Search Results (49)

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

Wood is a green and renewable bio-based building material, but its hygroscopicity affects its dimensional stability, limiting its use in construction. Chemical modification can improve its properties, yet its effectiveness depends on wood permeability and traditional modifiers. This study first used a deep eutectic solvent (DES) to boost the permeability of North American alder wood. Then, methyl trimethoxysilane was impregnated under supercritical carbon dioxide (SCI), pressure (PI), vacuum (VI), and atmospheric pressure (AI) conditions. DES treatment damaged the cell structure, increasing wood permeability. Silane was deposited and polymerized in the cell lumen, chemically bonding with cell-wall components, filling walls and pits, and thickening walls. The VI group had the highest absolute density (0.59 g/cm³, +36.6%) and the lowest moisture absorption (4.4%, −33.3%). The AI group had the highest ASE (25%). The PI group showed the highest surface hardness (RL, 2592 N) and a water contact angle of 131.9°, much higher than natural wood. Overall, the VI group had the best performance. Silane reacts with cellulose, hemicellulose, and lignin in wood via hydrolysis and hydroxyl bonding, forming stable bonds that enhance the treated wood’s hydrophobicity, dimensional stability, and surface hardness. Full article

Lingonberry pomace (LP) is a by-product rich in valuable bioactive compounds and can be used in the food industry after various treatments and property characterization. This study aimed to evaluate the impact of commercially available enzymes (Viscozyme^® L, Pectinex^® Ultra Tropical, and Celluclast^® 1.5 L) and supercritical carbon dioxide (SFE-CO₂) extraction technology on the chemical composition and technological properties of treated LP products. The Megazyme kit was used to determine the soluble dietary fiber (SDS) and insoluble dietary fiber (IDF) contents, while the changes in mono-, disaccharide, and oligosaccharides were analyzed by applying high-pressure liquid chromatography with a refractive index detector. The analyzed properties were as follows: the water swelling capacity (WSC), water retention capacity (WRC), water solubility index (WSI), oil retention capacity (ORC), bulk density (BD), and emulsion stability of modified LP. The tested LP contained 8.49 g/100 g of SDF and 65.36 g/100 g of IDF (in dry matter). The partial separation of lipophilic substances during SFE-CO₂ extraction did not significantly affect the enzymatic hydrolysis efficiency. The amount of oligosaccharides in the LP increased using enzymes with pectinolytic activity (Viscozyme^® L and Pectinex^® Ultra Tropical), while cellulolytic enzymes (Celluclast^® 1.5 L) increased the amount of SDF and improved the IDF/SDF ratio. Enzymatic hydrolysis increased the SI, WRC, and ORC of LP powder. Emulsions with LP hydrolyzed with Pectinex^® Ultra Tropical demonstrated the highest stability during storage. This study demonstrates that the modification of LP powders provides diverse technological properties, which could expand the application of such products for further food production. Full article

Conventional PP with a linear chain structure is not suitable for foam processing due to its poor rheological properties. In this study, PP was modified with PE through reactive melt blending of maleic anhydride-grafted PP (MA-PP) with a small amount of PE bearing glycidyl groups on its backbone (G-PE), with the aim of enhancing the melt rheological properties of PP to make it suitable for foam processing. An anhydride–epoxy reaction occurred between MA-PP and G-PE during the melt processing, resulting in the formation of a crosslinked polymer network, which was confirmed by FTIR spectroscopy, a solubility test, and the presence of a rubbery plateau above the melting point. Melt rheological tests demonstrated that the modified PP showed a pronounced shear-thinning effect and higher elasticity compared to pristine PP. Foaming tests using supercritical carbon dioxide as a foaming agent in an autoclave demonstrated that the modified PP could produce a microcellular foam with a closed-cell structure, which was not achievable with neat PP. Full article

