Hun-Soo Byun

Phase behavior for the poly(2-methoxyethyl acrylate)+supercritical solvent+cosolvent mixture and CO2+2-methoxyethyl acrylate system at high pressure

High pressures phase equilibrium data were presented for the CO2+2-MEA system at temperatures ranging from (313.2 to 393.2) K and pressures up to ca. 17.97MPa. The CO2+2-MEA system exhibited type-I phase behavior and was modeled using the Peng-Robinson equation of state. The phase behavior data were reported for poly(2- methoxyethyl acrylate) [P(2-MEA)] in supercritical CO2 and dimethyl ether (DME), as well as for the P(2-MEA)+2-methoxyethyl acrylate (2-MEA) (or DME) in CO2. The cloud-point data were measured for the P(2-MEA)+DME in supercritical CO2 at temperature range of (333–453) K and a pressure range of (8.79–199.14) MPa. The P(2-MEA) in supercritical CO2 was soluble to 453 K and pressure of 199MPa. The phase behavior for the P(2-MEA)+CO2+2-MEA mixture was measured in changes of the pressure-temperature (p, T) slope and with 2-MEA mass fraction of 0.0 wt%, 8.4 wt%, 17.1 wt%, 45.4 wt% and 65.0wt%. With 74.5 wt% 2-MEA to the P(2-MEA)+CO2 solution, the cloud-point curves took on the appearance of a typical lower critical solution temperature boundary, liquid+liquid transition and liquid+vapor transition. The location of the P(2-MEA)+CO2 cloud-point curve shifted to lower temperatures and pressures upon the addition of 2-MEA or DME.

Monomer concentration effect on the phase behavior of poly(propyl acrylate) and poly(propyl methacrylate) with supercritical CO2 and C2H4

Experimental cloud-point data to temperature of 186 °C and pressure of ~2,500 bar are presented for ternary mixtures of poly(propyl acrylate)(PPA)-CO2-propyl acrylate (PA) PPA-C2H4-PA and poly(propyl methacrylate) (PPMA)-CO2-propyl methacrylate (PMA) systems. Cloud-point pressures of PPA-CO2-PA system were measured in the temperature range of 32 °C to 175 dgC and to pressures as high as 2,070 bar with PA concentrations of 0.0, 5.0, 11.7 and 30.4 wt%. Adding 34.1 wt% PA to the PPA-CO2 mixture significantly changes the phase behavior. This system changes the pressure-temperature slope of the phase behavior curves from U-LCST region to LCST region as the PA concentration increases. Cloud-point data to 170 °C and 1,400 bar are presented for PPA-C2H4-PA mixtures and with PA concentration of 0.0, 5.7, 15.5 and 22.2 wt%. The cloud-point curve of PPA-C2H4 system shows relatively flat at 730 bar for temperatures between 41 and 150 °C. With 15.5 and 22.2 wt% PA the cloud-point curve exhibits a positive slope that extends to 35 °C and ~180 bar. Also, the ternary PPMA-CO2-PMA system was measured below 186 °C and 2,484 bar, and with cosolvent of 5.2-20.1 wt%. PPMA does not dissolve in pure CO2 to 233 °C and 2,500 bar. Also, when 41.5 wt% PMA is added to the PPMA-CO2 solution, the cloud-point curve shows the typical appearance of a lower critical solution temperature (LCST) boundary.

Bubble-point measurement for the CO2+diethylene glycol diacrylate and CO2+diethylene glycol dimethacrylate systems at high pressure

Pressure-composition isotherms are measured by using a static apparatus for the phase behavior data for the CO2+diethylene glycol diacrylate (DEGDA) and CO2+diethylene glycol dimethacrylate (DEGDMA) systems. The experiments are performed at five temperatures of (313.2 to 393.2) K and pressures up to 28.3 MPa. The solubility of CO2 for the two systems decreases as the temperature increases at a fixed pressure. The CO2+DEGDA and CO2+ DEGDMA systems exhibit type-I phase behavior. The experimental results for the CO2+DEGDA and CO2+DEGDMA systems are correlated with Peng-Robinson equation of state using a mixing rule.

Vapor-Liquid Equilibria Measurement of Carbon Dioxide+1-Hexene and Carbon Dioxide+2-Ethyl-1-Butene Systems at High Pressure

Pressure-composition isotherms were obtained for the carbon dioxide+1-hexene system at 40, 60, 80, 100 and 120 ‡C and pressure up to 120 bar and for carbon dioxide+2-ethyl-1-butene system at 40, 75 and 100 ‡C and pressure up to 115 bar. The accuracy of the experimental apparatus was tested by comparing the measured phase equilibrium data of the carbon dioxide+ 1-hexene system at 40 ‡C and 60 ‡C with those of Wagner and Wichterle [1987], and Jennings and Teja [1989]. The solubility of 1-hexene and 2-ethyl-1-butene for the carbon dioxide + 1-hexene and carbon dioxide+2-ethyl-1-butene systems increases as the temperatures increases at constant pressure. These two carbon dioxide-polar solute systems exhibit type-I phase behavior, which is characterized by an uninterrupted critical mixture curve that has a maximum in pressure. The experimental data are modeled by using the Peng-Robinson equation of state. A good fit of the data is obtained with Peng-Robinson equation of state using two adjustable parameters for carbon dioxide+1-hexene and carbon dioxide+2-ethyl-1-butene systems.

