Intrinsic correlation between the generalized phase equilibrium condition and mechanical behaviors in hydrate-bearing sediments

The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs.In heating closed systems,the temperature-pressure path of hydrate-bearing sediment deviates from that of pure bulk hydrate,reflecting the porous media effect in phase equilibrium.A generalized phase equilibrium equation was established for hydrate-bearing sediments,which indicates that both capillary and osmotic pressures cause the phase equilibrium curve to shift leftward on the temperature-pressure plane.In contrast to bulk hydrate,hydrate-bearing sediment always contains a certain amount of unhydrated water,which keeps phase equilibrium with the hydrate within the hydrate stability field.With changes in temperature and pressure,a portion of pore hydrate and unhydrated water may transform into each other,affecting the shear strength of hydrate-bearing sediment.A shear strength model is proposed to consider not only hydrate saturation but also the change in temperature and pressure of hydrate-bearing sediment.The model is validated by experimental data with various hydrate saturation,temperature and pressure conditions.The deformation induced by partial dissociation was studied through depressurization tests under constant effective stress.The reduction in gas pressure within the hydrate stability field indeed caused sediment deformation.The dissociation-induced deformation can be reasonably estimated as the difference in volume between hydrate-bearing and hydrate-free sediments from the compression curves.

Calculation of the Phase Equilibrium of CO2–Hydrocarbon Binary Mixtures by PR-BM EOS and PR EOS

The phase equilibrium data of CO2 hydrocarbon binary mixtures are important for the design and operation of CO 2 ood- ing, coal liquefaction, and supercritical extraction processes. Numerous pieces of binary phase equilibrium data have been obtained. Thus, models for the accurate calculation of binary and multicomponent mixtures must be developed on the basis of existing data. In this work, 3578 vapor liquid phase equilibrium data points for 10 CO 2 hydrocarbon binary mixtures, including CO2 butane, CO 2 pentane, CO 2 isopentane, C O 2 hexane, CO 2 benzene, CO 2 heptane, CO 2 octane, C O 2 non- ane, CO 2 decane, and C O 2 undecane, were collected. The PR and PR-BM equations of state (EOS) in combination with relevant mixing rules were used to calculate the phase equilibrium data of the CO 2 hydrocarbon binary mixtures. The binary interaction parameter k ij in the PR EOS was temperature independent, whereas parameters in the PR-BM EOS were functions of temperature. Thus, the phase equilibrium data and other thermodynamic properties of the binary and multicomponent mixtures at di erent temperatures and pressures can be calculated by using the parameters obtained in this work. The PR-BM EOS performed better than the PR EOS, and the average absolute deviations over the temperature range of 255.98 408.15 K calculated by the PR EOS and PR-BM EOS were less than 5.74% and 3.36%, respectively. The results calculated by the two EOS were compared with those calculated by other models, such as PPR78, PR + LCVM + UNIFAC, KIE + PR EOS + HV, and PSRK. The phase equilibrium data of CO 2 butane decane, CO 2 hexane decane, and C O 2 octane decane ternary mixtures were calculated by the two EOS. The average overall deviations for the CO 2 mole fractions calculated by the two EOS were less than 7.66%.

Study on Phase Equilibrium Properties for CO_(2)^+ Cosolvent Binary Systems

In this study, the constant volume, visual method is used to measure the critical point of CO2+toluene, CO2+cyclohexane, CO2+n-butyraldehyde, CO2+i-butyraldehyde, CO2+methanol and CO2+alcohol binary systems. The relationship between critical point and the concentration of the entrainer for different substances has been discussed, and the comparison of the phase behavior of single component system and that of binary systems have been carried out.

