Effect of Cosolvent Concentration on Phase Behavior for the Poly(isodecyl acrylate) in Supercritical Carbon Dioxide,Propane, Propylene,Butane, 1‐Butene and Dimethyl Ether

High pressure phase behavior data of mixtures of poly(isodecyl acrylate) [P(IDA)] in supercritical carbon dioxide, dimethyl ether (DME), propane, propylene, butane and 1‐butene have been studied. The phase behaviors for these binary and ternary systems are shown for temperatures below ca. 200°C and pressures up to ca. 1920 bar. The location of the P(IDA)+CO₂ cloud‐point curve shifts to lower temperatures and pressures when isodecyl acrylate (IDA) or DME is added to the P(IDA)+CO₂ solution. High pressure phase behaviors for IDA in supercritical carbon dioxide were also performed for temperature ranging from 40–120°C and pressures from 38–217 bar. The experimental results in this work are modeled using the Peng‐Robinson equation of state.     

A Study of ibuprofen solubility in supercritical carbon dioxide by Fourier-transform infrared spectroscopy

In the work, a method of study of solubility of pharmaceutical substances in high-pressure gases and supercritical media with Fourier-transform IR spectroscopy has been developed. An investigation of the process of ibuprofen dissolution in supercritical carbon dioxide (SC CO₂) in a real-time scale has been performed. On the basis of analysis of the time dependences of the integral intensities of the selected IR-absorption bands of ibuprofen on the value of the initial weighed portion the value of solubility (molar fraction) of ibuprofen in SC CO₂ at a temperature of 35°C and pressure of 15.0 MPa was obtained, being equal to (8.9 ± 1.6) × 10^?3.     

Fabrication of highly porous bioresorbable polymer matrices using supercritical carbon dioxide

A new method for fabrication of highly porous bioresorbable polymer structures on the basis of various aliphatic polyesters for tissue engineering has been successfully designed and worked out. It has been shown that injection of polymer compositions plasticized in sub- or supercritical carbon dioxide into press forms at temperatures from 20 to 40°C through a nozzle of a certain diameter under atmospheric or elevated (up to 6 MPa) CO₂ pressure allows obtaining polymer matrices with a desired structure and morphology and mean porosity of up to 96 vol % with high reproducibility and avoiding the use of toxic organic solvents. The effect of chemical composition and molecular mass of starting polymers, as well as temperature and CO₂ pressure in the reaction cell and the receiver, on the morphology and internal structure of fabricated samples was studied using the method of scanning-electron microscopy.     

Spectral characteristics of subcritical carbon dioxide in nanopores

Coherent anti-Stokes Raman scattering spectra measured within the Q-branch of the vibrational transition ν₁ are used to gain insights into the state of carbon dioxide molecules in nanopores of Vycor™ glass at room temperature (20.5°C) and a subcritical temperature of 30.5°C and gas pressures up to the saturation point P _sat for each temperature. Along with the main spectral component, belonging to gaseous CO₂ molecules, the spectra recorded at pressures close to P _sat feature a second (low-frequency) component. The second component is associated with the contribution from the CO₂ molecules trapped inside pores. A spectral deconvolution with account for the interference of these two bands makes it possible to estimate the spectral characteristics of the second (low-frequency) component at each temperature. At 20.5°C, the bandwidth of the low-frequency component decreases with CO₂ pressure, a behavior that can be explained by the transition of CO₂ from the adsorbed to the condensed state in the pore. At the subcritical temperature of 30.5°C, the spectral width of the second component is pressure-independent and close to the value measured in the bulk of the supercritical fluid, a result likely associated with a low-temperature shift of the critical point of the substance trapped in nanopores.     

