An insight into the role of the association equations of states in gas hydrate modeling:a review

Encouraged by the wide spectrum of novel applications of gas hydrates,e.g.,energy recovery,gas separation,gas storage,gas transportation,water desalination,and hydrogen hydrate as a green energy resource,as well as CO2 capturing,many scientists have focused their attention on investigating this important phenomenon.Of course,from an engineering viewpoint,the mathematical modeling of gas hydrates is of paramount importance,as anticipation of gas hydrate stability conditions is effective in the design and control of industrial processes.Overall,the thermodynamic modeling of gas hydrate can be tackled as an equilibration of three phases,i.e.,liquid,gas,and solid hydrate.The inseparable component in all hydrate systems,water,is highly polar and non-ideal,necessitating the use of more advanced equation of states(EoSs) that take into account more intermolecular forces for thermodynamic modeling of these systems.Motivated by the ever-increasing number of publications on this topic,this study aims to review the application of associating EoSs for the thermodynamic modeling of gas hydrates.Three most important hydrate-based models available in the literature including the van der Waals-Platteeuw(vdW-P) model,Chen-Guo model,and Klauda-Sandler model coupled with and SAFT EoSs were investigated and compared with cubic EoSs.It was concluded that the CPA and SAFT EoSs gave very accurate results for hydrate systems as they take into account the association interactions,which are very crucial in gas hydrate systems in which water,methanol,glycols,and other types of associating compounds are available.Moreover,it was concluded that the CPA EoS is easier to use than the SAFT-type EoSs and our suggestion for the gas hydrate systems is the CPA EoS.

New insight into prediction of phase behavior of natural gas hydrate by different cubic equations of state coupled with various mixing rules

Progress in hydrate thermodynamic study necessitates robust and fast models to be incorporated in reservoir simulation softwares. However, numerous models presented in the literature makes selection of the best,proper predictive model a cumbersome task. It is of industrial interest to make use of cubic equations of state(EOS) for modeling hydrate equilibria. In this regard, this study focuses on evaluation of three common EOSs including Peng–Robinson, Soave–Redlich–Kwong and Valderrama–Patel–Teja coupled with van der Waals and Platteeuw theory to predict hydrate P–T equilibrium of a real natural gas sample. Each EOS was accompanied with three mixing rules, including van der Waals(vd W),Avlonitis non-density dependent(ANDD) and general nonquadratic(GNQ). The prediction of cubic EOSs was in sufficient agreement with experimental data and with overall AARD% of less than unity. In addition, PR plus ANDD proved to be the most accurate model in this study for prediction of hydrate equilibria with AARD% of 0.166.It was observed that the accuracy of cubic EOSs studied in this paper depends on mixing rule coupled with them,especially at high-pressure conditions. Lastly, the present study does not include any adjustable parameter to be correlated with hydrate phase equilibrium data.

Evaluation of attraction terms in equations of state on the prediction of solubility of some biomolecules in supercritical carbon dioxide

In the present work, effect of the attraction terms of four recently modified Peng-Robinson （MPR） equations of state on the prediction of solubility of caffeine, cholesterol, uracil and erythromycin was studied. The attraction terms of two of these equations are linear relative to the acentric factor and for the other two are exponential. It is found that the later show less deviation. Also interaction parameters for the studied systems are obtained and the percentage of average absolute relative deviation （%AARD） in each calculation is displayed.

How far away are accurate equations of state determinations? Some issues on pressure scales and non-hydrostaticity in diamond anvil cells

The equations of state(EOSs)of materials are the cornerstone of condensed matter physics,material science,and geophysics.However,acquiring an accurate EOS in diamond anvil cell(DAC)experiments continues to prove problematic because the current lack of an accurate pressure scale with clarified sources of uncertainty makes it difficult to determine a precise pressure value at high pressure,and nonhydrostaticity affects both the volume and pressure determination.This study will discuss the advantages and drawbacks of various pressure scales,and propose an absolute pressure scale and correction methods for the effects of non-hydrostaticity.At the end of this paper,we analyze the accuracy of the determined EOS in the DAC experiments we can achieve to date.

