Synthetic methods in phase equilibria: A new apparatus and error analysis of the method

A new apparatus for the study of high-pressure phase equilibria using a synthetic method is described. The apparatus was especially developed for the study of solubilities of gases in condensed phases, at temperatures ranging from 243 K to 353 K and pressures up to 20 MPa. The quality of the equipment was confirmed through several tests, including measurements along the three phase co-existence line for the system ethane + methanol, the study of the solubility of methane in water, and of carbon dioxide in water.An analysis regarding the application of the synthetic isothermal method in the study of gas solubilities was performed, in order to evaluate the influence of common assumptions and of various experimental aspects on the final solubility results. The analysis revealed that the largest influence on the precision of the solubility results is related to the ratio between the volumes of the two phases in equilibrium. Experiments with small volume of the vapour phase are less susceptible to the influence of other sources of errors, resulting in a higher precision of the final results.     

Experimental study of the phase relationships in the SrO-SiO2 system

The phase relationships in the SiO₂-SrO system were determined experimentally using the quenching technique in the temperature range between 1573?K (1300?°C) and 1898?K (1625?°C). The phases in the quenched samples were examined and identified using light optical microscopy (LOM), scanning electron microscope (SEM) and energy dispersive x-ray spectroscopy (EDS). The presence of solid phases and their nature were further confirmed using X-ray Diffraction (XRD). Based on the experimental results, the phase diagram was constructed. The phase diagram shows a congruent melting of the SrSiO₃ at 1840?K (1567?°C). The eutectic between the SrSiO₃, SiO₂ and liquid happens at 1608?K (1335?°C) and 67?mol% SiO₂ and the eutectic between the SrSiO₃, Sr₂SiO₄ and liquid at 1835?K (1562?°C) and 46.5?mol% SiO₂.     

Influence of compositional gradient on the phase behavior of ternary symmetric homopolymer-copolymer blends: A Monte Carlo study

The formation of bicontinuous microemulsions (BUEs) in ternary symmetric blends including two immiscible homopolymers A and B as well as a linear gradient copolymer G is verified by Monte Carlo simulations. Four phase diagrams as a function of segregation strength and blend composition are constructed to show the effects of compositional gradient. Compared with the blends of A/B/diblock copolymers, the BUE phase occupies a broader region in the phase diagram of the A/B/G blends and is replaced by the three-phase coexistence phases of A + B + L or A + B + D at a much lower chain length ratio. Moreover, the lamellar phase is formed at a higher value of segregation strength, has a shorter periodic length and lower orientational order, and spans a narrower range of the phase diagram. A “counteraction effect” is proposed to explain those discrepancies caused by gradient copolymers.     

Operating zone segregation of chemical reaction systems based on stability and non-minimum phase behavior analysis

Many chemical reaction systems exhibit input/output multiplicity characteristics and non-minimum phase behavior. These inherent characteristics are known to cause limitations in process operation, so it is useful to have some knowledge of these at the early design stage of a chemical reaction process. Focusing on inherently safer designs, this paper addresses a strategy for classifying the process operating region into distinct zones at the early stage of process design, based on stability/instability and minimum/non-minimum phase behavior analysis. The strategy is illustrated by two case studies, where the operating spaces of an isothermal CSTR and an exothermic CSTR are classified into zones with different characteristics. The results provide information that is very important for guiding process design and operation about how the inherent properties of a process change with changes in its operating conditions.     

Monte Carlo simulations of phase behavior and microscopic structure for supercritical CO2 and thiophene mixtures

The phase equilibria of thiophene in supercritical carbon dioxide are calculated by Monte Carlo simulations in Gibbs ensemble using a united atom force field. To validate the simulations, binary vapor–liquid coexistence curves were computed for two different temperatures using Monte Carlo simulations. An excellent agreement between simulations and experimental data is obtained. The effects of pressure on structural properties were studied for thiophene–CO₂ binary mixtures. The radial distribution functions and local composition of thiophene in CO₂ were investigated over a range of pressures. A weak dependence of thiophene structural properties with pressure was observed in supercritical phase. Local solution structure of thiophene in supercritical CO₂ was studied by computing angular–radial distribution functions and spatial distribution functions with three-dimensional probability distributions. The characteristic angular–radial distributions show a mutually parallel arrangement between thiophene plane and CO₂ molecules within the first solvation shell. Spatial distribution functions (SDFs) results show that CO₂ molecules have two higher probability distributions around thiophene molecules located above and below the thiophene ring.     

