Extraction of Taiheiyo coal with supercritical water–phenol mixtures

Taiheiyo Japanese sub-bituminous coal was extracted with supercritical water (SCW) and phenol mixtures at 673 K and at over fluid densities ranging from 0 to 0.5 g/cm³. The extraction yield with SCW was 0.55–0.60, but increased with increasing the ratio of phenol to water, showing a maximum of 0.7 at water–phenol ratio of 4.5:0.5 and then decreased to 0.50–0.55 for pure phenol.The main products for the SCW–phenol extraction were bisphenol alkyl compounds, while these compounds could not be detected when SCW was used as the solvent. For elucidating the mechanism of SCW–phenol extractions, reactions between phenol and model compounds of hydrolysis products (formaldehyde, acetone, propionic acid, and 2-propanol) were conducted. In SCW, formaldehyde reacted with phenol to produce polymers, while neither acetone nor propionic acid reacted with phenol. The 2-propanol dehydrated to form propene, which reacted with phenol to form 2-isopropylphenol. The reaction rate increased with increasing water density. In SCW–phenol extraction of coal, phenol seems to inhibit reactions that lead to hydrolysis products or those that might cross-link to form the macromolecules. Phenol can be used with SCW to reduce retrograde reactions in residual coals.     

Synthesis of higher alcohols from syngas over Zn–Cr–K catalyst in supercritical fluids

An investigation was carried out on the selective synthesis of higher alcohols from syngas in a supercritical fluid (a mixture of C₁₀–C₁₃ alkanes) by using a fixed bed reactor. Experiments were conducted over Zn–Cr–K catalyst in the temperature range of 360–400°C, a partial pressure of syngas of 7.5 MPa and a partial pressure of supercritical medium of 1.78 MPa. Comparison of results in the gas phase with those in the supercritical phase indicated that CO conversion was higher in the supercritical phase reaction. Alcohol selectivity decreased slowly with increasing temperature in the supercritical phase reaction but decreased rapidly in the gas phase reaction, due to the special properties of supercritical fluids (SCF). Product distributions were different in both reaction phases. The introduction of the supercritical medium promoted carbon chain growth and the content of C₂⁺OH was increased. The product distribution features with high methanol content of the gas phase synthesis were changed.     

Improved thermal interface property of carbon nanotube–Cu composite based on supercritical fluid deposition

In this paper, we present a new synthesis method of carbon nanotubes (CNTs)-copper (Cu) composite on a silicon substrate using combination of supercritical fluid deposition (SCFD) and electrochemical plating (ECP) process. Deposition of a Cu layer onto CNTs is carried out under supercritical condition, and the CNTs–Cu composite with high-density Cu is synthesized by additional ECP process. The Cu layer deposited by SCFD functions as a seed layer for ECP, and spaces between neighboring CNTs are filled by Cu. The measured density of the CNTs–Cu composite is 8.2 ± 0.3 g/cm³, and the volume percentage of voids is 3–6%. The evaluated thermal resistance including the thermal interface resistance and bulk resistance of the composite is as low as 28.4 mm² K W⁻¹ at a contact pressure of 0.2 MPa. A CNT brush formed on the composite surface can reduce the thermal resistance to be 68.4 mm² K W⁻¹ at a contact pressure of 0.25 MPa. The CNTs–Cu composite shows the ability applicable to many microelectronics applications as a thermal interface material.     

Probabilistic assessment of the safety profile of the Fischer–Tropsch process with a supercritical solvent

Inherent safety assessment during the design stage of chemical processes is typically conducted based on average values for design parameters. Under those conditions, the single-point deterministic process performance assessment may be affected by the phenomenon known as the ‘flaw of averages’ in the presence of irreducible sources of uncertainty (performance evaluated at average conditions does not represent average performance). In this work, an inherent process safety assessment developed under a probabilistic formulation is presented. An evaluation of the proposed approach is performed in the case of a gas-to-liquid process system using a supercritical solvent for Fischer–Tropsch reactor systems. The pertinent uncertainty analysis is carried out using Monte Carlo simulation techniques to account for the propagation of uncertainty through the inherent process safety model and the derivation of probability distribution profiles for the associated metrics, thus statistically characterizing ranges of potential performance outcomes. The response variables were the autothermal reactor and the syngas flows. The results show that the input variables associated to the autothermal flow potentially generate the most hazardous conditions for the process. The results also show how the metrics are affected when uncertainty is explicitly taken into account at the design stage of the process, offering a more nuanced assessment and characterization of the inherent process safety profile.     