Influence of Different Equations of State on Simulation Results of Supercritical CO_(2) Centrifugal Compressor

Supercritical CO_(2)(SCO_(2))Brayton cycle has received more and more attention in the field of power generation due to its high cycle efficiency and compact structure.SCO_(2) compressor is the core component of the cycle,and the improvement of its performance is the key to improving the efficiency of the entire cycle.However,the operation of the SCO_(2) compressor near the critical point has brought many design and operation problems.Based on the Reynolds Averaged Navier-Stokes(RANS)model,the performance and flow field of SCO_(2) centrifugal compressors based on different CO_(2) working fluid models are numerically investigated in this paper.The stability and convergence of the compressor steady-state simulation are also discussed.The results show that the fluid based on the Span-Wanger(SW)equation can obtain a more ideal compressor performance curve and capture a more accurate flow field structure,while the CO_(2) ideal gas is not suitable for the calculation of SCO_(2) centrifugal compressors.But its flow field can be used as the initial flow field for numerical calculation of centrifugal compressor based on CO_(2) real gas.

Implications of neutron skin measurements on Skyrme equations of state

The recent measurements of neutron skins via parity violation in electron scattering have extracted an abnormally thick neutron skin for 208 Pb,which has significant consequences in nuclear equation of state(EoS)and neutron star observations.In this study,we perform optimizations of extended Skyrme forces in a consistent manner by including neutron skin thicknesses from PREX-Ⅱand CREX experiments and investigate nuclear EoSs and neutron stars in the GW170817 event By varying the fitting weights of neutron skins,several new Skyrme parameterizations are obtained.Our results show the competition in the fitting procedure to simultaneously describe neutron skins,other properties of finite nuclei,and neutron star observations.The prospects of resolving neutron skin issues are also discussed.

Experimental study on the size effect on the equation of state of concretes under shock loading

Adopting the classical theory of hydrocodes,the constitutive relations of concretes are separated into an equation of state(EoS)which describes the volumetric behavior of concrete material and a strength model which depicts the shear properties of concrete.The experiments on the EoS of concrete is always challenging due to the technical difficulties and equipment limitations,especially for the specimen size effect on the EoS.Although some researchers investigate the shock properties of concretes by fly-plate impact tests,the specimens used in their tests are usually in one size.In this paper,the fly-plate impact tests on concrete specimens with different sizes are performed to investigate the size effect on the shock properties of concrete materials.The mechanical background of the size effect on the shock properties are revealed,which is related to the lateral rarefaction effect and the deviatoric stress produced in the specimen.According to the tests results,the modified EoS considering the size effect on the shock properties of concrete are proposed,which the bulk modulus of concrete is unpredicted by up to 20% if size effects are not accounted for.

Semiempirical equations of state of H_(2)O/CO_(2) binary mixtures in graphite nanoslits

The existence of confining walls limits the prediction accuracy of nanoconfined fluids using macroscopic equations of state(EOSs);moreover,appropriate EOSs for multicomponent mixture fluids in nanoconfined spaces are missing.Here,we derive the EOS of multicomponent mixture fluids confined in nanospaces at high temperatures and pressures,mainly considering the nanoconfinement effect and the competitive adsorption effect between different components.Then,the EOSs are validated through comparison with the molecular dynamics-simulated Pv T data of CO_(2)/H_(2)O mixtures in graphite nanoslits.To consider the above effects,we derive two EOSs via two modeling methods:EOS I is obtained through modification of the actual component occupation volume in the Peng-Robinson equation of state(PR EOS)by fitting the binary component interaction coefficient and the number of adsorbed molecules according to a selectivity coefficient,while EOS II is obtained by considering the decreased pressure of the fluids in PR EOS by adding an attractive term between components and walls.With the simulation results as a benchmark,the two EOSs exhibited good prediction accuracies under low CO_(2) concentrations,and generally,EOS II was more accurate than EOS I.This study fills the gap in the EOSs of nanoconfined mixture fluids,and the obtained equations can help to further describe the thermodynamic properties of confined mixture fluids.