Effect of thermodynamic parameters on prediction of phase behavior and process design of extractive distillation

Extractive distillation was investigated for separation of the minimum azeotrope of n-propanol/water,via the Aspen Plus simulation platform.Experimental data of n-propanol/water,which could pass the thermodynamic consistency test,were regressed to get suitable binary interaction parameters (BIPs) by the UNIQUAC thermodynamic model.The azeotrope system was heterogeneous in the simulation with built-in BIPs,which was contrary to the experimental data.The study focused on the effect of thermodynamic parameters on the prediction of phase behavior,and process design of extractive distillation.N-methyl-2-pyrrolidone (NMP) and ethylene glycol were used as solvents to implement the separation.Processes with built-in and regressed BIPs were explored,based on the minimum total annual cost (TAC).There were significant differences in the phase behavior simulation using different thermodynamic parameters,which showed the importance of BIPs in the design and optimization of extractive distillation.     

Modelling the solubility in Bayer liquors: A critical review and new models

An accurate and tractable model of solubility is a pre-requisite for any careful study of precipitation. Reviewing the abundant literature on the sodium aluminate solutions and Bayer Liquor, the authors point out the need for a new model for the apparent solubility of aluminium in actual Bayer Liquors and propose such a model, based on the well established Wesolowski's expression for the infinite dilution solubility and extended Debye–Hückel expression including a large empirical b I term for the “activity coefficient effect”. They suggest a chemical interpretation for this feature.     

Supercritical phase behavior for biotransformation processing

In recent works, supercritical carbon dioxide turned out to offer innovative and highly effective alternatives for the workup of biphasic whole-cell biotransformation reaction mixtures. Further optimization of the downstream processing, e.g. by supercritical extraction of the product, requires a reliable simulation of the phase behavior in those systems. In this work, binary and ternary systems containing carbon dioxide and organic components from the biotransformation reaction mixture, such as styrene (substrate), (S)-styrene oxide (product), 2-phenylethanol (byproduct), octane (inducer), and bis-2(ethylhexyl)phthalate (solvent) were measured and modeled for temperatures ranging from 308.15 to 350.15 K and pressures ranging from 5 to 70 MPa using the PC-SAFT equation of state. The obtained results offer the possibility to precisely predict the phase behavior in this system, thus enabling the modeling of e.g. supercritical-fluid extraction steps.     

一种新型水气蒸馏回流仪

提出了一种新型水气蒸馏回流仪,该仪器具有水气蒸馏、回流提取及分水等多种功能,且便于操作。经试用,效果良好。     

Role of phase behavior in micronization of lysozyme via a supercritical anti-solvent process

Ultra-fine particles of protein lysozyme were prepared with a supercritical anti-solvent (SAS) apparatus by using dimethyl sulfoxide (DMSO) as solvent and carbon dioxide as anti-solvent. The influences of various experimental factors on the morphology and the mean size of particulate products were investigated. As evidenced from the experimental results, phase behavior of the mixtures in precipitator during the particle formation stage played a crucial role in the SAS processes. Uniform networked nano-particles were obtained when the precipitations were conducted in the supercritical region of carbon dioxide + DMSO mixture. Several different types of morphologies were produced simultaneously as the precipitations were operated near the critical region. Spherical micron-scale clusters were formed in the superheated vapor region, while submicron-particles were aggregated as dense cake when lysozyme precipitated in the vapor–liquid coexistence region. The wide angle X-ray scattering (WAXS) patterns indicated that both the raw lysozyme and the processed particulate samples were amorphous. The differential scanning calorimeter (DSC) thermograms showed that the dehydration peak was disappeared after SAS treatment. Moreover, the networked primary particles could be disintegrated and dispersed well in water through ultrasonication, which were confirmed by analysis with dynamic laser scattering (DLS). A continuous stirred tank reactor (CSTR) model was used to calculate the dynamic composition variations of the mixtures in precipitator during the particle formation period.     