A systematic study on the interactions between carnosic acid and ethylpyrrolidine methacrylate–methyl methacrylate copolymer in supercritical media

In the present work, a systematic study on the interactions between carnosic acid (potent natural antioxidant from rosemary) and ethylpyrrolidine methacrylate–methyl methacrylate (EPyM/MMA) copolymer (synthesized in our laboratory) has been performed using different spectroscopic and thermogravimetric techniques. By comparing data obtained for the reference sample (carnosic acid + copolymer) with data of carnosic acid and copolymer alone, a polar interaction could be observed between the carboxylic acid group of carnosic acid with the tertiary amine of the EPyM/MMA copolymer, thus suggesting a charge-transfer complex of the carnosic acid molecules with the pyrrolidine nitrogen (conclusion supported by NMR, FT-IR and TGA data). In order to evaluate the possibility of using, in the near future, the copolymer as a selective stationary phase for preparative-SFC (supercritical fluid chromatography), the work has been completed by studying the remaining interactions, in the reference sample, once treated under several supercritical conditions. After the supercritical treatment (using CO₂ at different pressures and temperatures), depressurization takes place in the extraction cell and the samples remaining were characterized by ¹H NMR, TGA and FT-IR. From the results obtained, it can be inferred that interactions remain after supercritical treatment, thus allowing the design of selective polymers to be used in the purification of carnosic acid.     

The effect of ethyl-lactate and ethyl-acetate plasticizers on PCL and PCL–HA composites foamed with supercritical CO2

The present study reports foaming of polycaprolactone (PCL) and PCL nano- and micro-composites with dispersed hydroxyapatite (HA) particles by means of binary mixtures of supercritical CO₂ (scCO₂) and either ethyl lactate (EL) or ethyl acetate (EA) as plasticizer. The effect of the size and concentration of HA particles, as well as the effects of the plasticizer type and the incorporation route were investigated aiming to fabricate porous scaffolds with uniform morphology and controlled pore size distribution. For this purpose, foaming experiments were carried out by selecting two operating temperatures, 40 and 45 °C, and two soaking times, 1 and 17 h. Furthermore, a double step of depressurization was used to promote the development of a double-scale pore size structure in porous scaffolds useful for tissue engineering.The results of this study indicated that supercritical foaming of PCL and PCL–HA composites is enhanced when the selected operating temperature and time are 45 °C and 17 h, respectively. Furthermore, although both EL and EA plasticizers enhanced the low temperature foaming of the materials, we demonstrated that the route of incorporation of the plasticizer is a critical aspect for enhancing composite foaming and scaffold fabrication. From this point of view, the best results were achieved when EA was pre-mixed with the polymeric powder for preparing a dough for the foaming process.     

Estimation of solubility of solids in supercritical carbon dioxide

Peng-Robinson equation of state(PR EOS)was chosen for modeling the thermodynamic be-havior of supercritical(SC)-CO_2/Solid systems.The necessary critical constants and acentric factorof the solute were obtained by the Sigmund and Trebble(1992)method based on the molecular weightand boiling temperature,and the vapor pressure of the solute was calculated by its meltingtemperature and heat of fusion.This approach compared very favorably with the conventional corres-ponding state theory,but without using critical constants and vapor pressure of solutes.Four mixingrules were tested for the calculation of solid solubility in SC-CO_2.van der Waals(vdW)mixing rulewith one parameter was considered to be most suitable for the estimation of solubility.A simplecorrelation was developed for the SC-CO_2/solid binary interaction coefficient k_(ij) with the meltingtemperature of pure solutes.The solubilities of solids in SC-CO_2 were estimated for eleven binarysystems at various temperatures,the total absolute average     

Measurement and correlation of solid drugs solubility in supercritical systems

A dynamic experimental set-up was utilized to measure ibuprofen solubility in supercritical CO2 at the pressure range of 8-13 MPa and the temperatures of 308, 313 and 318 K. Mole fraction values varied from 0.015＆#215;10^-3 to 3.261＆#215;10^-3 and correlated by using seven different semi empirical equations of state （Bartle, Modi-fied Bartle, Mendez-Teja, Modified Mendez-Teja, Kumar-Johnson, Sung-shim and Gordillo） as well as seven cubic equations of state （van der Waals, Redlich-Kwong, Soave-Redlich-Kwong, Peng-Robinson, Stryjek-Vera, Patel-Teja-Valderana and Pazuki）. Single and twin-parametric van der Walls mixing rules （vdW1, vdW2） were ap-plied in order to estimate the supercritical solution properties. The physicochemical properties were also obtained using Joback, Lydersen and Ambrose methods. Absolute average relatives deviation （AARD） were calculated and compared for all the correlating systems. Results showed that among the cubic equations of state （EOSs） the Pazuki equation （AARD=19.85% using vdW1 and AARD=8.79% using vdW2） and SRK equation （AARD=19.20%using vdW1 and AARD=10.03%using vdW2） predicted the ibuprofen solubility in supercritical CO2 with the least error in comparison to the others. Among the semi-empirical EOSs the most desirable deviation （AARD〈10%） was obtained by using Modified Bartle and Modified Mendez-Teja equations in all the studied temperatures.     

