Solubility of iron(Ⅲ) and nickel(Ⅱ) acetylacetonates in supercritical carbon dioxide

As a common precursor for supercritical CO_(2)(scCO_(2))deposition techniques,solubility data of organometallic complexes in scCO_(2)is crucial for the preparation of nanocomposites.Recently,metal acetylacetonates have shown great potential for the preparation of single-atom catalytic materials.In this study,the solubilities of iron(Ⅲ)acetylacetonate(Fe(acac)3)and nickel(Ⅱ)acetylacetonate(Ni(acac)2)were measured at the temperature from 313.15 to 333.15 K and in the pressure range of 9.5–25.2 MPa to accumulate new solubility data.Solubility was measured using a static weight loss method.The semi-empirical models proposed by Chrastil and Sung et al.were used to correlate the solubility data of Fe(acac)3 and Ni(acac)2.The equations obtained can be used to predict the solubility of the same system in the experimental range.

Anti-Melanogenesis Activity of Supercritical Carbon Dioxide Extract from Perilla frutescens Seeds

Perilla frutescens seed (PFS) oil is reported to inhibit skin photoaging;however, its effect on melanogenesis has not yet been investigated. Herein, we tested the anti-melanogenesis activity of an oil-based extract from PFS with supercritical carbon dioxide (scCO2). In a cell culture system, B16 mouse melanoma cells were treated with the PFS scCO2 extract and other samples. The PFS scCO2 extract decreased melanin production by approximately 90% in B16 mouse melanoma cells without cytotoxicity at 100 μg/mL. This effect was greater than that of the well-known melanogenesis inhibitor, kojic acid. Although a hexane-extracted PFS oil and a squeezed PFS oil also decreased melanin production in the B16 cells, the inhibitory effect of the PFS scCO2 extract was higher than both of these. Chemical analysis of the PFS scCO2 extract and squeezed PFS oil showed that almost 90% of the components of both oils were α-linolenic acid, linoleic acid, and oleic acid. Furthermore, the ratio of those three fatty acids across both samples was almost the same. When the three fatty acids were mixed in the same ratio as in the PFS scCO2 extract, the IC50 of the mixture for melanin production in B16 melanoma cells was identical to that of the PFS scCO2 extract. However, the IC50 of the squeezed PFS oil was approximately 6.6 times higher than that of the mixture. Although those fatty acids are the main inhibitory ingredients against melanin production in all of the extracts, some factor(s) in the squeezed PFS reduce their affinity with the cells. These results indicated that the PFS scCO2 extract could be a superior melanogenesis inhibitor. Although its main ingredients are probably the same as those of the squeezed PFS oil, it is necessary to extract with scCO2 for stronger anti-melanogenesis activity.

Experimental Research on Supercritical Carbon Dioxide Fracturing of Sedimentary Rock:A Critical Review

Supercritical carbon dioxide(ScCO_(2))fracturing has great advantages and prospects in both shale gas exploitation and CO_(2)storage.This paper reviews current laboratory experimental methods and results for sedimentary rocks fractured by ScCO_(2).The breakdown pressure,fracture parameters,mineral composition,bedding plane angle and permeability are discussed.We also compare the differences between sedimentary rock and granite fractured by ScCO_(2),ultimately noting problems and suggesting solutions and strategies for the future.The analysis found that the breakdown pressure of ScCO_(2)was reduced 6.52%–52.31%compared with that of using water.ScCO_(2)tends to produce a complex fracture morphology with significantly higher permeability.When compared with water,the fracture aperture of ScCO_(2)was decreased by 4.10%–72.33%,the tortuosity of ScCO_(2)was increased by 5.41%–70.98%and the fractal dimension of ScCO_(2)was increased by 4.55%–8.41%.The breakdown pressure of sandstone is more sensitive to the nature of the fracturing fluid,but fracture aperture is less sensitive to fracturing fluid than for shale and coal.Compared with granite,the tortuosity of sedimentary rock is more sensitive to the fracturing fluid and the fracture fractal dimension is less sensitive to the fracturing fluid.Existing research shows that ScCO_(2)has the advantages of low breakdown pressure,good fracture creation and environmental protection.It is recommended that research be conducted in terms of sample terms,experimental conditions,effectiveness evaluation and theoretical derivation in order to promote the application of ScCO_(2)reformed reservoirs in the future.