Hydration Effect on Equations of State for Minerals in the Peridotite System:Implication for Geotherms in the Mantle

Water in the deep Earth’s interior has important and profound impacts on the geodynamical properties at high-temperature(T)and high-pressure(P)conditions.A series of dense hydrous Mg-silicate(DHMS)phases are generated from dehydration of serpentines in subduction slabs below the lithosphere,including phase A,chondrodite,clinohumite,phase E,superhydrous phase B and phase D.On the other hand,olivine and its high-P polymorphs of wadsleyite and ringwoodite are dominant nominally anhydrous minerals(NAMs)in the upper mantle and transition zone,which could contain significant amount of water in the forms of hydroxyl group(OH-)defects.The water solubilities in wadsleyite and ringwoodite are up to about 3 weight percent(wt.%),making the transition zone a most important layer for water storage in the mantle.Hydration can significantly affect the pressure-volumetemperature equations of state(P-V-T EOSs)for the DHMS and NAM phases,including the thermal expansivities and isothermal bulk moduli.In this work,we collected the reported datasets for the DHMS and NAM phases,and reconstruct internally consistent EOSs.Next,we further evaluated the thermodynamic Grüneisen parameters,which are fundamental for constraining the temperature distribution in an isentropic process,such as mantle convection.The adiabatic temperature profiles are computed for these minerals in the geological settings of normal mantle and subduction zone,and our calculation indicates that temperature is the dominant factor in determining the gradient of a geotherm,rather than the mineralogical composition.

LOCV calculation of the equations of state and properties of rapidly rotating neutron stars

In this paper, we have investigated the structural properties of rotating neutron stars using the numerical RNS code and equations of state which have been calculated within the lowest order constrained variational（LOCV）approach. In order to calculate the equation of state of nuclear matter, we have used UV（14） ＋TNI and AV（18） potentials.We have computed the maximum mass of the neutron star and the corresponding equatorial radius at different angular velocities. We have also computed the structural properties of Keplerian rotating neutron stars for the maximum mass configuration, MK, RK, fK and jmax.

Thermodynamic study of fluid in terms of equation of state containing physical parameters

We introduce a simple condition for one mole fluid by considering the thermodynamics of molecules pointing towards the effective potential for the cluster. Efforts are made to estimate new physical parameter f in liquid state using the equation of state containing only two physical parameters such as the hard sphere diameter and binding energy. The temperature dependence of the structural properties and the thermodynamic behavior of the clusters are studied. Computations based on f predict the variation of numbers of particles at the contact point of the molecular cavity（radial distribution function）.From the thermodynamic profile of the fluid, the model results are discussed in terms of the cavity due to the closed surface along with suitable energy. The present calculation is based upon the sample thermodynamic data for n-hexanol, such as the ultrasonic wave, density, volume expansion coefficient, and ratio of specific heat in the liquid state, and it is consistent with the thermodynamic relations containing physical parameters such as size and energy. Since the data is restricted to n-hexanol, we avoid giving the physical meaning of f, which is the key parameter studied in the present work.

