Phase equilibrium data prediction and process optimizationin butadiene extraction process

In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction,a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile.The accuracy of five prediction methods,UNIFAC(UNIQUAC Functional-group Activity Coefficients),UNIFAC-LL,UNIFAC-LBY,UNIFAC-DMD and COSMO-RS,applied to the butadiene extraction process was verified using partial phase equilibrium data.The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system.COSMO-RS-predicted multiple systems showed good accuracy,and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method.The predicted phase equilibrium data were checked for consistency.The NRTL-RK(non-Random Two Liquid-Redlich-Kwong Equation of State)and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data.Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process.The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2%compared to that using the commercial simulation software,Aspen Plus and its database.The average deviation was much smaller than that of the simulations using the Aspen Plus database(>10%),indicating that the obtained phase equilibrium data are highly accurate and reliable.The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided.This improves the accuracy and reliability of the design,optimization and control of the process,and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.

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.

Alloy gene Gibbs energy partition function and equilibrium holographic network phase diagrams of Au_3Cu-type sublattice system

Taking Au3Cu-type sublattice system as an example, three discoveries have been presented. First, the fourth barrier to hinder the progress of metal materials science is that today’s researchers do not understand that the Gibbs energy function of an alloy phase should be derived from Gibbs energy partition function constructed of alloy gene sequence and their Gibbs energy sequence. Second, the six rules for establishing alloy gene Gibbs energy partition function have been discovered, and it has been specially proved that the probabilities of structure units occupied at the Gibbs energy levels in the degeneracy factor for calculating configuration entropy should be degenerated as ones of component atoms occupied at the lattice points. Third, the main characteristics unexpected by today’s researchers are as follows. There exists a single-phase boundary curve without two-phase region coexisting by the ordered and disordered phases. The composition and temperature of the top point on the phase-boundary curve are far away from those of the critical point of the Au3Cu compound; At 0 K, the composition of the lowest point on the composition-dependent Gibbs energy curve is notably deviated from that of the Au3Cu compounds. The theoretical limit composition range of long range ordered Au3Cu-type alloys is determined by the first jumping order degree.

Alloy gene Gibbs energy partition function and equilibrium holographic network phase diagrams of AuCu_3-type sublattice system

Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing experimental phenomena of alloy phase transitions during extremely slow variation in temperature by equilibrium thinking mode and then taking erroneous knowledge of experimental phenomena as selected information for establishing Gibbs energy function and so-called equilibrium phase diagram. Second, the equilibrium holographic network phase diagrams of AuCu3-type sublattice system may be used to describe systematic correlativity of the composition?temperature-dependent alloy gene arranging structures and complete thermodynamic properties, and to be a standard for studying experimental subequilibrium order-disorder transition. Third, the equilibrium transition of each alloy is a homogeneous single-phase rather than a heterogeneous two-phase, and there exists a single-phase boundary curve without two-phase region of the ordered and disordered phases; the composition and temperature of the top point on the phase-boundary curve are far away from the ones of the critical point of the AuCu3 compound.

Purification of Inositol. Studies on the Phase Equilibrium of the System C 6H 12 O 6 NH 4Cl C 2H 5OH H 2O(C 2H 5 OH/H 2O =0.90, by wt ) at 35℃

The solubilities and the refractive indices of the saturated solution in the system C 6H 12 O 6 NH 4Cl C 2H 5OH-H 2O ( C 2H 5OH / H 2O=0.90, by wt ) at 35℃ have been determined. The isotherms and refractive indices of the system at 35℃ consist of 2 branches, corresponding to C 6H 12 O 6( H 2O and NH 4Cl. The composition of eutectic solution is C 6H 12 O 6: 4.40 %, NH 4Cl: 13.86 %, C 2H 5OH: 38.88 %.

