Supercritical Carbon Dioxide Research Articles

Use of supercritical CO2 to improve the quality of lupin protein isolate

Lupins are an excellent source of protein which can be used to obtain protein isolates with potential use in the food industry. Some studies use supercritical CO2 (SC-CO2) to defat legume flours, but no study analyzes the effect of applying this technology directly to the protein isolate. This article has proposed the use of SC-CO2 to improve lupin protein isolate (LPI) quality. SC-CO2 increased the LPI purity while reducing oil and other antitechnological factors (saponins and polyphenols). The treatment significantly improved the LPI color due to the elimination of the lipid fraction and lipophilic pigments (carotenoids). No changes in amino acid contents or chemical score were observed due to the SC-CO2. Finally, the treatment improved or did not affect the main LPI technofunctional properties. Therefore, SC-CO2 is a promising technique to enhance the quality of protein isolates, without affecting or improving their functional properties.

Sequential extraction as a pioneering method to separate resin from bacuri fruit shell

Sequential extraction (SE) using supercritical CO2 plus ethanol was applied to separate resin from bacuri fruit shell, where process parameters such as particle size, pressure and cosolvent use were studied. The extracts obtained were also analyzed for phenolic compounds and antioxidant capacity. The extraction results showed that SE was able to separate the resin, which is the first report described in the literature, resulting in a patent. Furthermore, the smaller particle size (0.25 mm) showed the higher extraction rates, providing good yields of lipid extracts (up to 10.09 wt%) and ethanolic extracts (up to 13.78 wt%). The extracts presented good levels of phenolic compounds, which was associated with its high antioxidant capacity. Thus, the application of SE added value to bacuri fruit shell, enabling new strands for potential applications in the food, pharmaceutical and cosmetic industries, placing this by-product in the Amazon bioeconomy scenario.

Simulation of boost path and phase control method in supercritical CO2 pipeline commissioning process

CO2 pipeline can be applied to Enhanced Oil Recovery (EOR) projects and CO2 geological storage projects, and has high engineering application value. However, pipeline transportation of CO2 is a high-risk link in CO2 storage projects. The phase state commonly used to transport CO2 is a supercritical state with both gaseous and liquid characteristics, and there are also great challenges in the field of pipeline transportation. The existing researches have carried out a lot of exploration and application development in the heat transfer, phase change, transient and special conditions of supercritical CO2 pipeline operation.In this paper, the modeling and exploration of the commissioning process before the formal operation of the supercritical CO2 pipeline are carried out, and the boost path of the supercritical CO2 pipeline in the phase diagram under different working conditions is obtained. The model developed in this paper is based on the sensitivity analysis of the effects of variables such as ground temperature, filling pressure speed, and whether to perform pressure-stabilizing leak detection operations. The step-up path in the phase diagram of the CO2 pipeline commissioning process and the adjustment control method are obtained. And the critical temperature of each working condition that cannot avoid phase transition, thus contributing to the existing knowledge system in this field.

Adsorption Equilibrium Data of Hexyl Acetate on Activated Carbon under Supercritical CO2 Conditions

Adsorption Equilibrium Data of Hexyl Acetate on Activated Carbon under Supercritical CO₂ Conditions

Simulation and optimization of fatty acid extraction parameters from Nannochloropsis sp. using supercritical carbon dioxide

Microalgae, which are rich in fatty acids, have potential applications in various sectors such as bioenergy, health, food, and biomaterials. The Supercritical Fluid Extraction (SFE) method is commonly used to extract microalgae. This research estimated the process parameters of desorption rate constant (kd) and binary diffusion coefficient (DAB) for SFE fatty acid from Nannochloropsis sp. using a mathematical model called as hot sphere diffusion. Desorption models were used to model the release of fatty acids into the solvent (supercritical carbon dioxide). The parameter estimation process was conducted at temperatures of 313 and 333 K and pressures of 12.5, 20, and 30 MPa. The value of kd increased with increasing pressure and temperature and DAB values were obtained at varying pressures and temperatures.