Discussion on the Non-Equilibrium Phase of the Gliding Arc Plasma Driven by the Transverse Magnetic Field

a gliding arc driven by the transverse magnetic field was ignited between the electrodes with a complicated shape at atmospheric pressure and a non-equilibrium plasma was gencrated. Under our experimental conditions, a phenomenon was clearly observed where the arc power decreased with the increase in arc voltage. As the arc voltage was higher than 3.375 kV, the are power acquired from the power supply decreased, and the arc plasma began to switch to a non-equilibrium phase. The existence of the non-equilibrium arc plasma was very short, about 10 ms in one gliding arc discharge cycle.

Equilibrium Diagram in the Presence of a Gaseous Phase and Its Application(Overview Part Ⅰ)

T or logp1/T diagrams showing the influence of temperature and pressure in a gaseous phase were presented in part Ⅰ of the overview. In part Ⅱ, the relationship between ET and Kellogg diagrams or between ET and EPh diagrams is discussed. ET diagrams cover larger field of application than the other two. The practical use of ET or logp1/T diagrams is also investigated, which includes: the calculation of polycomponent equilibria in a gaseous phase, the prediction of corrosion products, the interpretation of catalytic mechanism, the exploration for the possibility of producing aluminum with carbothermic method, etc. The limitation of this kind of diagrams is also discussed.

Phase Equilibrium and Phase Diagram of the Ternary System（MgCl2 + MgB2O4 + H2O） at 288 and 298 K

1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(Zheng&Tang,1988).Although some works on the ternary system

PHASE EQUILIBRIUM FOR THE TERNARY SYSTEM VINYL CHLORIDE-CHLORINATED POLYETHYLENE-POLY(VINYL CHLORIDE)

Swelling capacity of vinyl chloride (VC) in chlorinated polyethylene (CPE) with 25—40 wt% Cl at temperature 30—57℃ was studied and their relationships were correlated with Langmuir and Freundlich adsorption equations. A ternary phase diagram for VC-CPE-PVC was also established. In-situ polymerization conditions of CPE-g-VC were proposed and CPE content control was analyzed for the manufacturing process of CPE-g-VC graft product based on results of phase equilibrium study.

Phase Equilibrium of Isobutanol in Supercritical CO2

Vapor-liquid phase equilibrium data including composition,densities,molar volume and equilibrium constant of isobutanol in supercritical carbon dioxide from 313.2K to 353.2K were measured in a variable-volume visual cell.The properties of critical point were obtained by extrapolation.The results showed that critical temperature,critical pressure and critical compressibility factor of CO2-isobutanol system decreased with the increase of critical CO2 content.The phase equilibrium model was established by Peng-Robinson equation of state and van der Waals-2 mixing regulation,and model parameters were determined by optimization calculation of nonlinear least square method.The correlation between calculated values and the experimental data showed good agreement.

Non-equilibrium State Salt-forming Phase Diagram：Utilization of Bittern Resource in High Efficiency

Salt-forming regions for a complex salt-water system in non-equilibrium state of evaporation process are usually different from those in solubility diagrams.To understand the solid-forming region of NaCl and improve the utilization of bittern resources,experiments were carried out to evaporate 20 representative mixture solution samples of Na +,Mg 2+ //Cl-,2 4 SO-H2O system with an average evaporation intensity of(1.4±0.4) g·L-1 ·min-1(water) at boiling temperature 348 K,and determine the NaCl solid-forming regions in non-equilibrium state.Because of the complexity of salt-forming region,a maximal region and a minimal region were proposed to express the non-equilibrium state salt-forming region with different crystal seed,and a conditional salt-forming region was proposed to present the characteristic region of non-equilibrium salt-forming phase diagram.The areas of the maximal and minimal regions are 2.00 and 1.56 times those in solubility diagram,so it is possible to utilize bittern resources in high efficiency.The recovery rates of NaCl were 99.65%,93.14%,88.57%,72.76%,and 83.68%for six typical bittern sources from Tulantai Salt Lake(China),Dongtai Salt Lake(China) ,Jilantai Salt Lake(China),Qarun Salt Lake(Egypt) and seawater,respectively.It is testified that the non-equilibrium state salt-forming phase diagram can be used in industrial processes.