Phase equilibrium of CaSO_4Ca(OH)_2-H_2O system

In order to provide the theoretical guidance for applying the neutralization method to treatment of heavy metals wastewater with high concentration of sulfate, and to better understand the mechanism of calcium sulfate scale formation, the equilibrium solubility data of CaSOa-Ca（OH）2-H2O system at 298.15 K were theoretically calculated via the Pitzer semi-empirical ion-interaction theory, and determined experimentally by the optical method combining with X-ray diffractometry, and the calculated and determined phase diagrams of CaSOa-Ca（OH）2-H2O system were plotted and compared. Physical definition of each area was studied, and the physical law of characteristic point and line was explained in detail. Adjusting the pH value of neutralization-hydrolysis solution depended on the SO4z- concentration in the system. And interaction characteristics between the solubilities of CaSO4（s）and Ca（OH）2（s）were found out.

Phase equilibria of slag systems“FeO”−SiO_(2)−CaO−Al_(2)O_(3)and“FeO”−SiO_(2)−CaO−MgO at 1200℃and p(O_(2))of 10^(−7)kPa

High-temperature experiments were carried out for the slag systems of“FeO”−SiO_(2)−CaO−Al_(2)O_(3)and“FeO”−SiO_(2)−CaO−MgO at 1200℃and p(O_(2))of 10^(−7)kPa.The equilibrated samples were quenched,and the phase compositions were measured by electron probe microanalysis(EPMA).A series of pseudo-ternary and pseudo-binary phase diagrams are constructed to demonstrate their applications in copper smelting process and evaluation of the thermodynamic database.Spinel and tridymite are identified to be the major primary phases in the composition range related to the copper smelting slags.It is found that the operating window of the smelting slag is primarily determined by w_(Fe)/w_(SiO_(2))ratio in the slag.Both MgO and Al_(2)O_(3)in the slag reduce the operating window which requires extra fluxing agent to keep the slag to be fully liquid.Complex spinel solid solutions cause inaccurate predictions of the current thermodynamic database.

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.

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

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.

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.

Deviation of Carbon Dioxide-Water Gas-Liquid Balance from Thermodynamic Equilibrium in Turbulence h Experiment and Correlation

The carbon dioxide-water system was used to investigate the flowing gas-liquid metastable state. The experiment was carded out in a constant volume vessel with a horizontal circulation pipe and a peristaltic pump forced CO2 saturated water to flow. The temperature and pressure were recorded. The results showed that some CO2 escaped from the water in the flow process and the pressure increased, indicating that the gas-liquid equilibrium was broken. The amount of escaped CO2 varied with flow speed and reached a limit in a few minutes, entitled dy- namic equilibrium. Temperature and liquid movement played the same important role in breaking the phase equilib- rium. Under the experimental conditions, the ratio of the excessive carbon dioxide in the gas phase to its thermody- namic equilibrium amount in the liquid could achieve 15%.

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 studies of titanomagnetite and ilmenite smelting slags

The phase equilibrium information of slag plays an important role in pyrometallurgical processes to obtain optimum fluxing conditions and operating temperatures.The smelting reduction of titanomagnetite and ilmenite ores in an iron blast furnace(BF)can form Ti(C,N)particles,causing the increased viscosities of slag and hot metal.HIsmelt has been developed in recent years for ironmaking and does not need coke and sinter.The formation of Ti(C,N)in the HIsmelt process is avoided because the oxygen partial pressure in the process is higher than that in the BF.The smelting of TiO_(2)-containing ores in the HIsmelt process results in Al_(2)O_(3)-MgO-SiO_(2)-CaO-TiO_(2)slag.Phase equilibrium in this slag system has been investigated using equilibration,quenching,and electron probe microanalysis techniques.The experimental results were presented in two pseudo-binary sections,which represent the process of HIsmelt for the treatment of 100%titanomagnetite ore and mixed titanomagnetite+ilmenite ore(mass ratio of 2:1),respectively.The primary phases observed in the composition range investigated include pseudo-brookite M_(3)O_(5)(MgO·2TiO_(2)-Al_(2)O_(3)·TiO_(2)),spinel(MgO·Al_(2)O_(3)),perovskite CaTiO_(3),and rutile TiO_(2).The results show that the liquidus temperatures decrease in the TiO_(2)and M_(3)O_(5) primary phase fields and increase in the spinel and CaTiO_(3)primary phase fields with the increase in CaO concentration.The calculation of solid-phase fractions from the experimental data has been demonstrated.The effect of basicity on the liquidus temperatures of the slag has been discussed.The smelting of titanomagnetite plus ilmenite ores has significant advantages to obtain low-sulfur hot metal and high-TiO_(2)slag.Experimentally determined liquidus temperatures were compared with the FactSage predictions to evaluate the existing thermodynamic databases.