Three-phase catalytic hydrogenation of α-methylstyrene in supercritical carbon dioxide

The three-phase catalytic hydrogenation (TPCH) of α-methylstyrene using supercritical carbon dioxide (scCO₂) in a slurry reactor is reported. Kinetic data are presented for the reaction at 323 K over the range of pressure from 7.0 to 13.0 MPa using a carbon-supported palladium catalyst. The experimental data are fitted to a first-order power-law model. A detailed explanation of the methodology used to isolate the effect of CO₂ on the rate of reaction is presented. Particular attention is given to the phase behaviour of the reaction system and the volumetric expansion of the liquid phase with CO₂. It is shown that scCO₂ significantly enhances the rate of reaction. This effect is attributed to the enhancement of the solubility of hydrogen in the liquid phase.     

Continuous oxidation of benzyl alcohol in “supercritical” carbon dioxide

Supercritical (dense) carbon dioxide has been applied as solvent for the partial oxidation of benzyl alcohol with molecular oxygen in a fixed-bed reactor. High rate and good selectivity to benzaldehyde (93–97%) has been achieved with 0.5 wt% Pd/alumina or 0.5 wt% Pd/C, at around 100C and 100 bar, using only moderate excess of oxygen. The by-product benzoic acid has an autocatalytic effect on the hydration of benzaldehyde, and the subsequent oxidative dehydrogenation leads to benzoic acid, and benzyl benzoate by esterification. Promotion of Pd by Pb improves the selectivity. No catalyst deactivation or metal leaching has been observed. The method provides reasonable yields at much lower temperature than that applied in conventional gas phase oxidation, showing a potential for the synthesis of thermolabile, water-insoluble aromatic aldehydes.     

A numerical study of capillary pressure–saturation relationship for supercritical carbon dioxide (CO2) injection in deep saline aquifer

Carbon capture and sequestration (CCS) is expected to play a major role in reducing greenhouse gas in the atmosphere. It is applied using different methods including geological, oceanic and mineral sequestration. Geological sequestration refers to storing of CO₂ in underground geological formations including deep saline aquifers (DSAs). This process induces multiphase fluid flow and solute transport behaviour besides some geochemical reactions between the fluids and minerals in the geological formation. In this work, a series of numerical simulations are carried out to investigate the injection and transport behaviour of supercritical CO₂ in DSAs as a two-phase flow in porous media in addition to studying the influence of different parameters such as time scale, temperature, pressure, permeability and geochemical condition on the supercritical CO₂ injection in underground domains. In contrast to most works which are focussed on determining mass fraction of CO₂, this paper focuses on determining CO₂ gas saturation (i.e., volume fraction) at various time scales, temperatures and pressure conditions taking into consideration the effects of porosity/permeability, heterogeneity and capillarity for CO₂–water system. A series of numerical simulations is carried out to illustrate how the saturation, capillary pressure and the amount of dissolved CO₂ change with the change of injection process, hydrostatic pressure and geothermal gradient. For example, the obtained results are used to correlate how increase in the mean permeability of the geological formation allows greater injectivity and mobility of CO₂ which should lead to increase in CO₂ dissolution into the resident brine in the subsurface.     

The 20th anniversary of the Journal of Supercritical Fluids–A special issue on future directions in supercritical fluid science and technology

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Bitter potato starch-based film enriched with copaiba leaf extract obtained using supercritical carbon dioxide: Physical–mechanical,antioxidant, and disintegrability properties

Films based on bitter potato starch (BPS) and its blends with chitosan (BPS-Ch) or soy protein isolate (BPS-SPI) loaded with copaiba leaf extract (E) are prepared via the casting method. The physical–mechanical and antioxidant properties of the as-prepared films are compared with those of a control. Moreover, the half-maximal degradation (t₅₀) of the prepared films is calculated by fitting the Hill model to disintegrability kinetic data. Among the analyzed films, BPS-Ch-E exhibits the lowest (p < 0.05) solubility in water and opacity, strongest water vapor-barrier (3.58 × 10⁻¹¹ g m⁻¹ s⁻¹ Pa⁻¹), and highest tensile strength and elongation at break. The Fourier transform infrared spectra of BPS-Ch-E and BPS-SPI-E demonstrate new peaks at 1550, 1239, and 1070 cm⁻¹ corresponding to N H and C O stretching. The BPS-E and BPS-Ch-E surfaces are devoid of scratches and phase separation. The incorporation of E significantly increases the antioxidant activity of the films. BPS-SPI-E and BPS-Ch-E demonstrate the lowest (t₅₀ ≈ 1.4 days) and highest (t₅₀ ≈ 3.5 days) disintegration rates, respectively, among the prepared films. E loading facilitates the development of films possessing beneficial physical–mechanical and antioxidant properties as well as rapid disintegrability, enabling their potential application as a eco-friendly packaging material.     