Numerical simulations of supercritical carbon dioxide fracturing:A review

As an emerging waterless fracturing technology,supercritical carbon dioxide(SC-CO_(2))fracturing can reduce reservoir damage and dependence on water resources,and can also promote the reservoir stimulation and geological storage of carbon dioxide(CO_(2)).It is vital to figure out the laws in SC-CO_(2)fracturing for the large-scale field implementation of this technology.This paper reviews the numerical simulations of wellbore flow and heat transfer,fracture initiation and propagation,and proppant transport in SC-CO_(2)fracturing,including the numerical approaches and the obtained findings.It shows that the variations of wellbore temperature and pressure are complex and strongly transient.The wellhead pressure can be reduced by tubing and annulus co-injection or adding drag reducers into the fracturing fluid.Increasing the temperature of CO_(2)with wellhead heating can promote CO_(2)to reach the well bottom in the supercritical state.Compared with hydraulic fracturing,SC-CO_(2)fracturing has a lower fracture initiation pressure and can form a more complex fracture network,but the fracture width is narrower.The technology of SC-CO_(2)fracturing followed by thickened SC-CO_(2)fracturing,which combines with high injection rates and ultra-light proppants,can improve the placement effect of proppants while improving the complexity and width of fractures.The follow-up research is required to get a deeper insight into the SC-CO_(2)fracturing mechanisms and develop cost-effective drag reducers,thickeners,and ultra-light proppants.This paper can guide further research and promote the field application of SC-CO_(2)fracturing technology.

Optimization of Supercritical Carbon dioxide Extraction of Ginger Essential Oil by Response Surface Method

[Objective] Ginger essential oil （GEO） is widely used in food production and medical field in recent years due to its prominent biological functions, and this study was conducted to obtain high-quality and high-purity ginger essential oil from the fresh ginger. [Method] GEO was extracted from ginger roots by supercritical fluid extraction （SFE） method. The effects of flow rate of CO2, mesh size of ginger powder and volume of entrainer were investigated by single-factor experiments and response surface method. The content and extraction rate of 6-gingerol represented the extraction index of GEO. [Result] The conditions were optimized as follows： flow rate of CO2 at 25 L/h, mesh size of ginger power of 80 mesh, and volume of anhydrous ethanol as entrainer of 92.46 ml. The optimal extraction rate of 6-gingerol was 3.21%, which was predicted by RSM. [Conclusion] The optimal process of supercritical carbon dioxide extraction of ginger essential oil was identified by singlefactor experiments and response surface method. The present study provides a satisfactory method for purifying GEO from ginger for industrial purpose.

Effects of Silica Aerogel Content on Microstructural and Mechanical Properties of Poly(methyl methacrylate)/Silica Aerogel Dual-scale Cellular Foams Processed in Supercritical Carbon Dioxide

A novel poly（methyl-methacrylate）/silica aerogel（PMMA/SA） dual-scale cellular foam was synthesized with internal mixing followed by the supercritical carbon dioxide foaming process.The effects of silica aerogel content on the microstructural and mechanical performance of the foams were investigated by SEM,TEM analysis,and mechanical tests.The experimental results suggest that the employment of silica aerogel granule as addictive can distinctly improve the morphological feature as well as the mechanical performance in comparison to neat PMMA foam by uniformizing cell size distribution,decreasing cell size and increasing cell density.And dual-scale cells including micrometric cells of 3-10 μm and nanometric cells of about 50 nm existed in the structure of foams resulting from the retained original framework structure of silica aerogel,which has not been described in other studies with the addition of various fillers.Furthermore,the mechanical strength was significantly elevated even with a small amount of silica aerogel resulting from the unique microstructure,decreased cell size and enhanced cell walls.The compressive strength was 18.12 MPa and the flexural strength was 18.90 MPa by adding 5wt% and 2wt% silica aerogel,respectively.These results demonstrate the potential to synthesize PMMA/SA dual-scale cellular foams to be used as structural materials with the advantages of low density and high strength.

Extraction of Perilla Seed Oil Using Supercritical Carbon Dioxide and GC-MS Analysis

[Objective] This study was aimed to determine the optimal parameters for the extraction of perilla seed oil to obtain high-quality perilla seed oil and analyze its compositions. [Method] In this study, perilla seed oil was extracted using supercritical CO2 （SC-CO2）. The effects of extraction time, temperature and pressure were investigated by single-factor experiments and orthogonal array testing （ORT）. The chemical compositions of extracted perilla seed oil were investigated by GC-MS. [Result] The optimal conditions for the extraction of perilla seed oil using SC-CO2 were extraction time of 4 h, extraction temperature at 40 ℃, and extraction pressure at 23 MPa. Under these conditions, the extraction yield of perilla seed oil was maximized to 12.43%. GC-MS analysis revealed that perilla seed oil was a complex mixture containing 76.183% α-linolenic acid. [Conclusion] Supercritical CO2 extraction was proven to be an effective technology to extract oil from perilla seed, and GCMS was also a satisfactory method for analyzing the compositions of perilla seed oil.