CARS diagnostics of molecular media under nanoporous confinement

The CARS spectroscopy is used for the diagnostics of carbon dioxide in a nanoporous glass at temperatures ranging from room temperature (20.5°C) to the subcritical temperature (30.5°C) in the pressure range below the saturated-vapor pressure. The contributions of the gas-phase molecules, the molecular layer adsorbed from the gas phase on the pore surface, the condensed liquid-like phase, and the liquid interface in the vicinity of the pore surface can be selected using the analysis of the nonlinear spectral response. The spectral behavior of the carbon dioxide confined in nanopores at the subcritical temperature indicates a state that is similar to the supercritical fluid. This corresponds to a low-temperature shift of the critical point of the medium confined in nanopores.     

Aerogel–copper nanocomposites prepared using the adsorption of a polyfluorinated complex from supercritical CO2

A supercritical deposition method has been used to synthesize aerogel?Ccopper nanocomposites. Carbon, resorcinol?Cformaldehyde, and silica aerogels (CAs, RFAs, and SAs) were impregnated with a new polyfluorinated copper precursor (CuDI6), which has a high solubility in supercritical carbon dioxide (scCO₂). Adsorption isotherms of CuDI6 onto various aerogels from scCO₂ were determined at 35?°C and 10.6?MPa using a batch method which is based on the measurement of the fluid phase concentration. The relative affinity between CuDI6 and different aerogels changed in the following order: CA?>?RFA?>?SA. The effect of temperature on the adsorption isotherms for the CuDI6?CCO₂?CCA system was also studied at 35 and 55?°C and at a CO₂ density of 736.1?kg/m³. The CuDI6 uptake at a particular CuDI6 concentration increased with increasing temperature. Adsorbed CuDI6 was found to convert into Cu and Cu/Cu₂O nanoparticles on the aerogel supports after chemical or thermal treatments at ambient pressure and at temperatures ranging from 200 to 400?°C.     

Study of the parameters of the collisionally broadened R22 absorption line of the 1000-0001 transition in CO2 molecules: I. Experiment

Unsaturated absorption coefficients in pure carbon dioxide at pressures of 1 and 100 Torr and in CO₂-N₂ and CO₂-He binary mixtures at a pressure of 100 Torr have been measured in the temperature range of 296?C700 K using a frequency-stabilized tunable CO₂ laser. The collisional self-broadening coefficient, the relative coefficients of collisional broadening caused by N₂ and He buffer gases, and their temperature dependences have been determined for the R22 absorption line of the 10⁰0?C00⁰1 transition in CO₂ molecules.     

An investigation of the dissolution of acetylsalicylic acid in supercritical carbon dioxide

The dissolution of acetylsalicylic acid in supercritical carbon dioxide (SC–CO₂) is investigated using Fourier transform IR spectroscopy. Temporal dependences of integrated intensities of the absorption band of acetylsalicylic acid (ASA) near 1199 cm^–1 are measured for various ASA charges placed into a cuvette. Molar fractions of ASA in the saturated solution in SC–CO₂ are determined at a temperature of 40°C and pressures of 10.0 and 15.0 MPa, and the components are 2.10 ± 0.25 × 10^–4 and 11.0 ± 1.5 × 10^–4, respectively.     

The solubility of synthetic asymmetric allyl disulfides in subcritical and supercritical media

The solubility of two synthetic asymmetric allyl disulfides, allyl 8-quinolyl disulfide and allyl benzothiazol-2-yl disulfide, in subcritical Freon R22 and Freon R410a, as well as supercritical carbon dioxide, at a temperature of 40°C and a pressure of 200 bar is determined by a dynamic flow method. It is shown that Freon R22 is a promising solvent for practical applications of allyl disulfides.     

Sorption and Diffusion of Sub/Supercritical Carbon Dioxide in Poly(methyl methacrylate)

Sorption and desorption processes of subcritical and supercritical carbon dioxide in poly(methyl methacrylate) (PMMA) at various temperatures and pressures were investigated systematically. The gravimetric method was used to study the desorption and sorption diffusivities. It was found that there existed a characteristic value of pressure in the sorption isotherm of PMMA, above which saturation was observed to increase more rapidly with pressure. From the measured diffusivities of sorption and desorption under a wide range of operating conditions, the diffusivities of sorption was found to increase with increasing temperature, whereas the diffusivities of desorption showed a contrary trend.     