A comparative metabolomic study of three varieties of wild Rosa (Rosa acicularis, Rosa amblyotis, and Rosa rugosa) from a Kamchatka expedition (2024) was conducted via extraction with supercritical carbon dioxide modified with ethanol (EtOH), and detection of bioactive compounds was realized via tandem mass spectrometry. Several experimental conditions were investigated in the pressure range 50–350 bar, with the used volume of co-solvent ethanol in the amount of 2% in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions are the following: pressure 200 Bar and temperature 55 °C for Rosa acicularis; pressure 250 Bar and temperature 60 °C for Rosa amblyotis; pressure 200 Bar and temperature 60 °C for Rosa rugosa. Three varieties of wild Rosa contain various phenolic compounds and compounds of other chemical groups with valuable biological activity. Tandem mass spectrometry (HPLC-ESI–ion trap) was applied to detect the target analytes. A total of 283 bioactive compounds (two hundred seventeen compounds from the polyphenol group and sixty-six compounds from other chemical groups) were tentatively identified in extracts from berries of wild Rosa. For the first time, forty-eight chemical constituents from the polyphenol group (15 flavones, 14 flavonols, 4 flavan-3-ols, 3 flavanones, 1 phenylpropanoid, 2 gallotannins, 1 ellagitannin, 4 phenolic acids, 1 dihydrochalcone, and 3 coumarins) were identified in supercritical extracts of R. acicularis, R. amblyotis, and R. rugosa. Full article

Supercritical multicomponent thermal fluid injection is a new technology with great potential for offshore heavy oil thermal recovery. In the process of thermal fluid generation, the reaction conditions including temperature, pressure, and the organic mass concentration in the reaction material will significantly affect its composition and injection rate and will further affect the thermal recovery and development quality of heavy oil. However, there is a lack of relevant research on the variation rules and control methods of the composition and injection rate of supercritical multicomponent thermal fluids, resulting in a lack of technical mechanisms for effective optimization. To fill this gap, a reaction molecular dynamics simulation method was used to simulate thermal fluid generation under different temperatures, pressures, and organic mass concentrations. The changes in thermal fluid composition and yield with reaction conditions were studied, and a control model of thermal fluid composition and yield was established. The proportional relationship between the thermal fluid generation scale of an offshore heavy oil platform and the simulated thermal fluid generation scale is analyzed, and a collaborative optimization method of thermal fluid composition and injection rate in field applications is proposed. The results show the following: (1) The higher the mass concentration of organic matter, the higher the content of supercritical carbon dioxide and supercritical nitrogen in thermal fluids, and the lower the content of supercritical water. (2) The higher the temperature and pressure, the higher the thermal fluid yield, and the higher the organic mass concentration, the lower the thermal fluid yield. (3) The component fitting model conforms to the power function relationship, and the coefficient of determination R² is greater than 0.9; the yield fitting model conforms to the modified inverse linear logarithmic function relationship, the determination coefficient R² is greater than 0.8, and the fitting degree is high. (4) The ratio between the actual injection rate of thermal fluids in the mine field and the molecular simulated thermal fluid yield is the ratio of organic matter mass in the platform thermal fluid generator and organic matter mass in the simulated box. (5) Based on the composition and yield control model, combined with the simulation of the ratio relationship between yield and injection rate in the field, a collaborative optimization method of thermal fluid composition and injection rate was established. The research results can provide an effective technical method for predicting, controlling, and optimizing the composition and injection rate of supercritical multicomponent thermal fluids. Full article