NON-CUBIC EQUATION OF STATE FOR PHASE EQUILIBRIUM CALCULATIONS

A new non-cubic equation of state is proposed for calculation of the thermodynamic properties ofnonpolar and polar fluids and their mixtures,including,saturated vapor pressure,saturated liquid volume,saturated vapor volume,heats of vaporization and vapor-liquid equilibria.The new equation is derived from thegeneralized van der Waals partition function in which the repulsive terms are expressed with the Carnahan andStarling equation for hard spheres,and the attractive terms are made up of the dispersive energy and theChemical association energy. The rules of dependence of parameters α and σ and on temperature are considered broadly so that the newequation yields good agreement with experimental saturated properties of 20 nonpolar and 27 polar fluids in therange of reduced temperatures of 0.5 to 1.0 The new equation with parameters group-contributed generally givessatisfactory predictions on saturated properties. Correlations of vapor-liquid equilibrium data for alcohol-containing systems by using van

PHASE EQUILIBRIUM OF COMPLEX MIXTURES WITH EQUATIONS OF STATE:AN UPDATE

Here we review a new class of mixing rules that have extended range of mixtures and condi-tions that can now be described by equation of state models.One characteristic of these mixing rulesis that they simultaneously satisfy the boundary conditions of producing a second virial coefficientthat is quadratic in mole fraction,and a free energy of mixing like that of an activity coefficientmodel at high density,though the mixing rule is itself independent of density.We show that usingthis mixing rule,various asymmetric,highly nonideal mixtures can be accurately described.Oneserendipitous result is that the parameters in this mixing rule model are almost independent oftemperature,which allows accurate extrapolations of phase behavior to be made over large ranges oftemperature and pressure.

EFFECTS OF ENTRAINERS ON THE PHASE EQUILIBRIUM OF SUPERCRITICAL FLUID EXTRACTION PROCESS

A flow apparatus was set up for measuring the solubility of a solid solute in a supercritical fluid withthe presence of a small amount of entrainer.The solubilities of biphenyl,diphenylamine and benzoic acid insupercritical carbon dioxide with one of the selected entrainers which were ethanol,acetone and n-hexanerespectively,were obtained in the pressure range of 10—32 MPa and the temperature range of 308—318K.Asolvolytic association theory has been proposed to explain the mechanism of entrainer effect,and theexperimental results were reasonably analysed.According to the solvolytic association theory,the association equa-tion of state was adopted to correlate the experimental data with good accuracy.

Phase Equilibrium of Mg-Zn-La System in Mg-Rich Corner from 200 to 350 ℃

Alloys of Mg-Zn-La system in Mg rich corner were prepared, and the phase relationship was investigated at different temperatures such as 200, 300 and 350 ℃ by scanning electron microscopy(SEM), X-ray diffraction(XRD) and electron probe microanalysis with energy dispersive X-ray spectroscopy (EPMA). Two types of phase equilibrium were identified at the different temperatures. One is two-phase equilibrium contained the Mg solid solution and T-phase. The other is three-phase equilibrium which contained the Mg solid solution, MgZn phase and T-phase. T-phase was stable as the temperature changed. The La content in T-phase is constant which is about 8±0.3% (atom fraction); but the Mg content and Zn content of that is changed, and the Zn content in T-phase was from 16.1% to 44%. The solubility of La in MgZn phase was increased from 1.2% to 1.6% as the temperature increasing from 200 to 350 ℃.

Stable Phase Equilibrium of the Aqueous Ternary System Li+//Cl-,borate- H2O at 348 K

The Sichuan Basin,with an area of about 20×104 km2,is situated at 102.5°~110°E and 27.67°~32.67°N.The underground brine resources in Sichuan basin are a type of comprehensive liquid mineral resource.Pingluo

Equilibrium Diagram in the Presence of a Gaseous Phase and Its Application(Overview Part Ⅱ)

オhis paper is the first part of an overview to introduce ET or logP-1/T thermodynamic diagrams which show the chemical and electrochemical equilibria in the presence of a gaseous phase. The established principles and methods of these two types of diagrams are explained. Some examples are also discussed.