The viscosity and diffusion coefficients of eighteen binary gaseous systems

The paper reports accurate measurements of the viscosity of the eighteen binary gaseous systems: CF₄ with He, Ne, Ar, N₂, CO₂, CH₄; SF₆ with He, Ne, Ar, N₂, CO₂, CH₄, CF₄ and O₂ with He, Ne, CO₂, CF₄, SF₆. The measurements were performed in a high-precision oscillating-disk viscometer at atmospheric pressure and in the temperature range 25–200°C for the systems containing CH₄ or SF₆ and in the temperature range 25–400°C for the remainder. The reported viscosities are believed to be accurate to within ±0.1% at room temperature and to within ±0.2% at 400°C.It is shown that the data conform to the extended law of corresponding states developed by Kestin, Ro and Wakeham despite the complexity of some of the component gases. The standard deviation between the experimental values and those calculated from the law of corresponding states is only 0.3% which is commensurate with the uncertainty in the experimental results.Binary diffusion coefficients derived from the mixture viscosity data are also presented; they have an estimated uncertainty of ±2%.     

Polyester Fabric’s Fluorescent Dyeing in Supercritical Carbon Dioxide and its Fluorescence Imaging

As one of the most important coumarin-like dyes, disperse fluorescent Yellow 82 exhibits exceptionally large two-photon effects. Here, it was firstly introduced into the supercritical CO₂ dyeing polyester fabrics in this work. Results of the present work showed that the dyeing parameters such as the dyeing time, pressure and temperature had remarkable influences on the color strength of fabrics. The optimized dyeing condition in supercritical CO₂ dyeing has been proposed that the dyeing time was 60 min; the pressure was 25 MPa and the temperature was 120 °C. As a result, acceptable products were obtained with the wash and rub fastness rating at 5 or 4–5. The polyester fabrics dyed with fluorescent dyes can be satisfied for the requirement of manufacturing warning clothing. Importantly, the confocal microscopy imaging technology was successfully introduced into textile fields to observe the distribution and fluorescence intensity of disperse fluorescent Yellow 82 on polyester fabrics. As far as we know, this is the first report about supercritical CO₂ dyeing polyester fabrics based on disperse fluorescent dyes. It will be very helpful for the further design of new fluorescent functional dyes suitable for supercritical CO₂ dyeing technique.     

Optimization of a New Design of Molten Salt-to-CO2 Heat Exchanger Using Exergy Destruction Minimization

One of the ways to make cost-competitive electricity, from concentrated solar thermal energy, is increasing the thermoelectric conversion efficiency. To achieve this objective, the most promising scheme is a molten salt central receiver, coupled to a supercritical carbon dioxide cycle. A key element to be developed in this scheme is the molten salt-to-CO₂ heat exchanger. This paper presents a heat exchanger design that avoids the molten salt plugging and the mechanical stress due to the high pressure of the CO₂, while improving the heat transfer of the supercritical phase, due to its compactness with a high heat transfer area. This design is based on a honeycomb-like configuration, in which a thermal unit consists of a circular channel for the molten salt surrounded by six smaller trapezoidal ducts for the CO₂. Further, an optimization based on the exergy destruction minimization has been accomplished, obtained the best working conditions of this heat exchanger: a temperature approach of 50 °C between both streams and a CO₂ pressure drop of 2.7 bar.     

Catalytic oxidative coupling of dimethyl ether under supercritical conditions

Catalytic oxidative coupling of dimethyl ether (DME) is studied for the first time under supercritical conditions. The oxidation of DME with molecular oxygen of air in the presence of the CaO-SnO₂ catalyst is carried out in a substrate (DME) medium and in its mixtures with CO₂ under the supercritical conditions (100 atm, 250–300°C). At 255°C, the maximum conversion of DME (≈40% at the ratio of the yields of monoglim and diglim about 2: 1) is achieved at a 20-fold (by volume) dilution of DME with supercritical CO₂.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