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.

Phase behavior measurement of the binary carbon dioxide-N, N-dimethylacetamide and carbon dioxide-N, N-diethylacetamide systems at high pressure

Abstract Pressure-composition isotherms are obtained for the carbon dioxide– N , N -dimethylacetamide ( N , N -DMA) and for the carbon dioxide– N , N -diethylacetamide ( N , N -DEA) systems at 40, 60, 80, and 100°C. These two carbon dioxide–polar solute systems have continuous critical mixture curves that exhibit maximums in pressure at temperatures between the critical temperatures of carbon dioxide and N , N -DMA or N , N -DEA. The experimental data are modeled using the multi-fluid-nonrandom lattice fluid (MF-NLF) equation of state. The coefficient of energy and volume parameters for each pure N , N -DMA or N , N -DEA is determined from a fit of the vapor pressure curve and saturated liquid densities. A good fit of the data is obtained with the MF-NLF equation using one adjustable mixture parameter that is temperature-independent, for the carbon dioxide– N , N -DMA and carbon dioxide– N , N -DEA systems.

Experimental measurement and correlation of phase behavior for the CO2+heptafluorobutyl acrylate and CO2+heptafluorobutyl methacrylate systems at high pressure

Experimental data of high pressure phase behavior from 313.2 to 393.2 K and pressures up to about 14.3 MPa were reported for binary mixture of 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (HFBMA) in supercritical carbon dioxide. The high pressure experiment was performed by static method using variable-volume view cell apparatus. The CO2+HFBA and CO2+HFBMA systems are correlated with the Peng-Robinson equation of state using a van der Waals one-fluid mixing rule. The CO2+HFBA and CO2+HFBMA systems exhibit type-I phase behavior with continuous critical mixture curves.

High pressure phase behavior for the binary mixture of pentafluoropropyl methacrylate and poly(pentafluoropropyl methacrylate) in supercritical carbon dioxide and dimethyl ether

Pressure-composition isotherm is obtained for the carbon dioxide+2,2,3,3,3-pentafluoropropyl methacrylate (PFPMA) using static apparatus with a variable volume view cell at temperature range from 40 °C to 120 °C and pressure up to 130 bar. This system exhibits type-I phase behavior with a continuous mixture-critical curve. The experimental result for carbon dioxide+PFPMA mixture was modeled using the Peng-Robinson (P-R) and multi-fluid nonrandom lattice fluid (MF-NLF) equation of state. Experimental cloud-point data of pressure up 470 bar and temperature to 182 °C were reported for the binary mixture of poly(2,2,3,3,3-pentafluoropropyl methacrylate) [Poly(PFPMA)] in supercritical carbon dioxide and dimethyl ether (DME). The Poly(PFPMA)+carbon dioxide and Poly(PFPMA)+DME systems showed LCST behavior.

Phase behavior for the poly(alkyl methacrylate)+supercritical CO2+DME mixture at high pressures

The phase behavior curves of binary and ternary system were measured for poly(alkyl methacrylate) in supercritical CO2, as well as for the poly(alkyl methacrylate)+dimethyl ether (DME) (or 1-butene) in CO2. The solubility curves are reported for the poly(alkyl methacrylate)+DME in supercritical CO2 at temperature from (300 to 465) K and a pressure from (3.66 to 248) MPa. Also, The high-pressure static-type apparatus of cloud-point curve was tested by comparing the measured phase behavior data of the poly(methyl methacrylate) [PMMA]+CO2+20.0 and 30.4 wt% methyl methacrylate (MMA) system with literature data of 10.4, 28.8 and 48.4 wt% MMA concentration. The phase behavior data for the poly(alkyl methacrylate)+CO2+DME mixture were measured in changes of the pressure-temperature (p, T) slope and with DME concentrations. Also, the cloud-point pressure for the poly(alkyl methacrylate)+1- butene solution containing supercritical CO2 shows from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region at concentration range from (0.0 to 95) wt% 1-butene at below 455 K and at below 245MPa.

Synthesis and adsorption properties of carbamazepine imprinted polymer by dispersion polymerization in supercritical carbon dioxide

We synthesized molecularly imprinted polymers (MIPs) which can selectively separate carbamazepine (CMZ) as a pharmaceutically active compound by using supercritical fluid technology in supercritical carbon dioxide (scCO2), and also evaluated the adsorption properties of the prepared CMZ imprinted polymers (CMZ-IPs). CMZIPs is prepared with methacrylic acid (MAA) as a functional monomer, CMZ as a template, and ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent. The binding characteristics of CMZ-IPs are evaluated using equilibrium binding experiments. The adsorption ability in aqueous solution of CMZ-IPs was investigated by HPLC analysis, measuring the adsorbed amounts for the template and its structural analogue, the selectivity factor (α), and the imprinting-induced promotion of binding (IPB). The adsorption properties with the change of pH and temperature of aqueous solution were also examined. The results of the evaluation analysis indicate that the prepared CMZ-IPs have high selectivity (102, 94, 75 and 44 µmol/g) and separation abilities.