This study investigates the modeling and experimental validation of cell morphology in microcellular-foamed polycaprolactone (PCL) using supercritical carbon dioxide (scCO₂) as the blowing agent. The microcellular foaming process (MCP) was conducted using a solid-state batch foaming process, where PCL was saturated with scCO₂ at 6 to 9 MPa and 313 K, followed by depressurization at a rate of −0.3 and −1 MPa/s. This study utilized the Sanchez–Lacombe equation of state and the Peng–Robinson–Stryjek–Vera equation of state to model the solubility and density of the PCL-CO₂ mixture. Classical nucleation theory was modified and combined with numerical analysis to predict cell density, incorporating factors such as gas absorption kinetics, the role of scCO₂ in promoting nucleation, and the impact of depressurization rate and saturation pressure on cell growth. The validity of the model was confirmed by comparing the theoretical predictions with experimental and reference data, with the cell density determined through field-emission scanning electron microscopy analysis of foamed PCL samples. This study proposes a method for predicting cell density that can be applied to various polymers, with the potential for wide-ranging applications in biomaterials and industrial settings. This research also introduces a Python-based numerical analysis tool that allows for easy calculation of solubility and cell density based on the material properties of polymers and penetrant gases, offering a practical solution for optimizing MCP conditions in different contexts. Full article

A comparative metabolomic study of three varieties of alfalfa (Medicago varia Mart.) was performed via extraction with supercritical carbon dioxide modified with ethanol (EtOH) and the detection of bioactive compounds via tandem mass spectrometry. Several experimental conditions were investigated in the pressure range of 50–250 bar, with ethanol used as a co-solvent in an amount of 1% of the total volume in the liquid phase at a temperature in the range of 31–70 °C. The most effective extraction conditions were as follows: a pressure of 250 Bar and a temperature of 60 °C for M. varia. M. varia contains various phenolic compounds and sulfated polyphenols with valuable biological activity. Tandem mass spectrometry (HPLC-ESI–ion trap) was applied to detect the target analytes. A total of 103 bioactive compounds (59 polyphenols and 44 compounds belonging to other chemical groups) were tentatively identified in extracts from aerial parts of alfalfa. For the first time, twenty-one chemical constituents from the polyphenol group (flavones: Formononetin, Chrysoeriol, Cirsimaritin, Cirsiliol, Cirsilineol, tricin-O-hexoside, Apigenin C-glucose C-deoxyhexoside, Apigenin 7-O-diglucuronide, 2′-Hydroxygenistein 4′,7-O-diglucoside, etc.) and six from other chemical groups (saponins: Soyasaponin II, Soyasaponin gamma g, Soyasaponin I, Soyasaponin Bd, Soyaysaponin beta g, etc.) were identified in the aerial parts of M. varia. Full article

In this study, water was used as an additive in the methanol-modified carbon dioxide-based eluent for the elution of some basic organic compounds from a hybrid silica column via supercritical fluid chromatography (SFC). The experiments were applied to sulfonamides, propranolol, and other organic nitrogen compounds involving aromatic rings from different classes of amine, pyrimidine, and purine with different pKa values (the pKa values for the studied analytes range from 4.6 to 10.4). The results revealed different responses to the different percentages of water addition. Adding 1~2% of water to the modifier (methanol) led to a positive effect manifested by more symmetrical peak shapes and reduced retention times for most compounds. The key factor for this improvement in the properties of chromatographic peaks is due to the adsorption of water on the silanol groups of the stationary phase, consequently resembling the phenomena observed in hydrophilic interaction liquid chromatography (HILIC). Moreover, the availability of hydrogen bond acceptor and donor sites in the analyte structure is an important factor to be considered when adding water as an additive to the modifier for improving the chromatographic peaks. However, introducing water in an amount higher than 3% resulted in perturbed chromatographic signals. It was also found that water as an additive alone could not successfully elute propranolol from the hybrid silica column with an acceptable peak shape; thus, the addition of a strong base such as amine salts was also necessary. The proposed use of a particular amount of water in the mobile phase could have a positive effect compared to the same mobile phase without water, improving the chromatographic peak properties of the elution of some basic organic compounds from the hybrid silica column. Full article

