The third industrial fluid properties simulation challenge

The third industrial fluid properties simulation challenge was held from March to September 2006. As in the previous two events contestants were challenged to predict specific, industrially relevant, properties of fluid systems. Their efforts were judged based on the agreement of the predicted values with previously unpublished experimental data (provided by researchers at ExxonMobil and DuPont). The focus of this contest was on the transferability of modeling methods—the ability to predict properties for materials that are chemically different, or at different state points, to those used in model parameterization and validation. Nine groups attempted to compute bubble point pressures for mixtures of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and ethanol at 343 K, given data for mixtures at 283 K, and given the pure component vapor pressures. They used a range of different techniques including statistical mechanical and molecular simulations-based approaches. Four of the groups were recognized for providing predictions that were significantly more accurate than would be obtained by extrapolation using the NRTL model (the standard engineering approach). Three groups undertook the more challenging “molecular transferability” problem, attempting to predict shear viscosities at two different state points for a range of diols and triols for which little experimental data was available.     

Study on volatility and flash point of the pseudo binary mixtures of sunflower-based biodiesel + methylcyclohexane

The transesterification of sunflower seed oil was carried out in supercritical ethanol without using any catalyst to produce biodiesel. In the present work, methylcyclohexane was added to enhance the vapor pressure of biodiesel. The vapor pressures of mixtures of biodiesel + methylcyclohexane as a function of temperature were measured by comparative ebulliometry with an inclined ebulliometer. The vapor pressures versus composition at different temperatures were obtained. Experimental data of vapor pressures and equilibrium temperatures were correlated by the Antoine equation. A mathematical model was used to predict the flash point of the pseudo binary mixtures. With the regular solution theory, the predictive flash point displays agreement with the experimental data obtained by closed cup test.     

Hydrogen analysis in solid samples by utilizing He metastable atoms induced by TEA CO2 laser plasma in He gas at 1 atm

A TEA CO₂ laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO₂ laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO₂ laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO₂ laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens.     

Vapor–liquid equilibria for pentafluoroethane + propane and difluoromethane + propane systems over a temperature range from 253.15 to 323.15 K

This paper provides vapor–liquid equilibrium (VLE) data obtained for two binary systems of pentafluoroethane (R125)+propane (R290) and difluoromethane (R32)+R290 over a temperature range from 253.15 to 323.15 K. The measurement of VLE was performed at isothermal conditions in a vapor recirculation apparatus. Both systems form azeotropes in the temperature range of this study. The experimental results were well correlated with the Peng–Robinson equation of state (PR EoS) using one parameter van der Waals one fluid model. The binary interaction parameters were optimized using the experimental data of bubble point pressure. A comparison with published experimental VLE data has been carried out by means of the PR equation of state.     

Partial molar volumes of organic solutes in water. XII. Methanol(aq), ethanol(aq), 1-propanol(aq), and 2-propanol(aq) at T = (298 to 573) K and at pressures up to 30 MPa

Density data for dilute aqueous solutions of methanol, ethanol, 1-propanol, and 2-propanol are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at from T = (298.15 up to 573.15) K and at pressure close to the saturated vapor pressure of water, at p = 30 MPa and at pressure between these limits. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter.     

High-pressure phase behavior of CO2 + 1-butyl-3-methylimidazolium chloride system

The phase behavior of carbon dioxide (CO₂) and the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) was measured and correlated at high pressures up to ∼40 MPa and at temperatures between 353.15 K and 373.15 K. The solubility data of CO₂ in [bmim][Cl] were obtained by observing the bubble point pressure at specific temperatures. A variable-volume view cell, which is a high-pressure equilibrium apparatus, was used to measure the CO₂ + [bmim][Cl] system solubility under varying pressure and temperature conditions. In addition, liquid–liquid–vapor (LLV) three-phase behavior was investigated using the equilibrium cell to be able to determine the classification of phase-behavior type by Scott and Van Konynenburg. Based on the LLV phase behavior, this system most likely has type III phase-behavior which is common for IL + CO₂ systems. The resulting data showed that CO₂ dissolved well in the IL at low CO₂ concentrations, but that the pressure derivative of CO₂ solubility dramatically decreased as the mole fraction of CO₂ was increased. The experimental data were well fitted by the Peng–Robinson equation of state with a quadratic mixing rule and cubic parameters estimated by the Joback method.     

Prediction of vapor-liquid equilibrium data of the system MTBE + methanol + ethanol by PRSV2 EOS

The Stryjek and Vera (1986) [9] modification of Peng-Robinson (PRSV2) equation of state has been applied for modeling vapor-liquid equilibrium of the systems MTBE + methanol, MTBE + ethanol and methanol + ethanol. Binary interaction parameters for mixing rules have been estimated by using experimental data at the atmospheric pressure. The calculated binary interaction parameters were used for predicting azeotropic behavior at high pressure and also for isobaric equilibrium points which showed an excellent agreement with experimental data. In addition, estimated binary interaction parameters for binary systems were used for ternary system (MTBE + methanol + ethanol). The predictions deviated only slightly from the experimental data. The results show PRSV2 can be used for VLE prediction of polar systems.     