LOCAL EQUILIBRIUM METHOD IN STUDYING PHASE DIAGRAM OF Mn-MnO SYSTEM

A special method based on the local equilibrium principle has been introduced in the research of the phase diagram of Mn-MnO system.With this method,the problems of volatilization of Mn and the corrosion of Mn and MnO to refractory materials were prevented efficiently.The solubility of oxygen in Mn and the composition of the interface between MnO and Mn were determined.Partial phase diagram of Mn-MnO system were constructed according to pres- ent experimental results.

Phase Equilibrium of Ternary Systems LaX_3-C_(18)H_(16)N_3O_2Cl-H_2O

Solubilities and refractive indices of saturated solutions of the ternary systems LaX 3 C 18 H 16 N 3O 2Cl(4 ( p chlorobenzoyl) aminoantipyrine H 2O(30 ℃; X=NO 3 -, Cl -) were determined. The incongruent compound, LaL 3(NO 3) 3 was discovered in the system LaL 3(NO 3) 3 L H 2O, while LaCl 3 L H 2O(L=4 ( p chlorobenzoyl) aminoantipyrine H 2O) is a simple eutonic system.

Relationship between CO_2 Sensor Voltage Response and Phase Equilibrium of Solid Electrolyte Na,K-β/β″-Al_2O_3

A type of CO2 sensor based on oxygen concentration cell was designed as following: Cell I: Pt | Au, O2, CO2| Na2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt or Cell lI: Pt|Au, O2, CO2|K2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt. (Na,K-β/β'-AI2O3 is named by NKBA). The sensor signal is consistent with the Nernstian slope within the region of phase equilibrium for Na, K-β/β'-AI2O3 material. The relationship between CO2 sensor voltage response and phase equilibrium of solid electrolyte Na, K-β/β-AI2O3 is discussed in this paper.

Influence of residual stress on the phase equilibrium of Ti(C_xN_y) thin films

In order to provide a theoretic basis for the research of Ti(C_xN_y) thinfilms, the thermodynamic database of Ti-C-N ternary system is established and the phase diagramsections are calculated. In addition to the assessed thermodynamic properties of Ti-C-N system, theinfluence of the residual strain energy of Ti(C_xN_y) thin films on the phase equilibria isanalyzed. The classical formula for calculating the elastic strain energy is expressed into aRedlich-Kister form in order to perform the thermodynamic and equilibrium calculations using theThermo-Calc software. Isothermal sections at 900 and 1100 K are calculated with this database andcompared with those calculated without considering the residual stress. As a result, with theaddition of strain energy delta-fcc Ti(C_xN_y) phase area shrinks. It is therefore concluded thatwith the influence of the residual stress in Ti(C_xN_y) thin solid film, the precipitation of puredelta film requires more precise control of composition.

EQUILIBRIUM PHASE DIAGRAMS IN SYSTEM CuO-PbO-Ag

Phase equilibrium in the ternary CuO-PbO-Ag system has been investigated using differential thermal analysis(DTA),thermogravimetry(TG),scanning electron microscopy(SEM) and X-ray diffraction(XRD) techniques.In the ternary CuO-PbO-Ag system,there is a eutectic reaction CuO+PbO+Ag=L at 750℃ and a composition of 12.04 mol.% Ag,16.35 mol.% CuO and 71.61 mol.% PbO.Two miscibility gaps near the two binary tie lines PbO-Ag and CuO-Ag were detected. No binary or ternary compound was detected in the ternary system.SEM and energy dispersive spectroscopy(EDS) confirm the presence of two liquid phases and the eutectic point.