The gas turbine is a crucial piece of equipment in the energy and power industry. The exhaust gas has a sufficiently high temperature to be recovered for energy cascade use. The supercritical carbon dioxide (S-CO₂) Brayton cycle is an advanced power system that offers benefits in terms of efficiency, volume, and flexibility. It may be utilized for waste heat recovery (WHR) in gas turbines. This study involved the design of a 5 MW S-CO₂ recompression cycle specifically for the purpose of operational control. The dynamic models for the printed circuit heat exchangers, compressors, and turbines were developed. The stability and dynamic behavior of the components were validated. The suggested control strategies entail utilizing the cooling water controller to maintain the compressor inlet temperature above the critical temperature of CO₂ (304.13 K). Additionally, the circulating mass flow rate is regulated to modify the output power, while the exhaust gas flow rate is controlled to ensure that the turbine inlet temperature remains within safe limits. The simulations compare the performance of PI controllers tuned using the SIMC rule and ADRC controllers tuned using the bandwidth method. The findings demonstrated that both controllers are capable of adjusting operating conditions and effectively suppressing fluctuations in the exhaust gas. The ADRC controllers exhibit a superior control performance, resulting in a 55% reduction in settling time under the load-tracking scenario. Full article

Pomegranate (Punica granatum L.) is a widely used fruit in the dietary supplement industry due to its richness in bioactive compounds. In this study, an experimental design was applied to optimize supercritical fluid extraction (SFE) of polar compounds of interest (ellagic acid and punicalagins), known for antioxidant and skin care properties from pomegranate’s pericarp. The effects of temperature, modifier percentage, and water additive percentage added in the modifier were explored through a Box–Behnken design, followed by a study of the extraction kinetics. The results indicated that 40 °C, 20% EtOH:H₂O 80:20 v:v, with an extraction duration of 60 min allowed for the highest recovery of the above-mentioned molecules (19.59 mg/g). Due to solubilization issues encountered by the extract, a screening of cosmetic solvents was carried out to solubilize SFE pomegranate extracts and a composition of Gly:H₂O 80:20 v:v was selected. Furthermore, an integrated SFE pre-formulation process of pomegranate pericarp extract (PPE) was elaborated. This allowed for the recovery of the extracts in cosmetic solvent, avoiding a full evaporation. Finally, the stability of the pre-formulated extracts was evaluated and showed high stability for over 3 months at 5 °C. Full article

The interaction between shale and various fluids is crucial as it modifies pore structures, which govern the effective development of shale gas and the geological storage of carbon dioxide in shale formations. In this study, samples from the Longmaxi Formation shale in Sichuan Basin of China were exposed to different fluids, including 6 MPa CO₂, 12 MPa CO₂, 6 MPa CO₂+brine, and 12 MPa CO₂+brine, at 45 °C for 100 days. Various methods, including X-ray diffraction (XRD), X-ray fluorescence (XRF), field-emission scanning electron microscopy (FESEM), and the low-pressure gas adsorption (N₂) test, were adopted to evaluate chemical and structural changes during the exposure process. After being treated with supercritical CO₂+brine and subcritical CO₂+brine, the shale underwent significant changes in its major element composition. The content of Ca, Al, and K in shale saturated with supercritical CO₂+brine decreased from 13.00% to 10.34%, from 3.65% to 3.36%, and from 1.56% to 1.37%, respectively. Meanwhile, the content of Si and Na in the same shale increased slightly after saturation. The amount of quartz and dolomite increased, while the levels of clay and calcite slightly decreased. The surface of the shale sample became rougher and small bumps and cracks appeared after saturation with different fluids, as shown by the FESEM analysis results. Furthermore, the changes in both the total pore volume and pore size followed a similar pattern to the alterations in the specific surface areas. The highest level of variation occurred with the shale that was saturated with 12 MPa of CO₂, indicating that gas pressure and CO₂ phase state have a significant influence on the shale’s pore structure. In addition, the distribution of pore sizes showed a bias towards larger sizes across all diameters; this suggests that the reaction resulted in a decrease in the number of micropores. This also highlights that the impact of varying fluid saturation was primarily focused on micropores and macropores. The results of this study provided experimental evidence to further test the mechanisms and permeability of geological storage of CO₂ in organic-rich self-sourced shale. Full article