Basic quantities of the equation of state in isospin asymmetric nuclear matter

Based on the Hugenholtz-Van Hove theorem six basic quantities of the EoS in isospin asymmetric nuclear matter are expressed in terms of the nucleon kinetic energy t(k),the isospin symmetric and asymmetric parts of the single-nucleon potentials U_(0)(ρ,k)and U_(sym,i)(ρ,k).The six basic quantities include the quadratic symmetry energy E_(sym,2)(ρ),the quartic symmetry energy E_(sym,4)(ρ),their corresponding density slopes L_(2)(ρ)and L_(4)(ρ),and the incompressibility coefficients K_(2)(ρ)and K_(4)(ρ).By using four types of well-known effective nucleon-nucleon interaction models,namely the BGBD,MDI,Skyrme,and Gogny forces,the density-and isospin-dependent properties of these basic quantities are systematically calculated and their values at the saturation density q_(0)are explicitly given.The contributions to these quantities from t(k)U_(0)(ρ,k),and U_(sym,i)(ρ,k)are also analyzed at the norma nuclear density q_(0).It is clearly shown that the first-order asymmetric term U_(sym,1)(ρ,k)(also known as the symmetry potential in the Lane potential)plays a vital role in determining the density dependence of the quadratic symmetry energy E_(sym,2)(ρ).It is also shown that the contributions from the high-order asymmetric parts of the single-nucleon potentials(U_(sym,i)(ρ,k)with i>1)cannot be neglected in the calculations of the other five basic quantities Moreover,by analyzing the properties of asymmetric nuclear matter at the exact saturation densityρ_(sat)(δ),the corresponding quadratic incompressibility coefficient is found to have a simple empirical relation K_(sat,2)=K_(2)(ρ_(0))-4.14L_(2)(ρ_(0))

Validation for equation of state in wide regime:Copper as prototype

In this paper we introduce the wide regime equation of state(WEOS)developed in Institute of Applied Physics and Computational Mathematics(IAPCM).A semi-empirical model of the WEOS is given by a thermodynamically complete potential of the Helmholtz free energy which combines several theoretical models and has some adjustable parameters calibrated via some experimental and theoretical data.The validation methods of the equation of state in wide regime are presented using copper as a prototype.The results of the WEOS are well consistent with the available theoretical and experimental data,including ab initio cold curve under compression,isotherm,Hugoniot,off-Hugoniot and sound velocity data.It enhances our confidence in the accuracy of the WEOS,which is very important for the validation and verification of equation of state in high temperature and pressure technology.

A compositional model for CO_(2) ooding including CO_(2) equilibria between water and oil using the Peng–Robinson equation of state with the Wong–Sandler mixing rule

This paper presents a three-dimensional, three-phase compositional model considering CO2 phase equilibrium between water and oil. In this model, CO2 is mutually soluble in aqueous and hydrocarbon phases, while other components, except water,exist in hydrocarbon phase. The Peng–Robinson(PR) equation of state and the Wong–Sandler mixing rule with non-random two-liquid parameters are used to calculate CO2 fugacity in the aqueous phase. One-dimensional and three-dimensional CO2 flooding examples show that a significant amount of injected CO2 is dissolved in water. Our simulation shows 7% of injected CO2 can be dissolved in the aqueous phase, which delays oil recovery by 4%. The gas rate predicted by the model is smaller than the conventional model as long as water is undersaturated by CO2, which can be considered as 'lost' in the aqueous phase. The model also predicts that the delayed oil can be recovered after the gas breakthrough, indicating that delayed oil is hard to recover in field applications. A three-dimensional example reveals that a highly stratified reservoir causes uneven displacement and serious CO2 breakthrough. If mobility control measures like water alternating gas are undertaken, the solubility e ects will be more pronounced than this example.

Derivation of Martin-Hou Equation of State from Hard-particle Perturbation Theory

In this paper, the Martin-Hou equation of state is derived by using a power series representation of radial distribution function and an analytic representation of multi-section potential based on the Barker-Henderson hard-particle perturbation theory including high-order terms. In the derivation, a theoretical form of Martin-Hou equation was obtained. It had a similar form and the same capability to predict P-V-T properties as the Martin-Hou equation and no additional data were required for evaluating the constants. The characteristic constants of the theoretical expression have certain relationships with the molecular parameters.

Thermal equation of state for lattice Boltzmann gases

The Galilean invariance and the induced thermo-hydrodynamics of the lattice Boltzmann Bhatnagar-Gross-Krook model are proposed together with their rigorous theoretical background. From the viewpoint of group invariance, recovering the Galilean invariance for the isothermal lattice Boltzmann Bhatnagar-Gross-Krook equation （LBGKE） induces a new natural thermal-dynamical system, which is compatible with the elementary statistical thermodynamics.

