be derived from Henry's law constant, such as the Gibbs energy of solvation ΔsolG, the enthalpy of solvation ΔsolH, the entropy of solvation ΔsolS, and the heat capacity of solvation ΔsolCp, were calculated.
This work aims to address the technical aspects related to the thermodynamic characterization of natural gas mixtures blended with hydrogen for the introduction of alternative energy sources within the Power-to-Gas framework. For that purpose, new experimental speed of sound data are presented in the pressure range between (0.1 up to 13) MPa and at temperatures of (260, 273.16, 300, 325, and 350) K for two mixtures qualified as primary calibration standards: a 11 component synthetic natural gas mixture (11 M), and another low-calorific H2-enriched natural gas mixture with a nominal molar percentage x(H2) = 3 %.
Measurements have been gathered using a spherical acoustic resonator with an experimental expanded (k = 2) uncertainty better than 200 parts in 106 (0.02 %) in the speed of sound. The heat capacity ratio as perfect-gas gammapg, the molar heat capacity as perfect-gas Cp,m pg, and the second betaa and third gammaa acoustic virial coefficients are derived from the speed of sound values. All the results are compared with the reference mixture models for natural gas-like mixtures, the AGA8-DC92 EoS and the GERG-2008 EoS, with Special attention to the impact of hydrogen on those properties. Data are found to be mostly consistent within the model uncertainty in the 11 M synthetic mixture as expected, but for the hydrogen-enriched mixture in the limit of the model uncertainty at the highest measuring pressures.
Novel MnS nanoclusters were synthesized on nickel foam (NF) using a successive ionic layer adsorption and reaction (SILAR) method. MnS nanoclusters with different sizes were obtained by varying the number of deposition cycles. The crystal structure, chemical composition, and surface microstructure of the electrodes were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field Emission scanning electron microscopy, and high-resolution transmission electron microscopy. The electrochemical behavior of the MnS nanoclusters was examined by cyclic voltammetry, galvanostatic charge–discharge, cycling test, and electrochemical impedance spectroscopy. The MnS nanoclusters prepared with 90 SILAR cycles showed the best supercapacitance in a 6 M KOH aqueous electrolyte with a specific capacitance of 828 F/g at a scan rate of 5 mV/s and cycling stability of 85.2 % after 5000 charge–discharge cycles.
Moreover, an asymmetric supercapacitor (ASC) was assembled with the as-prepared MnS electrode on NF as the positive electrode, hydrothermally prepared reduced graphene oxide (rGO) on NF as the negative electrode, and PVA–KOH gel as the electrolyte. The MnS@NF//rGO@NF ASC showed excellent electrochemical performance with maximum energy and power densities of 34.1 Wh/kg and 12.8 kW/kg, respectively. The ASC also showed a capacitive retention of 86.5 % after 2000 charge–discharge cycles, highlighting its practical application for energy storage.
Three-dimensional (3D) γ-MnO2@ZnFe2O4/reduced graphene oxide (rGO) nanohybrids were synthesized using a one-pot hydrothermal self-assembly method. The morphology and properties of the nanohybrids were investigated.
The synergistic interactions among γ-MnO2, ZnFe2O4, and rGO resulted in 3D nanoflakes distributed uniformly in the rGO structure with a thickness of approximately 2–5 nm, leading to a high surface area. The nanohybrid containing 10 wt. % rGO exhibited superior catalytic activities for phenol degradation through the activation of peroxymonosulfate (PMS) to generate active sulfate radicals (SO4 •–). Typically, 50 mL of a 20 ppm phenol solution was degraded completely and 85% of the carbon content had been mineralized in 30 min at 25 °C using 10 mg of the nanohybrid. The nanohybrid could be recovered easily using a magnet and reused, maintaining high stability during catalytic oxidation. The 3D γ-MnO2@ZnFe2O4/rGO nanohybrid catalyst could be applied to the removal of hard-to-degrade waste materials owing to its high efficiency and excellent reusability.
Supercapacitors are an emerging energy-storage system with a wide range of potential applications. In this study, highly porous nickel-cobalt-oxide@reduced graphene oxide (Ni-Co-O@RGO-s) nanosheets were synthesized as an active material for supercapacitors using a surfactant-assisted microwave irradiation technique. The RGO-modified nanocomposite showed a larger specific area, better conductivity, and lower resistivity than the unmodified nanocomposite because the RGO facilitated faster ion diffusion/transport for improved redox activity. The synergistic effect of Ni-Co-O@RGO-s resulted in a high capacitance of 1903 F/g (at 0.8 A/g) in a mixed KOH/redox active K3Fe(CN)6 electrolyte. The asymmetric Ni-Co-O@RGO-s//AC supercapacitor device yielded a high energy density and power density of 39 Wh/kg and 7500 W/kg, respectively. The porous structure and combination of redox couples from both the electrode and electrolyte provided a highly synergistic effect, which improved the performance of the supercapacitor device.
The present study investigated decoration of Cu(OH)₂ with different morphologies by copper precursors on 3D nickel foam. The Cu(OH)₂-A (nano flower)electrode showed an excellent capacitance of 1332 Fg⁻¹ at current density of 2 Ag⁻¹ compared to the Cu(OH)₂-C (nano ribbon, 1100 Fg⁻¹) and Cu(OH)₂-S (nano Long leaf, 1013 Fg⁻¹) electrodes. An asymmetric supercapacitor (ASC) was fabricated and showed a Maximum capacitance of 165 Fg⁻¹ at current density of 2 Ag⁻¹ with high energy density of 66.7 Wh kg⁻¹ and power density of 5698 W kg⁻¹ with excellent stability of 80 % after 10,000 cycles.
The GERG-2008 equation of state is the approved ISO standard (ISO 20765-2) for the calculation of thermophysical properties of natural gas mixtures. The composition of natural gas can vary considerably due to the diversity of origin. Further diversification was generated by adding hydrogen, biogas, or other non-conventional energy gases. In this work, high-precision experimental (p, rho, T) data for two gravimetrically prepared synthetic natural gas mixtures are reported. One mixture resembled a conventional natural gas of 11 components (11 M) with a nominal mixture composition (amount-of-substance fraction) of 0.8845 for methane as the matrix compound with the other compounds being 0.005 for oxygen, 0.04 for nitrogen, 0.015 for carbon dioxide, 0.04 for ethane, 0.01 for propane, 0.002 each for n- and isobutane, and ultimately 0.0005 each for isopentane, n-pentane, and nhexane. The other mixture was a 13-component hydrogen-enriched natural gas with a low calorific value featuring a nominal composition of 0.7885 for methane, 0.03 for hydrogen, 0.005 for helium, 0.12 for nitrogen, 0.04 for carbon dioxide, 0.0075 for ethane, 0.003 for propane, 0.002 each for n- and isobutane, and 0.0005 each for neopentane, isopentane, npentane, and n-hexane. Density measurements were performed in an isothermal operational mode at temperatures between 260 and 350 K and at pressures up to 20 MPa by using a single-sinker densimeter with magnetic suspension coupling. The data were compared with the corresponding densities calculated from both GERG-2008 and AGA8-DC92 equations of state to test their performance on real mixtures. The average absolute Deviation from GERG-2008 (AGA8-DC92) is 0.027% (0.078%) for 11 M and 0.095% (0.062%) for the 13-component H2-enriched mixture, respectively. The corresponding maximum relative Deviation from GERG-2008 (AGA8-DC92) amounts to 0.095% (0.127%) for 11 M and 0.291% (0.193%) for the H2-enriched mixture.