A study of the mechanism of enhancing oil recovery using supercritical carbon dioxide microemulsions

Supercritical carbon dioxide （scCO2） microemulsion was formed by supercritical CO2, H20, sodium bis（2-ethylhexyl） sulfosuccinate （AOT, surfactant） and C2HsOH （co-surfactant） under pressures higher than 8 MPa at 45 ℃. The fundamental characteristics of the scCO2 microemulsion and the minimum miscibility pressure （MMP） with Daqing oil were investigated with a high-pressure falling sphere viscometer, a high-pressure interfacial tension meter, a PVT cell and a slim tube test. The mechanism of the scCO2 microemulsion for enhancing oil recovery is discussed. The results showed that the viscosity and density of the scCO2 microemulsion were higher than those of the scCO2 fluid at the same pressure and temperature. The results of interfacial tension and slim tube tests indicated that the MMP of the scCO2 microemulsion and crude oil was lower than that of the scCO2 and crude oil at 45 ℃. It is the combined action of viscosity, density and MMP which made the oil recovery efficiency of the scCO2 microemulsion higher than that of the scCO2 fluid.

Supercritical carbon dioxide as a new working medium for pneumatic launch:A theoretical study

Compared with the conventionally gaseous or liquid working media,the specific internal energy of supercritical carbon dioxide(SCD)is higher at the same temperature and pressure,and the critical temperature of carbon dioxide is close to room temperature,making SCD a potential new working medium for pneumatic launch.To analyze the feasibility of this conception,an analytical model of a pneumatic catapult is established on basis of the conservations of mass and energy.The model consists of a high-pressure chamber and a low-pressure chamber connected by multiple valves,and there is a movable piston in the low-pressure chamber that can push an aircraft to accelerate.The effects of the launch readiness state of SCD in the high-pressure chamber,the initial volume of the low-pressure chamber and the valve control on the movement of the aircraft are analyzed.It is found that there is a restrictive relation between the temperature and pressure of the launch readiness state of SCD,i.e.,there is a maximum allowable launch readiness pressure when the launch readiness temperature is fixed.If this restrictive relation is not satisfied,the working medium in the low-pressure chamber will drop to its triple point within a few milliseconds,leading to a launch failure.Owing to this restrictive relation,there is an optimal launch readiness state of SCD with the highest working capacity for any allowable launch readiness temperature.The pressure of the low-pressure chamber will decrease significantly as the initial volume increases,leading to a decreased acceleration of the aircraft.The acceleration can be controlled below a critical value by a designed sequential blasting technique of multiple valves.The calculated results show that a 500 kg aircraft can be accelerated from 0 to 58 m/s in 0.9 s with 36 kg of carbon dioxide.This research provides a new technique for the controllable cold launch of an aircraft.

Supercritical Carbon Dioxide Extraction of Andrographolide from Andrographis paniculata： Effect of the Solvent Flow Rate, Pressure, and Temperature

Andrographis paniculata Nees has been extensively used for traditional medicine and help against fever dysentery, diarrhoea, inflammation, and sore throat. In this study, andrographolide, the main component of this plant was extracted from the leaves of A. paniculata using supercritical carbon dioxide. The operating pressures were varied from 7.50 to 20MPa, the temperatures were varied from 30℃ to 60℃, and the flow rates were varied from 0.5 to 4ml.min^-1. The best extraction condition occurred at 10MPa, 40℃, and a flow rate of 2ml.min^-1 for a 3g sample of A. paniculata ground-dried leaves. The measured extraction rate was found to be about 0.0174g of andrographolide per gram of andrographolide present in the leaves per hour of operation. The future studies must focus on the interaction between the various operating parameters such as temperature, pressure, and flow rate of supercritical carbon dioxide.

Kinetics of Reactive Extraction of Nd from Nd2O3 with TBP-HNO3 Complex in Supercritical Carbon Dioxide

The process based on supercritical fluid extraction for reprocessing of the spent nuclear fuel has some remarkable advantages over the plutonium-uranium extraction(PUREX) process.Especially,it can minimize the generation of secondary waste.Dynamic reactive extraction of neodymium oxide(Nd2O3) in supercritical carbon dioxide(SC-CO2) containing tri-n-butyl phosphate-nitric acid(TBP-HNO3) complex was investigated.Temperature showed a positive effect on the extraction efficiency,while pressure showed a negative effect when the unsaturated TBP-HNO3 complex was employed for the dynamic reactive extraction of Nd2O3 in SC-CO2.Both temperature and pressure effects indicated that the kinetic process of the reactive extraction was controlled by the chemical reaction.A kinetic model was proposed to describe the extraction process.