Spotlight on Secondary Metabolites Produced by an Early-Flowering Apulian Artichoke Ecotype Sanitized from Virus Infection by Meristem-Tip-Culture and Thermotherapy.

Globe artichoke (Cynara cardunculus L. subsp. scolymus) is an important crop of the Mediterranean basin characterized by many properties, like hepatoprotective, anticarcinogenic, antioxidant, antibacterial, and beneficial to human health. The high bioactive compounds (BACs) content, as polyphenols, has attracted the research interest in artichoke extracts. We analysed the changes in polyphenol transcriptome profile between sanitized (S) virus-free and non-sanitized (NS) artichoke plants, focusing on genes involved in phenylpropanoid metabolic pathway and flavonoid biosynthesis. A total of 2458 upregulated and 2154 downregulated differentially expressed genes (DEGs) were functionally characterized. Among them, 31 and 35 KEGG orthology entries characterized by upregulated and downregulated DEGs, respectively, were involved in the biosynthesis of other secondary metabolites. A downregulation of PAL, C4H, 4CL, HST/HQT, C3'H, CCoAMT, CCR1, and F5H, was observed in S artichoke compared to NS one, whereas the CSE, CHS, and CHI genes were upregulated in S samples. Transcriptome results were compared to the polyphenols accumulation in S and NS artichoke leaves. A higher content of total polyphenols was observed in older leaves of NS samples, compared to extracts obtained from young leaves or from S plants, and this result was associated with the presence of viral infections in NS plants. In all the conditions tested, the most represented compound was chlorogenic acid, followed by luteolin-7-O-glucoside. The different composition of each extract was evaluated by a polyphenol dose-response treatment on the rodent hepatoma FaO cell line to the accumulation of reactive oxygen species (ROS). A significant reduction in ROS content ranging between -40% and -48% was observed when 10-20 mg/L of polyphenols from NS or S plants were used, characterized by a specific profile of compounds. To reduce MetOH residues in polyphenol extracts, a supercritical fluid CO2 extraction was evaluated to propose a sustainable green extraction.

A Review of the Utilization of CO2 as a Cushion Gas in Underground Natural Gas Storage

A cushion gas is an indispensable and the most expensive part of underground natural gas storage. Using CO2 injection to provide a cushion gas, not only can the investment in natural gas storage construction be reduced but the greenhouse effect can also be reduced. Currently, the related research about the mechanism and laws of CO2 as a cushion gas in gas storage is not sufficient. Consequently, the difference in the physical properties of CO2 and CH4, and the mixing factors between CO2 and natural gas, including the geological conditions and injection–production parameters, are comprehensively discussed. Additionally, the impact of CO2 as a cushion gas on the reservoir stability and gas storage capacity is also analyzed by comparing the current research findings. The difference in the viscosity, density, and compressibility factor between CO2 and CH4 ensures a low degree of mixing between CO2 and natural gas underground, thereby improving the recovery of CH4 in the operation process of gas storage. In the pressure range of 5 MPa–13 MPa and temperature range of 303.15 K–323.15 K, the density of CO2 increases five to eight times, while the density of natural gas only increases two to three times, and the viscosity of CO2 is more than 10 times that of CH4. The operation temperature and pressure in gas storage should be higher than the temperature and pressure in the supercritical conditions of CO2 because the diffusion ability between the gas molecules is increased in these conditions. However, the temperature and pressure have little effect on the mixing degree of CO2 and CH4 when the pressure is over the limited pressure of supercritical CO2. The CO2, with higher compressibility, can quickly replenish the energy of the gas storage facility and provide sufficient elastic energy during the natural gas production process. In addition, the physical properties of the reservoir also have a significant impact on the mixing and production of gases in gas storage facilities. The higher porosity reduces the migration speed of CO2 and CH4. However, the higher permeability promotes diffusion between gases, resulting in a higher degree of gas mixing. For a large inclination angle or thick reservoir structure, the mixed zone width of CO2 and CH4 is small under the action of gravity. An increase in the injection–production rate intensifies the mixing of CO2 and CH4. The injection of CO2 into reservoirs also induces the CO2–water–rock reactions, which improves the porosity and is beneficial in increasing the storage capacity of natural gas.