The Effect of Supercritical CO2 on the Macromolecules Parallel Conformation and Its Relation to the Electrical Conductivity and Dielectric Behavior of Epichlorohydrin Terpolymer

The effect of supercritical CO₂ on the electrical conductivity of poly(epichlorohydrin–Ethylene oxide–Allyl glycidal ether) terpolymer is investigated using dielectric spectroscopy. Impedance measurements were carried out in the frequency range from 100–10 MHz and the temperature range of ?35–70°C with intervals of 5°C. The experimental results of the dielectric constant and the dielectric loss were fitted with the Cole–Cole equation to obtain the maximum relaxation frequencies of the different relaxation processes. As a result of the CO₂ treatment process, enhancement in the polymer chain mobility without noteworthy change in the glass transition temperature was determined. In addition, the level of the DC conductivity and the dielectric strength were increased. These effects were attributed to improvement in the chain dynamics, which arises from enhancement in the parallel conformation of macromolecules.     

Some thermodynamic processes of anthracite–carbon dioxide mixture in supercritical fluid state

In the context of the development of the catalyst regeneration procedure via supercritical fluid CO₂ extraction, some thermodynamic properties of the anthracene–carbon dioxide mixture in supercritical fluid state have been studied. Data on anthracene solubility in pure and modified (dimethyl sulfoxide, 5 wt %) supercritical carbon dioxide (SC–CO₂), the heat capacity of anthracene and its mixtures with carbon dioxide, and the heat of solution of anthracene in SC–CO₂ are presented. Anthracene solubility in SC–CO₂ is described satisfactorily using the Peng–Robinson equation of state.     

Activated carbon from coconut leaves for electrical double-layer capacitor

This study investigates the potential of coconut leaves as a precursor to obtain activated carbon. Coconut leaf-activated carbon (CLAC) has been prepared through gas activation process starting with carbonization at 400 °C in nitrogen flow for 3 h. The carbonized coconut leaves were milled using planetary ball milling followed by activation with carbon dioxide (CO₂) at different temperatures ranging from 700 to 1000 °C. The Brunauer–Emmett–Teller (BET) characterization reveals that the surface area of CLACs increases with the increase in activation temperature. Electrodes prepared from CLACs have been used to fabricate electrochemical double-layer capacitors (EDLCs) in order to study the electrochemical behavior using galvanostatic charge–discharge measurements and cyclic voltammetry. The carbon activated at 900 °C delivered the best specific capacitance of 133.4 F/g at current density of 200 mA/g.     

Effect of thermobaric conditions in a uniform bed on the displacement of low-viscosity oil by supercritical carbon dioxide

An experimental setup was constructed that makes it possible to study oil displacement over wide pressure (up to 20 MPa) and temperature (up to 373 K) ranges under conditions reproducing the thermobaric, geological, and physicochemical conditions in real oil beds, as well as the parameters of displacing agents. Experiments on the displacement of kerosene from a model oil bed with supercritical carbon dioxide at temperatures of 313–353 K and pressures within 7–12 MPa were performed. The results are indicative of a high efficiency of recovery of low-viscosity oils with supercritical carbon dioxide.     

The dispersion of polymeric materials with the use of supercritical fluids

The dispersion of polyisobutylene was studied on a Thar RESS-100-2 test bench over the temperature and pressure ranges 45–120°C and 100–350 bar; 30–1000 nm particles were obtained. Particle size could be controlled by varying process parameters. A procedure for modifying polymer particles during rapid expansion of supercritical solutions was suggested. Modification suppressed agglomeration and caused particle coating with a modifier (NaCl). The use of supercritical fluid antisolvents was shown to be promising for the dispersion of polymers to nanosized particles. An experimental bench for performing such processes was described. A procedure for trapping nanoparticles prepared using antisolvents was suggested. Particles with sizes of 10 to 150 nm were obtained in the dispersion of polystyrene in the toluene-polystyrene-supercritical carbon dioxide system at 40–150 bar and temperatures of 40 and 100°C.