Solid–liquid equilibrium of dimethyl terephthalate(DMT), dimethyl isophthalate(DMI) and dimethyl phthalate(DMP) in melt crystallization process

The binary solid-liquid equilibrium of Dimethyl Terephthalate （DMT）, Dimethyl lsophthalate （DMI） and Dimeth- yl Phthalate （DMP） was investigated by experiment and differential scanning calorimetry （DSC）. The result demonstrated DMT/DMI and DMT/DMP systems are eutectic while DMI/DMP is a solid-solution system. The eutectic temperature of DMT/DMI system is 336.7 K and that of DMT/DMP is 271.1 K. Furthermore, a classical solid-liquid phase equilibrium model was used to fit the experimental data of the eutectic systems of DMT/DMI and DMT/ DMP and the theoretical model could describe the eutectic solid-liquid phase diagrams properly.

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

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 ℃.

Phase equilibrium modelling of the amphibolite facies metamorphism in the Yelapa-Chimo Metamorphic Complex, Mexico

The Yelapa-Chimo Metamorphic Complex forms part of the Jalisco Block in western Mexico and exposes a wide range of Early Cretaceous metamorphic rocks;such as paragneiss,orthogneiss,amphibolites,and migmatites.However,the pressure-temperature(P-T)conditions of metamorphism and partial melting remain poorly studied in the region.To elucidate metamorphic P-T conditions,phase equilibrium modelling was applied to two sillimanite-garnet paragneisses,one amphibole-orthogneiss,and one amphibolite.Sillimanite-garnet paragneisses exhibit a lepidoblastic texture with a biotite+sillimanite+kyanite+garnet+quartz+plagioclase+K-feldspar mineral assemblage.Amphibole-orthogneiss and amphibolite display a nematoblastic texture with an amphibole+(1)plagioclase+quartz+(1)titanite assemblage and an amphibole+(2)plagioclase+(2)titanite+ilmenite retrograde mineral assemblage.Pseudosections calculated for the two sillimanite-garnet paragneiss samples show P-T peak conditions at~6-7.5 kbar and~725-740℃.The results for amphibole-orthogneiss and the amphibolite yield P-T peak conditions at~8.5-10 kbar and~690-710℃.The mode models imply that metasedimentary and metaigneous units can produce up to~20 vol%and~10 vol%of melt,respectively.Modelling within a closed system during isobaric heating suggests that melt compositions of metasedimentary and metaigneous units are likely to have direct implications for the petrogenesis of the Puerto Vallarta Batholith.Our new data indicate that the Yelapa-Chimo Metamorphic Complex evolved through a metamorphic gradient between~23-33℃km^-1and the metamorphic rocks formed at depths between~22 km and~30 km with a burial rate of~2.0 km Ma^-1.Finally,the P-T data for both metasedimentary and metaigneous rocks provide new constraints on an accretionary framework,which is responsible for generating metamorphism and partial melting in the YelapaChimo Metamorphic Complex during the Early Cretaceous.

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.

Ternary Liquid-Liquid Equilibrium for Systems of Fatty Acid Methyl Ester(Methyl Palmitate/Methyl Stearate)+Ethanol+Glycerol at Atmospheric Pressure

Liquid-liquid equilibrium data of two ternary systems methyl palmitate+ethanol+glycerol and methyl stearate+ethanol+glycerol at(318.2 and 333.2)K and atmospheric pressure were measured. The values of distribution coefficient and selectivity were calculated, which indicates that glycerol can be separated from fatty acid ester by using ethanol as an extraction solvent. The consistency of the isothermal tie-line data were checked by the Othmer-Tobias equation. The correlation coefficients R2 are higher than 0.993,9 for all the fitted curves. The NRTL activity coefficient model was applied to the correlation of the measured tie-line data. The root mean square deviation(RMSD)values are less than 0.007 for all the systems, which shows a good predictive capability of this model for such systems.