Binary phase behavior of select organosulfur compounds in supercritical carbon dioxide: A Monte Carlo molecular simulation study.

Pressure-composition binary phase diagrams were determined for methanethiol, dimethyl sulfide, thiophene, benzothiophene, or dibenzothiophene with carbon dioxide at temperatures from 363 to 453K and pressures from 2 to 20 MPa. Utilizing Gibbs ensemble Monte Carlo molecular simulation, phase coexistence compositions were determined, along with the impact of 4% water cosolvent on select results. Solution structure as a function of pressure and temperature is characterized via radial distribution functions. Comparison to available experimental composition data gives overall mean absolute percentage deviations of 2.2% for thiophene, 37% for methanethiol, and 99% for benzothiophene. Solubilities in a CO2-rich phase are calculated to be sufficient to allow extraction and detection of the compounds studied here via supercritical fluid chromatography and mass spectrometry as a possible analysis approach for future Mars rover missions.

Convective Cooling of Blades in a Turbine Driven by Supercritical Carbon Dioxide

Convective Cooling of Blades in a Turbine Driven by Supercritical Carbon Dioxide

Enhancing foamability and flame‐retardancy of polylactic acid bead foams through inter‐beads bulk polymerization and continuous phase dispersion of LDHs

AbstractPoly (lactic acid) (PLA) bead foam has a promising application because of its renewable and naturally degradable nature. However, its processing is greatly limited by inherent shortcomings such as the complex polycrystals‐inducing strategy. Herein, we developed a strategy of bulk polymerization reaction of polyvinyl acetate (PVAc) to sinter PLA beads to prepare EPLA foams accompanied by supercritical CO2 foaming technology. In order to enhance the sintering behavior and flame‐retardancy of EPLA foams, two‐dimensional nanolayered double hydroxides (LDHs) were introduced and dispersed in the continuous phase of the sintering layers. The formation of unique dispersion of LDHs and sintering structure of PVAc generated substantial increase in the crystallinity, melt elasticity, and sintering strength of EPLA foams, which facilitated the growth and stabilization of cells. Thus, the cell‐density and expansion ratio could be increased to 8.62 × 106 cell/cm3 to 9.31‐fold, respectively. Moreover, the mechanical properties of the EPLA foams were improved. The tensile strength and the compression strength increased to 2.96 and 62.5 MPa. Additionally, with adding 7 wt.% LDH, the EPLA foam reached UL‐94 V‐0 rating with high limiting oxygen index value of 29.1% and char residue of 20.4%. This study provides a novel strategy for the preparation of flame‐retardant EPLA foams with low density, three dimensional complex shapes, as well as excellent mechanical properties.

A molecular dynamics investigation into the polymer tackifiers in supercritical CO2 fracturing fluids under wellbore conditions

SC-CO2 fracturing technology is a feasible method for green extraction of unconventional oil and gas reservoirs. However, due to a series of problems such as sand transportation during SC-CO2 fracturing, CO2 thickening has become the focus of current research. Polymer thickeners have been widely used in oilfields. Due to the macroscopic nature and limitations of laboratory experiments, we have not been able to elucidate the microscopic mechanism of polymer thickening CO2 and the viscosity change of the CO2 fracturing fluid system downhole after polymer addition. In this study, we used all-atom modeling and molecular simulation of the COMPASSII force field. We selected nine polymers to study their microscopic properties and the factors affecting their effects. Finally, we simulated the viscosity change of the CO2 system after the addition of polymer tackifiers in the wellbore under the CO2 fracturing construction conditions by combining the data from one well in the oilfield.