Complicated phase behavior and ionic conductivities of PVP-co-PMMA-based polymer electrolytes

We have used DSC, FTIR spectroscopy, and ac impedance techniques to investigate the interactions that occur within complexes of poly(vinylpyrrolidone-co-methyl methacrylate) (PVP-co-PMMA) and lithium perchlorate (LiClO₄) as well as these systems' phase behavior and ionic conductivities. The presence of MMA moieties in the PVP-co-PMMA random copolymer has an inert diluent effect that reduces the degree of self-association of the PVP molecules and causes a negative deviation in the glass transition temperature (T_g). In the binary LiClO₄/PVP blends, the presence of a small amount of LiClO₄ reduces the strong dipole-dipole interactions within PVP and leads to a lower T_g. Further addition of LiClO₄ increases T_g as a result of ion-dipole interactions between LiClO₄ and PVP. In LiClO₄/PVP-co-PMMA blend systems, for which the three individual systems—the PVP-co-PMMA copolymer and the LiClO₄/PVP and LiClO₄/PMMA blends—are miscible at all compositional ratios, a phase-separated loop exists at certain compositions due to a complicated series of interactions among the LiClO₄, PVP and PMMA units. The PMMA-rich component in the PVP-co-PMMA copolymer tends to be excluded, and this phenomenon results in phase separation. At a LiClO₄ content of 20 wt% salt, the maximum ionic conductivity occurred for a LiClO₄/VP57 blend (i.e., 57 mol% VP units in the PVP-co-PMMA copolymer).     

Modification of a thermodynamic model and an equation of state for accurate calculation of asphaltene precipitation phase behavior

In this study, DPTG (Dashtizadeh-Pazuki-Taghikhani-Ghotbi) equation of state has been modified for calculation of phase behavior of fluids and solubility parameter. The accuracy of the modified EOS has been proved by estimation of the properties of some hydrocarbons such as densities of methane and condensate gases, vaporization enthalpy, sublimation pressure, compressibility factor and comparison of the obtained results with the results of the present equations of state such as NJ (Nasrifar-Jalali), ZMJL (Zhi-Meiren-Jun-Lee) and PR (Peng-Robinson). Then, the Flory-Huggins model has been modified and asphaltene precipitation phase behavior at different ratios of solvents in the crude oil has been predicted by the modified EOS and the developed Flory-Huggins model. Comparison of the obtained results with the experimental data of asphaltene precipitation and the calculated ones by the main Flory-Huggins model shows the accuracy of the developed model.     

A new two-dimensional experimental apparatus for electrochemical remediation processes☆

Electrochemical extraction of contaminants from soils is a promising soil decontamination technology. Various experiments have been conducted to study electrochemical reactions and geochemical processes in the electro-chemical extraction using different experimental apparatuses. This paper presents the development of a new closed two-dimensional (2D) apparatus that can better simulate the field application of the technology and ac-curately monitor the most important electrochemical parameters to understand the process. The innovative fea-tures of the new apparatus include the outer and inner electrodes designed to apply a non-uniform electrical field across the specimen as in the field electrochemical remediation process, the probes installed to measure the 2D distribution of electrical voltage, and the gas and fluid volume measurement devices used to accurately monitor the gas generation and electroosmotic flow rates at both electrodes as a function of time. The components of this new apparatus and the features of each component are described. The operating procedure and some typical re-sults from three experiments with the apparatus are demonstrated. The results show that the variation of the gas generation rate is in good agreement with the electric current. Their relation provides a valid evaluation for elec-trochemical behavior of the system and Faraday's laws of electrolysis. The 2D profiles of cadmium concentration and voltage distribution at the end of the experiment reveal the great effects of a non-uniform electrical field on the contaminant mobilization.     

Controlling the phase behavior of block copolymers via sequential block growth

Block copolymers remain one of the most extensively investigated classes of polymers due to their abilities to self-organize into various nanostructures and modify polymer/polymer interfaces. Despite fundamental and technological interest in these materials, only a handful of experimental phase diagrams exist due to the laborious task of preparing such diagrams. In this work, two copolymer series are each synthesized from a single macromolecule via sequential living anionic polymerization to yield molecularly asymmetric diblock and triblock copolymers systematically varying in composition. The phase behavior and morphology of these copolymers are experimentally interrogated and quantitatively compared with predictions from mean-field theories, which probe copolymer phase behavior beyond current experimental conditions.     