Effect of pH, temperature and solvent mole ratio on solubility of disodium 5′-guanylate in water + ethanol system

Solubility of disodium 5′-guanylate in water + ethanol binary solvent mixtures was determined by a gravimetric method in the temperature range from 283.15 K to 323.15 K, pH range from 8 to 10 and at different water/ethanol mole ratios. The effects of pH, temperature and water/ethanol mole ratio on the solubility were investigated in detail. The modified Apelblat model and the combined nearly ideal binary solvent (CNIBS)/Redlich-Kister model were selected to correlate the experimental data. The results showed that the experimental data was satisfactorily correlated by the (CNIBS)/Redlich-Kister model, but for the modified Apelblat model, the correlation was not so satisfactory in some cases.     

VLE of CO2 + glycerol + (ethanol or 1-propanol or 1-butanol)

Vapour-liquid equilibrium of CO₂ + [0.00871 glycerol + 0.99129 (ethanol or 1-propanol or 1-butanol)] mixtures was measured at the temperatures of 313.15 K and 333.15 K, and close to the critical line, at pressures up to 12 MPa. On the liquid side, the bubble points measured for these ternary mixtures follow closely the behaviour of VLE reported by several authors for the corresponding binary mixtures without glycerol. On the vapour side, however, dew points for the ternary mixtures deviate significantly from VLE results for the binaries. A correlation of the results obtained for the CO₂ + glycerol + ethanol mixture with the Peng-Robinson equation of state, admitting quasi-binary behaviour, equally yields good agreement on the liquid side, and significant deviations on the vapour side.     

Vapor–liquid equilibrium measurement and modeling for the difluoromethane + pentafluoroethane + propane ternary mixture

Vapor–liquid equilibrium data for the difluoromethane (R32) + pentafluoroethane (R125) + propane (R290) ternary mixture were measured at 5 isotherms between 263.15 K and 323.15 K. The measurement was carried out using a circulation-type apparatus recently developed, which was validated with binary mixtures. With binary interaction parameters obtained for the three corresponding binary mixtures, VLE modeling and prediction were performed for the ternary mixture using the Peng–Robinson equation of state with the classical mixing rules and MHV1 mixing rules. Hou's group contribution model for VLE of new refrigerant mixtures was further tested with the experimental data for the ternary system. The predicted pressure and vapor phase composition were compared with experimental ones.     

Vapor–liquid equilibria of binary tri-potassium citrate + water and ternary polypropylene oxide 400 + tri-potassium citrate + water systems from isopiestic measurements over a range of temperatures

Water activity measurements have been carried out on the aqueous solutions of both tri-potassium citrate (K₃Cit) and polypropylene oxide (PPO) 400 + K₃Cit over a range of temperatures at atmospheric pressure. The data obtained is used to calculate the vapor pressure as a function of temperature and concentration. The effect of temperature on the constant water activity lines of aqueous PPO + K₃Cit systems has been studied and it was found that, at higher temperatures the higher concentration of polymer is in equilibrium with a certain concentration of the salt. Also it was found that the vapor pressure depression for an aqueous PPO + K₃Cit system is more than the sum of those for the corresponding binary solutions. The experimental water activities have been correlated successfully with the segment-based local composition Wilson model. The agreement between the correlation and the experimental data is good.     

Isothermal vapor–liquid equilibrium data for the binary mixture difluoromethane (HFC-32) + ethyl fluoride (HFC-161) over a temperature range from 253.15 K to 303.15 K

Isothermal vapor–liquid equilibrium data of difluoromethane (HFC-32) + ethyl fluoride (HFC-161) mixture in the range of temperatures from 253.15 K to 303.15 K have been measured in the wide range of compositions. The experimental method used for this work is the single-cycle type. Using Peng–Robinson (PR) equation of state, combined with the first Modified Huron-Vidal (MHV1) mixing rule and Wilson model, the vapor–liquid equilibrium data are correlated. The correlation results have a good agreement with the experiment results. The average absolute vapor composition deviation is within 0.0125, and its largest absolute deviation of the vapor composition is 0.0568; the average relative pressure deviation is within 0.76% and its largest relative pressure deviation is 2.87%. In addition, the results reveal that there is no azeotrope in the binary system, and their temperature glides are small.     