Optimization of Oil and Tocopherol Extraction from Maqui (Aristotelia chilensis (Mol.) Stuntz) by Supercritical CO2 Procedure.

This study focused on the oil extraction from freeze-dried maqui (Aristotelia chilensis) by supercritical fluid extraction with carbon dioxide (SFE-CO2). The basic objective was to optimize the oil yield and the tocopherol concentration. A Box/Behnken experimental design was developed with three processing variables: supercritical pressure (74, 187, and 300 bar), temperature (35, 48, and 60 °C), and extracting time (30, 135, and 240 min). Multiple optimizations, based on the combination of factor levels at 274 bar, 240 min, and 60 °C, led to the highest oil yield and tocopherol values. The validation of the optimized conditions of maqui oil extraction led to an oil yield of 8% and values of 735, 53, and 97 (mg·kg-1 oil) for α-tocopherol, α-tocotrienol, and γ-tocopherol, respectively. A higher concentration of tocopherol compounds was observed when compared to the employment of the conventional extracting method. The optimized SFE-CO2 method led to an oil extract exhibiting higher Hydrophilic-Oxygen Radical Absorbance Capacity (H-ORAC) assay and total phenol content (22 μmol Trolox equivalents·g-1 oil and 28 mg gallic acid equivalents·g-1 oil) than the oil obtained by the conventional procedure. A practical and accurate oil extraction is proposed for obtaining tocopherol-enriched oil including high concentrations of valuable lipophilic antioxidants.

Hierarchical microstructure changes of oriented poly(vinylidene fluoride) foam via supercritical carbon dioxide with increased piezoelectric performance

Light weight poly (vinylidene fluoride) (PVDF) has attracted wide attention for energy supply. In this work, oriented PVDF foams were prepared using supercritical carbon dioxide (CO2) physical foaming associated with a constraint mold. The corresponding micro-nanostructures and electrical performances were researched comprehensively. It reveals that the cell structure and molecular chains of PVDF foams are oriented due to the limitation of gas diffusion paths. Because of the realization of uniaxial stretching during cell growth, the β phase content is increased. Besides, after foaming, the regularity of the chain segments in amorphous region is improved, which is caused by the decrease in the quantity of free-volume cavities. The 1D-149 °C oriented PVDF foam exhibits a high voltage output (8 V), due to the ultralow dielectric constant (1.8) and high compressive strength. This study provides a theoretical foundation for the design of oriented PVDF foams, showing the potential of energy collector.

Phase Equilibria of Binary Mixtures of 3-Chloro-2-Hydroxypropyl Methacrylate and 2-N-Morpholinoethyl Methacrylate in Supercritical Carbon Dioxide

Phase Equilibria of Binary Mixtures of 3-Chloro-2-Hydroxypropyl Methacrylate and 2-N-Morpholinoethyl Methacrylate in Supercritical Carbon Dioxide

Diffusion coefficients of polycyclic aromatic hydrocarbons in supercritical carbon dioxide: A molecular dynamics simulation study

Supercritical carbon dioxide (SC-CO2) extraction technology is an effective way to deal with soil contamination problems. Among them, polycyclic aromatic hydrocarbons (PAHs) are one of the main pollutants in soil. Studying the diffusion coefficients of PAHs in SC-CO2 can help us better understand the mass transfer characteristics during the SC-CO2 extraction process. Molecular dynamics simulation was applied in this work to study the diffusion behavior of PAHs in the SC-CO2 environment. Under different SC-CO2 thermodynamic states (temperature: 313–373 K, pressure: 10–30 MPa) and molecule sizes, the diffusion coefficients of PAHs were calculated. The trend of the interaction energy between PAHs and SC-CO2 molecules as temperature, pressure, and molecule size changed was also investigated. The findings demonstrated that compared to heavy PAHs, light PAHs had a higher diffusion coefficient in SC-CO2. Changes in the system’s temperature and pressure have an important effect on the diffusion coefficients of PAHs in SC-CO2. The high-temperature and low-pressure conditions had a promoting effect on the diffusion behavior of PAHs molecules. The van der Waals energy accounts for the largest proportion of the intermolecular interaction energy, which was about 80 %. It can be concluded that the van der Waals interaction energy played an important impact on the diffusion process of PAHs molecules in SC-CO2.