EQUATION OF STATE CALCULATIONS FOR HOT, DENSE MATTER AT ARBITRARY DENSITIES AND TEMPERATURES

Within the approximations of spherical lattice cell, central-field, and relativistic Fermi statis- tics, an algorithm with average atom model is presented to calculate the electronic energy levels and equation of state for hot and dense matter at arbitrary densities and temperatures. Choosing Zink's analytical potential as initial potential, we have solved the Dirac-Slater equation which satisfies the Weigner-Seitz boundary condition. The electronic energy bands are not taken into account. Tak- ing energy level degeneracy as a continuous function of density, we have considered the pressure ionization effects for highly dense matter. Results for ^(13)Al atom are shown.

Numerical method of the Riemann problem for two-dimensional multi-fluid flows with general equation of state

Based on the classical Roe method, we develop an interface capture method according to the general equation of state, and extend the single-fluid Roe method to the two-dimensional （2D） multi-fluid flows, as well as construct the continuous Roe matrix for the whole flow field. The interface capture equations and fluid dynamic conservative equations are coupled together and solved by using any high-resolution schemes that usually suit for the single-fluid flows. Some numerical examples are given to illustrate the solution of 1D and 2D multi-fluid Riemann problems.

Thermal equation of state of a natural kyanite up to 8.55 GPa and 1273 K

The thermal equation of state of a natural kyanite has been investigated with a DIA-type,cubic-anvil apparatus(SAM85)combined with an energy-dispersive synchrotron X-ray radiation technique up to 8.55 GPa and 1273 K.No phase transition was observed in the studied pressure-temperature(P-T)range.The Le Bail full profile refinement technique was used to derive the unit-cell parameters.By fixing the bulk modulus K 0 as 196 GPa and its pressure derivative K0 as 4,our P-V(volume)-T data were fitted to the high temperature BircheMurnaghan equation of state.The obtained parameters for the kyanite are:V_(0)=294.05(9)Å^(3),a=2.53(11)×10^(-5)K^(-1) and(K/T)P=-0.021(8)GPa∙K^(-1).These parameters have been combined with other experimentally-measured thermodynamic data for the relevant phases to calculate the P-T locus of the reaction kyanite¼stishoviteþcorundum.With this thermodynamically constrained phase boundary,previous high-pressure phase equi-librium experimental studies with the multi-anvil press have been evaluated.

Coupled thermo-hydro-mechanical simulation of CO2 enhanced gas recovery with an extended equation of state module for TOUGH2MP-FLAC3D

As one of the most important ways to reduce the greenhouse gas emission,carbon dioxide（CO2）enhanced gas recovery（CO2-EGR） is attractive since the gas recovery can be enhanced simultaneously with CO2sequestration.Based on the existing equation of state（EOS） module of TOUGH2 MP,extEOS7C is developed to calculate the phase partition of H2O-CO2-CH4-NaCl mixtures accurately with consideration of dissolved NaCI and brine properties at high pressure and temperature conditions.Verifications show that it can be applied up to the pressure of 100 MPa and temperature of 150℃.The module was implemented in the linked simulator TOUGH2MP-FLAC3 D for the coupled hydro-mechanical simulations.A simplified three-dimensional（3D）1/4 model（2.2 km×1 km×1 km） which consists of the whole reservoir,caprock and baserock was generated based on the geological conditions of a gas field in the North German Basin.The simulation results show that,under an injection rate of 200,000 t/yr and production rate of 200,000 sm3/d,CO2breakthrough occurred in the case with the initial reservoir pressure of 5 MPa but did not occur in the case of 42 MPa.Under low pressure conditions,the pressure driven horizontal transport is the dominant process;while under high pressure conditions,the density driven vertical flow is dominant.Under the considered conditions,the CO2-EGR caused only small pressure changes.The largest pore pressure increase（2 MPa） and uplift（7 mm） occurred at the caprock bottom induced by only CO2injection.The caprock had still the primary stress state and its integrity was not affected.The formation water salinity and temperature variations of ±20℃ had small influences on the CO2-EGR process.In order to slow down the breakthrough,it is suggested that CO2-EGR should be carried out before the reservoir pressure drops below the critical pressure of CO2.