Polystyrene-poly(2-ethylhexylmethacrylate) block copolymers: Synthesis,bulk phase behavior,and thin film structure

Anionic polymerization was employed to synthesize well-defined diblock copolymers of polystyrene and poly(2-ethylhexylmethacrylate), PS-PEHMA. Diblock morphologies in bulk and in substrate-supported thin films were characterized by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM), respectively. PS-PEHMA diblocks exhibited thermotropic order-disorder transitions; one diblock showed a thermoreversible transition between lamellae and a higher-temperature morphology assigned as perforated lamellae. Unlike PS-poly(alkylmethacrylate) diblocks where the alkyl group is n-butyl or n-pentyl, PS-PEHMA diblocks showed a typical decreasing Flory interaction parameter with increasing temperature. Thin films of PS-cylinder-forming PS-PEHMA diblocks showed a strong preference for the cylinders to lie in the plane of the film; films of incommensurate thickness readily formed terraces. Films of commensurate thickness were easily aligned over macroscopic areas through the application of mechanical shear.     

Experimental study of the mass transfer behavior of carbon dioxide absorption into ternary phase change solution in a packed tower

Phase change absorbents for CO₂ are of great interest because they are expected to greatly reduce the heat energy consumption during the regeneration process. Compared with other phase change absorbents, monoethanolamine (MEA)-sulfolane-water is inexpensive and has a fast absorption rate. It is one of the most promising solvents for large-scale industrial applications. Therefore, this study investigates the mass transfer performance of this phase change system in the process of CO₂ absorption in a packed tower. By comparing the phase change absorbent and the ordinary absorbent, it is concluded that the use of MEA/sulfolane phase change absorbent has significantly improved mass transfer efficiency compared to a single MEA absorbent at the same concentration. In the 4 mol·L^-1 MEA/5 mol·L^-1 sulfolane system, the CO₂ loading of the upper liquid phase after phase separation is almost zero, while the volume of the lower liquid phase sent to the desorption operation is about half of the total volume of the absorbent, which greatly reduces the energy consumption. This study also investigates the influence of operating parameters such as lean CO₂ loading, gas and liquid flow rates, CO₂ partial pressure, and temperature on the volumetric mass transfer coefficient (K_Ga_V). The research shows that K_Ga_V increases with increasing liquid flow rate and decreases with the increase of lean CO₂ loading and CO₂ partial pressure, while the inert gas flow rate and temperature have little effect on K_Ga_V. In addition, based on the principle of phase change absorption, a predictive equation for the K_Ga_V of MEA-sulfolane in the packed tower was established. The K_Ga_V obtained from the experiment is consistent with the model prediction, and the absolute average deviation (AAD) is 7.8%.     

The phase behavior of n-alkane systems

Normal alkanes show very complicated phase transition kinetics and macroscopic phase equilibrium behavior. This paper focuses on the phase stability and equilibrium of complicated mixtures like n-alkanes and on the enabling global optimization technologies needed to gather problem knowledge. The new ideas contained in this paper include:

(1) novel level set methods for gathering encoded knowledge;

(2) the differential geometry for uncovering pathways to more subtle knowledge;

(3) all supporting non-linearly constrained optimization techniques;

(4) all data handling needed to unravel complex solution structure.

These new ideas are incorporated within the integral path methodology or terrain methods recently developed by Lucia, A., & Yang, F. (2003) [Lucia, A., & Yang F. (2003). Multivariable terrain methods. AIChE Journal 49, 2553] and Lucia, DiMaggio, and Depa (2004) [Lucia, A., DiMaggio, P.A., & Depa, P. (2004). A geometric terrain methodology for global optimization. Journal of Global Optimization 29, 297]. This framework provides global knowledge for understanding solution structure, like the complex solution structure of n-alkanes. In particular, it is shown that knowledge of the Newton and tangent vector fields, Gauss curvature, integral path bifurcation points, and non-differentiable manifolds provides a deterministic way of finding additional solutions, saddle points, and other information that might otherwise go undetected.It is shown that the optimization tools developed in this work provide all knowledge of interest on the appropriate hypothetical single-phase or composite surface (i.e., minima, saddle points, singular points, and integral paths) in phase stability applications. This knowledge can be obtained by solving the phase stability problem exactly once, in a pre-processing step, and used to reliably initialize any multi-phase equilibrium calculation for any feed. This removes the need to repeatedly solve the phase stability problem as the feed composition changes and greatly increases computational efficiency. Numerical examples and geometric illustrations are used to elucidate key ideas and to show how the proposed approach can be used to unravel the complicated phase behavior of n-alkane mixtures.     