Thermodynamic analysis of waste heat in a combined super-critical CO2 Brayton cycle for power and hydrogen production

The current investigation aims to propose a novel cycle to generate power and hydrogen using waste heat. For this purpose, super-critical carbon dioxide Brayton cycle, Organic Rankine Cycle (ORC) and proton exchange membrane (PEM) electrolyser systems are consideredin the cycle. Energy, exergy analyses along with parametric study are performed in the research. The best organic working fluid is selected for ORC based on the obtained results. Zero-dimensional modeling for components is performed and results are presented. Results show that the net power generation is 245.5 MW, thermal efficiency is 40.97 %, exergy efficiency is 56.73 %, and hydrogen and oxygen production is 9.04 kg/h and 74.2 kg/h, respectively. The optimum working pressure ratio and evaporator temperature are calculated. The effect of different working parameters on the system performance is obtained. It is shown that increasing the isentropic efficiency of the main and recompression compressors increases power generation, hydrogen production and system efficiency. Furthermore, increasing the turbine’s inlet temperature increases the power generation of the system.

Experimental study on pore structure evolution of thermally treated shales: implications for CO2 storage in underground thermally treated shale horizons

Extracting gas from unconventional shale reservoirs with low permeability is challenging. To overcome this, hydraulic fracturing (HF) is employed. Despite enhancing shale gas production, HF has drawbacks like groundwater pollution and induced earthquakes. Such issues highlight the need for ongoing exploration of novel shale gas extraction methods such as in situ heating through combustion or pyrolysis to mitigate operational and environmental concerns. In this study, thermally immature shales of contrasting organic richness from Rajmahal Basin of India were heated to different temperatures (pyrolysis at 350, 500 and 650 °C) to assess the temperature protocols necessary for hydrocarbon liberation and investigate the evolution of pore structural facets with implications for CO2 sequestration in underground thermally treated shale horizons. Our results from low-pressure N2 adsorption reveal reduced adsorption capacity in the shale splits treated at 350 and 500 ºC, which can be attributed to structural reworking of the organic matter within the samples leading to formation of complex pore structures that limits the access of nitrogen at low experimental temperatures. Consequently, for both the studied samples BET SSA decreased by ∼58% and 72% at 350 °C, and ∼67% and 68% at 500 °C, whereas average pore diameter increased by ∼45% and 91% at 350 °C, and ∼100% and 94% at 500 °C compared to their untreated counterparts. CO2 adsorption results, unlike N2, revealed a pronounced rise in micropore properties (surface area and volume) at 500 and 650 ºC (∼30%–35% and ∼41%–63%, respectively for both samples), contradicting the N2 adsorption outcomes. Scanning electron microscope (SEM) images complemented the findings, showing pore structures evolving from microcracks to collapsed pores with increasing thermal treatment. Analysis of the SEM images of both samples revealed a notable increase in average pore width (short axis): by ∼4 and 10 times at 350 °C, ∼5 and 12 times at 500 °C, and ∼10 and 28 times at 650 °C compared to the untreated samples. Rock-Eval analysis demonstrated the liberation of almost all pyrolyzable kerogen components in the shales heated to 650 °C. Additionally, the maximum micropore capacity, identified from CO2 gas adsorption analysis, indicated 650 °C as the ideal temperature for in situ conversion and CO2 sequestration. Nevertheless, project viability hinges on assessing other relevant aspects of shale gas development such as geomechanical stability and supercritical CO2 interactions in addition to thermal treatment.

Fabrication and Characterization of PLA/PBAT Blends, Blend-Based Nanocomposites, and Their Supercritical Carbon Dioxide-Induced Foams.