Synthesis of industrial scale NaY zeolite membranes and ethanol permeating performance in pervaporation and vapor permeation up to 130 °C and 570 kPa

NaY zeolite tubular membranes in an industrial scale of 80 cm long were synthesized on monolayer and asymmetric porous supports. The quality of synthesized membranes were evaluated by pervaporation (PV) experiments in 80 cm long at 75 °C in a mixture of water (10 wt.%)/ethanol (90 wt.%), resulting in higher permeation fluxes of 5.1 kg m⁻² h⁻¹ in the monolayer type membrane and of 9.1–10.1 kg m⁻² h⁻¹ in the asymmetric-type membranes, respectively. The uniformity with small performance fluctuation in longitudinal direction of the membranes were observed by PV for 10–12 cm long samples at 50 °C in a mixture of methanol (10 wt.%)/MTBE (90 wt.%). The ethanol single component permeation experiments in PV and vapor permeation (VP) up to 130 °C and 570 kPa were performed to determine the relations between the ethanol flux and the ethanol pressure difference across the membrane which is represented by permeance (Π, mol m⁻² s⁻¹ Pa⁻¹) for estimate of potential of ethanol extraction through the present NaY zeolite membranes applying feasible studies. Results indicate that (1) the permeation fluxes are linearly proportional to the driving force of vapor pressure for each sample in VP and PV. The permeances through an asymmetric support type membrane were rather constant of 0.6–1.2 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ in the wide temperature range of 90–130 °C in PV and VP, indicating that the ethanol permeances have weak temperature dependency with the feed at the saturated vapor pressure.

The results of superheating VP experiments showed that ethanol permeation fluxes are increased with increasing of the degree of superheating at a given constant feed vapor pressure. The ethanol permeances are increased with increasing of temperature at a given feed vapor pressure. The superheating VP could be a feasible process in industry.     

Vapor pressure of 1,1,1,2,3,3,3-heptafluoropropane

A total of 84 vapor pressure data points for 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) have been measured in the temperature range from 243 to 375 K. The maximum total pressure uncertainty of these data is estimated to be within ±1 kPa. The purity of the sample used in this work is 99.9 mol%. Based on this data set, a vapor pressure equation for HFC-227ea has been developed. The root-mean-square (RMS) deviation of the experimental data from the vapor pressure equation is 0.057%. The normal boiling point of HFC-227ea was also determined.     

Phase equilibria in binary mixtures with monoethyl succinate

Monoethyl succinate was produced by partial esterification of succinic anhydride with ethanol using Amberlyst 15^® as catalyst. After separation and purification, the purity of monoethyl succinate was confirmed by nuclear magnetic resonance (NMR). Vapor pressure of monoethyl succinate was measured and correlated with Antoine equation. Vapor-liquid equilibria at constant temperature were measured for the binary systems ethyl acetate + monoethyl succinate, acetic acid + monoethyl succinate, and water + monoethyl succinate at 323.15 K, and ethanol + monoethyl succinate at 313.15 K. Binary parameters for the NRTL equations were obtained by fitting experimental data using the regression tool in ASPEN Plus^® using the Hayden-O’Connell method for vapor phase fugacities. The model agrees reasonably well with the experimental data.     

Experimental measurement and thermodynamic modeling of liquid-liquid equilibrium for 1-pentanol + water + NaNO3 at 298.15 and 308.15 K

Experimental measurements have been performed for liquid-liquid equilibria in aqueous systems containing 1-pentanol and sodium nitrate at temperatures of 298.15 and 308.15 K and at atmospheric pressure. The results have been modeled using the extended UNIQUAC model and also a modified version of this model. Relevant model parameters have been adjusted using the experimental data. Both models are capable of correlating the experimental data with an average deviation of less than 0.8 weight percent, with the modified model producing slightly better results. The predictive nature of the models has also been verified.     

An activity coefficient model for predicting salt effects on vapor–liquid equilibria of mixed solvent systems

In the present study, an activity coefficient model, based on the concept of local volume fractions and the Gibbs–Helmholtz relation, has been developed. Some modifications were made from Tan–Wilson model (1987) and TK–Wilson model (1975) to represent activity coefficients in mixed solvent–electrolyte systems. The proposed model contains two groups of binary interaction parameters. One group for solvent–solvent interaction parameters corresponds to that given by the TK–Wilson model (1975) in salt-free systems. The other group of salt–solvent interaction parameters can be calculated either from vapor pressure or bubble temperature data in binary salt–solvent systems. It is shown that the present model can also be used to describe liquid–liquid equilibria. No ternary parameter is required to predict the salt effects on the vapor–liquid equilibria (VLE) of mixed solvent systems. By examining 643 sets of VLE data, the calculated results show that the prediction by the present model is as good as that by the Tan–Wilson model (1987), with an overall mean deviation of vapor phase composition of 1.76% and that of the bubble temperature of 0.74 K.     

Isobaric vapor–liquid equilibria for the quaternary reactive system: Ethanol + water + ethyl lactate + lactic acid at 101.33 kPa

Isobaric vapor–liquid equilibrium (VLE) data of the reactive quaternary system ethanol (1) + water (2) + ethyl lactate (3) + lactic acid (4) have been determined experimentally. Additionally, the reaction equilibrium constant was calculated for each VLE experimental data. The experimental VLE data were correlated using the UNIQUAC equation to describe the chemical and phase equilibria simultaneously. For some of the non-reactive binary systems, UNIQUAC binary interaction parameters were obtained from the literature. The rest of the binary UNIQUAC parameters were obtained by correlating the experimental quaternary VLE data obtained in this work. A maximum pressure azeotrope at high water concentration for the binary reactive system ethyl lactate + water has been calculated.