Sunflowers are among the world’s most widely cultivated oilseeds with an interesting nutritional composition. A biomass composed mainly of carbohydrates, fibers, and proteins is generated from sunflower oil production. In this context, the objective of this study was to investigate the application of emerging technologies to sunflower biomass to obtain an edible protein-rich flour with the potential to be exploited in the food industry. The effects of the optimized conditions for the sequential processing of sunflower meal using supercritical carbon dioxide (SCO₂) and high-intensity ultrasound (HIUS) were investigated. The protein structure was preserved even after the application of HIUS to the flour as verified through differential scanning calorimetry (DSC) and the electrophoresis curves. The fact that the HIUS treatment did not modify the protein structure demonstrates that this emerging technology could be incorporated into the processing chain of this new food ingredient (sunflower flour) without promoting damage to the nutritional value of the product regarding its protein content. At a pH of 7.0, the flour showed only 30% solubility, and HIUS application improved both the formation and the stability of the emulsion when compared to the other samples. The preliminary evaluation of cell viability (caco₂ cells) showed its protective potential against reactive oxygen species. Therefore, the flour resulting from the green processes presented the potential to be employed as an ingredient in the food industry, presenting a technological and nutritional potential when considering its chemical composition. In addition to the novel edible flour, the phenolic compounds obtained a present potential as a functional ingredient to be incorporated into foods. Full article

The use of bioactive plant extracts in cosmetic products is a common practice. Most of these extracts are obtained by maceration in organic solvents, and depending on which solvents are used, the polarity and the structure of the target molecules will vary. Polyphenols are polar compounds that often display antioxidant and/or antibacterial activities. To extract them, ethanol/water mixtures are usually selected as green solvents. This solid–liquid extraction (assisted or not) requires the use of high volumes of solvents and many additional steps like mixing, agitation, filtration, and evaporation. Alternatively, supercritical carbon dioxide (SC-CO₂) offers many benefits for plant extraction: economical, non-toxic, and naturally concentrated extracts. However, its low polarity is not suitable to solubilize polar compounds. In this study, an experimental design was used to optimize supercritical fluid extraction (SFE) of caffeine and catechins from Camellia sinensis. Catechins are recognized for skin care use (antioxidant) and caffeine is also used for its skin care properties and to prevent excess storage of fat in cells. The temperature, modifier content, and water additive percentage were used as independent variables. The results showed that while the temperature was an insignificant parameter, a higher percentage of water (up to 20% in ethanol) and modifier favored the extraction of the polar target molecules. Additionally, the SFE results were compared with ultrasound-assisted extraction (UAE). Finally, a sequential selective extraction of caffeine from catechins is also presented. Full article

In the context of food waste valorization, the purpose of this study is to demonstrate the complete valorization of soybean residue (okara) through supercritical carbon dioxide extraction (SCE). Okara oil (OKO) was separated from full-fat powder (FFP) using SCE with and without ethanol (EtOH) as a cosolvent. The kinetics of extraction, chemical composition, and physicochemical, functional, and health-promoting properties of OKO and defatted powder (DFP) were determined. The process yielded 18.5% oil after 450 min. The soluble dietary fiber and protein of the DFP increased significantly; its water and oil absorption capacities increased despite the decrease in swelling capacity corresponding to particle size reduction. The OKO was rich in linoleic and oleic acids, with a ratio of ω6-to-ω3 fatty acids = 9.53, and EtOH increased its phenolic content (0.45 mg GAE/g), aglycone content (239.6 μg/g), and antioxidant capacity (0.195 mg TE/g). The DFP paste showed gel-like consistency and shear-thinning flow behavior, whereas the OKO showed characteristic transition of the product and affected lubrication at contact zones. Both fractions showed potential as food ingredients based on their nutritional and functional properties, as well as the capability of modifying the microstructure of a model food system. Full article