In this study, a twin-screw extruder was used to fabricate poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and blend-based nanocomposites with carbon nanotube (CNT) or nanocarbon black (CB) as nanofillers. The fabricated samples were subsequently treated with supercritical carbon dioxide (scCO2) to fabricate the corresponding foams. Bi-phasic morphology and selective distribution of CNTs or CBs in the PBAT phase were observed in the blends/composites through scanning electron microscopy. After the scCO2 treatment, the selective foaming of the PBAT phase in the prepared blends/composites was confirmed. The cellular structure of PBAT phase in scCO2-treated blends is similar to the size/shape of PBAT domains in untreated blends or treated neat PBAT foam. The addition of CNTs or CBs in the blends led to a slight reduction in cell size of the foamed PBAT phase, demonstrating CNT/CB-induced cell nucleation. Differential scanning calorimetry (DSC) results showed that CNTs and CBs played as nucleating agents and increased the initial crystallization temperature up to 14 °C compared with neat PBAT for PBAT in different composites during cooling. The scCO2 treatment induced the bimodal stability of PBAT crystals in different samples, which melted mainly in two temperature regions in DSC studies. Thermogravimetric analyses revealed that compared with parent blends, the addition of CNTs or CBs increased the temperature at 80 wt.% loss (degradation of PBAT portion) up to 6 °C. The electrical resistivity decreased by more than six orders of magnitude for certain CNT- or CB-added composites compared with the parent blends. The hardness of the blends slightly increased after forming the corresponding composites and then declined after the scCO2 treatment.

Pressurized Hot Water Extraction as Green Technology for Natural Products as Key Technology with Regard to Hydrodistillation and Solid-Liquid Extraction.

Hydrodistillation and solid-liquid extraction with organic solvents or supercritical CO2 are standard technologies for natural product manufacturing. Within this technology, portfolio pressurized hot water technology is ranked as a green, sustainable, resilient, kosher and halal manufacturing process. Essential for sustainability is energy integration for heating and cooling the auxiliary water as well as product concentration without evaporation but with the aid of low energy consuming ultra- and nanofiltration membrane technology. The incorporation of modern unit operations, such as pressurized hot water extraction, along with inline measurement devices for Process Analytical Technology approaches, showcases a shift in traditional extraction processes. Traditional equipment and processes still dominate the manufacturing of plant extracts, yet leveraging innovative chemical process engineering methods offers promising avenues for the economic and ecological advancement of botanicals. Techniques such as modeling and process intensification with green technology hold potential in this regard. Digitalization and Industry 4.0 methodologies, including machine learning and artificial intelligence, play pivotal roles in sustaining natural product extraction manufacturing and can profoundly impact the future of human health.

A breakdown pressure model for supercritical CO2 fracturing considering fluid infiltration effect using the point stress criterion

Precisely predicting the breakdown pressure of rock fractured by supercritical CO2 (SC-CO2) is one of the major challenges for optimize in-situ fracturing schemes. However, the influence of the infiltration effect caused by the unique properties of SC-CO2 on the fracture mechanism remains unclear, which may lead to inaccurate prediction of breakdown pressure. In this work, a pressurization rate model considering the physical properties changes of SC-CO2 is proposed to describe the relationship between the pressurization rate and the injection pressure of the fracturing fluid in a wellbore. Ultimately, combined with the pressurization rate model and the point stress criterion, a breakdown pressure model is established by considering the changes in the in-situ stress of wellbore surrounding rock, the fluid injection pressure inside the wellbore, and the pore pressure distribution. The results show that for permeable reservoirs, the breakdown pressure increases as the viscosity and injection rate of fracturing fluid increase, but it decreases with increasing rock permeability. The low viscosity and pressurization rate of SC-CO2 effectively increase the stress generated by the infiltration effect, which is negatively correlated with the breakdown pressure. In addition, the unique pressurization rate of SC-CO2 is the key factor for the abnormal breakdown pressure at different injection rates.