Solubility of Δ-tetrahydrocannabinol in supercritical carbon dioxide: Experiments and modeling

The solubility of Δ⁹-tetrahydrocannabinol (Δ⁹-THC) in supercritical carbon dioxide has been determined at 315, 327, 334 and 345 K and in the pressure range from 13.2 to 25.1 MPa using an analytical method with a quasi-flow apparatus. Prior to performing these measurements, the method was validated by measuring anthracene solubilities and comparing these with literature values. The molar solubility for Δ⁹-THC ranged from 0.20 to 2.95 × 10⁻⁴. The data were correlated using the Peng-Robinson equation of state in combination with quadratic mixing rules. Deviations between calculated results and the experimental data ranged from 4.1 to 13.3% absolute average relative deviation (AARD).     

Maturation of a ketoprofen/β-cyclodextrin mixture with supercritical carbon dioxide

This work studies the maturation process of an association complex between an active compound, ketoprofen (KP) and a β-cyclodextrin (CD) with supercritical carbon dioxide (SC-CO₂). The process involves putting these two compounds into contact with a certain quantity of water, over a certain duration, to obtain the complex. We have studied the phenomena involved and the influence of several operating parameters on the complexation rate. The results enable us to suggest explanations for the phenomena involved in inclusion formation. An increase in the parameters related to the process: pressure, temperature, maturation period, agitation and density of SC-CO₂ resulted in an increase in the association rate of KP with CD in all cases. The water added at the end of the mixing procedure allowed a surface solubilization of CD where a ripening phenomenon can occur, but it is also a destabilizing agent for the water already adsorbed on the CD. The added water then favours an evolution towards a more stable energy state by enhancing the emptying of the CD cavities, and being replaced by KP. The mass ratio of the SC-CO₂/mixture had an effect on association, as the use of great volumes of CO₂ caused dilution of KP and was deleterious to the complexation rate. It was also found that the method of mixture preparation influenced the formation of the complex: adding water before KP onto CD inhibited complexation. The stoichiometry of complexation was found to be one molecule of KP with two molecules of CD. With control of both the operating conditions (pressure, temperature, maturation period, agitation and density of SC-CO₂) and the preparation of the mixing, this process leads to high percentages of complexation without the use of organic solvent.     

Extraction kinetics of pre-pelletized Jalapeño peppers with supercritical CO2

The aim of this work was to assess and model supercritical carbon dioxide (ScCO₂) extraction kinetics of pre-pelletized Jalapeño peppers (Capsicum annuum L.). Pepper flakes were conditioned to low moisture, ground finely and pelletized at high pressure, and pellets were subsequently ground and size classified. The effects of average sample particle size (D_p=0.28–3.19 mm) and superficial solvent velocity (U_s=0.14–2.62 mm s⁻¹) were evaluated at 40 °C and 120 or 320 bar. Extraction rate increased as a result of a decrease in D_p. It also increased as a result of an increase in U_s at 120 bar, but the effect was almost negligible at 320 bar. Integral extraction yields of capsicum oleoresin and capsaicinoids were ≈0.102 g g⁻¹ and ≈240 mg kg⁻¹, respectively, independent of extraction conditions. External mass transfer coefficients (k_f) increased with U_s, but this effect was less pronounced than commonly reported in the literature. Values of k_f increased as D_p or process pressure decreased, due respectively to increments in specific area and improvements in transport properties. Internal mass transfer coefficients, on the other hand, were 5.3×10⁻⁸ m s⁻¹ at 40 °C and 120 bar, and 34.7×10⁻⁸ m s⁻¹ at 40 °C and 320 bar. Solutes were effectively liberated from the original matrix with our multistage pretreatment, so that the fraction of free solute did not depend on D_p (α=0.46). Pseudosolubilities for capsicum oleoresin in ScCO₂ (≈2100 mg l⁻¹ at 40 °C and 120 bar; ≈13,700 mg l⁻¹ solute/CO₂ at 40 °C and 320 bar) were of the same order of magnitude as corresponding true solubilities of capsaicin (5600 and 11,800 mg l⁻¹, respectively). Estimated true solubilities of chlorophyll-a in ScCO₂ (2 mg l⁻¹ at 40 °C and 120 bar; 18 mg l⁻¹ at 40 °C and 320 bar), on the other hand, were orders of magnitude smaller, which justifies a much slower extraction rate for green pigments than pungent compounds. Thus, oleoresin obtained after 4 h at 40 °C and 120 bar had a very attractive light yellow tinge.