Tuned phase behavior of weakly interacting polystyrene-block-poly(n-pentyl methacrylate) by selective solvent

We investigated, via small angle X-ray scattering, depolarized light scattering, rheometry, and transmission electron microscopy, the phase behavior of the mixture of a symmetric polystyrene-block-poly(n-pentyl methacrylate) copolymer (PS-b-PnPMA) showing the closed-loop phase behavior and excellent baroplasticity, and dodecanol, a PnPMA-selective solvent. We found that the addition of a selective solvent is simple, but very effective to obtain various microdomains including hexagonally packed cylinders and gyroids. Also, with increasing temperature, the mixtures showed multiple ordered-to-ordered transitions (OOTs) in addition to upper ordered-to-disordered transition (UODT). The first observation of gyroid microdomains in PS-b-PnPMA is very important, although they have been widely reported in many block copolymers, for instance, PS-block-polyisoprene copolymer (PS-b-PI) and PS-block-poly(d,l-lactide) copolymer (PS-b-PLA). Since the gyroid microdomains of PS-b-PnPMA show excellent baroplasticity, external pressure instead of temperature could easily change the microdomains.     

High pressure phase behavior for carbon dioxide-1-butanol and carbon dioxide-1-octanol systems

Pressure-composition isotherms are obtained for binary mixtures of carbon dioxide-1-butanol and carbon dioxide-1-octanol systems at 40, 60, 80, 100, and 120 °C and pressures up to 220 bar. The accuracy of the experimental apparatus was tested by comparing the measured phase equilibria data of the carbon dioxide-1-butanol system at 40 °C with those of Ishihara et al. [1996]. The solubility of 1-butanol and 1-octanol for the carbon dioxide-1-butanol and carbon dioxide-1-octanol systems increases as the temperature increases at constant pressure. The carbon dioxide-1-butanol and carbon dioxide-1-octanol systems have continuous critical mixture curves that exhibit maximums in pressure at temperatures between the critical temperatures of carbon dioxideand 1-butanol or 1-octanol. The carbon dioxide-1-butanol system exhibits type-I phase behavior, characterized by a continuous critical line from pure carbon dioxide, to the second component with a maximum in pressure. Also, the carbon dioxide-1-octanol system exhibits type-I curve at 60–120 °C, and shows liquid-liquid-vapor phase behavior at 40 oC. The experimental results for the carbon dioxide-1-butanol and carbon dioxide-1-octanol systems have been modeled by the Peng-Robinson equation of state. A good fit of the data is obtained with the Peng-Robinson equation by using two adjustable interaction parameters for the carbon dioxide-1-butanol system and a poor fit using two adjustable parameters for the carbon dioxide-1-octanol mixture.     

Liquid phase behavior and its effect on crystalline morphology in the extruded poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blend

Morphology in an extruded poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) was investigated using time-resolved light scattering, optical microscope and small-angle X-ray scattering. During annealing at 280 °C, the domain structure via spinodal decomposition preceded, the transesterification followed, and then the transesterification between the two polyesters induced the dissolution of the liquid-liquid (L-L) phase separation, i.e. the homogenization. The annealed specimen for various time periods (t_s) at 280 °C was subjected to a temperature-drop to 120 °C for the isothermal crystallization and then the effects of liquid phase morphology on crystallization was investigated. With t_s, the H_ν (cross-polarization) light scattering patterns exhibited the dramatic change from a four-leaf clover pattern with maximum intensity at azimuthal angle 45° (×-type scattering pattern) to a diffuse pattern of circular symmetry and then a four-leaf clover pattern with maximum intensity at azimuthal angles 0 and 90° (+-type scattering pattern). This suggests that the crystalline structure depends on the level of the block and/or random copolymer produced by the transesterification during annealing. The H_ν scattering patterns reflected differences in the principle polarizability of the crystalline lamellae with respect to the spherulitic radius. On the other hand, the long period L_B, an average distance between two adjacent crystalline lamellae, increased with t_s at 280 °C. The dependence of L_B on t_s was explained by the change in the crystallization rate G.