Metal Ions Extraction with Glucose Derivatives as Chelating Reagents in Supercritical Carbon Dioxide

A series of glucose derivatives have been used as chelating reagents to extract metal ions in supercritical carbon dioxide. With perfluoro-l-octanesulfonic acid tetraethylammonium salt as additive, glucose derivatives were selective for Sr^2＋ and Pb^2＋ extraction in supercritical carbon dioxide.

Response Surface Optimization of Nigella glandulifera Freyn Seed Oil Yield by Supercritical Carbon Dioxide Extraction

Supercritical carbon dioxide （SC-CO2） extraction was employed to extract oil from Nigella glandulifera Freyn seed in this study. Response surface methodology （RSM） was applied to evaluate the effects of the process parameters （pressure, temperature, and CO2 flow rate） on oil yield of N. glandulifera seed. A Box-Behnken design was used to optimize the extraction parameters. The analysis of variance indicated that the linear coefficients of pressure and CO2 flow rate, the quadratic term coefficients of pressure and temperature and the interactions between pressure and temperature, as well as temperature and CO2 flow rate, had significant effects on the oil yield （P〈0.05）. The optimal conditions to obtain the maximum oil yield from N. glandulifera seed were pressure 30.84 MPa, temperature 40.57°C, and CO2 flow rate 22.00 L h-1. Under these optimal conditions, the yield of oil was predicted to be 38.19%. The validation experiment results agreed with the predicted values. The fatty acid composition of N. glandulifera seed oil extracted using SC-CO2 was compared with that of oil obtained by Soxhlet method. The results showed that the fatty acid compositions of oil extracted by the two methods were similar. Identification of oil compounds with gas chromatography-mass spectrometry （GC-MS） showed that the contents of unsaturated fatty acids linoleic acid （48.30%）, oleic acid （22.28%） and saturated fatty acids palmitic acid （16.65%）, stearic acid （4.17%） were the most abundant fatty acids in seed oil from N. glandulifera.

Preliminary Study on the Characteristics of Isotactic Polypropylene with Nucleating Agent Swollen by Supercritical Carbon Dioxide

Impregnation of isotactic polypropylene (iPP) with nucleating agent (NA21) using supercritical carbon dioxide as the swelling agent at different temperature and pressure and its non-isothermal crystallization kinetics were investigated. The results showed that NA21 was dispersed at a nanometer-scale in the PP matrix, resulting in the formation of different typesof crystal phases of iPP and the enhancement of its mechanical properties.

Solubility of red palm oil in supercritical carbon dioxide： Measurement and modelling

The solubility of red palm oil （RPO） in supercritical carbon dioxide （scCO2） was determined using a dynamic method at 8.5-25 MPa and, 313.15-333.15 K and at a fixed scCO2 flow rate of 2.9 g. mn -1 using a full factorial design. The solubility was determined under low pressures and temperatures as a preliminary study for RPO par- ticle formation using scCO2. The solubility of RPO was 0.5-11.3 mg. （g CO2） -1 and was significantly affected by the pressure and temperature. RPO solubility increased with pressure and decreased with temperature. The Adachi-Lu model showed the best-fit for RPO solubility data with an average relative deviation of 14% with a high coefficient of determination, R2 of 0.9667, whereas the Peng-Robinson equation of state thermodynamic model recorded deviations of 17%-30%.

Catalytic Formation of Propylene Carbonate from Supercritical Carbon Dioxide/Propylene Oxide Mixture

Propylene carbonate was synthesized from supercritical carbon dioxide (SC-CO2)/ propylene oxide mixture with phthalocyaninatoaluminium chloride (ClAlPc)/ tetrabutylstmmonium bromide (n-Bu4NBr) as catalyst. The high rate of reaction was attributed to rapid diffusion and the high miscibility of propylene oxide in SC-CO2 under employed conditions. Various reaction periods present different formation rate of propylene carbonate, mainly due to the existence of phase change during the reaction. The experimental results demonstrate that SC-CO2 could be used as not only an environmentally benign solvent but also a carbon precursor in synthesis.

Heat-fluid-solid coupling mechanism of supercritical carbon dioxide jet in rock-breaking

Aiming at the synergistic rock-breaking mechanism of supercritical carbon dioxide(SC-CO_(2))jet pressure and tem-perature difference,a heat-fluid-solid calculation model of rock-breaking stress was established and verified to be effective,and the variations of jet flow field and rock stress with jet standoff distance of SC-CO_(2),water and nitrogen were studied.With the increase of jet standoff distance,the jet pressure of SC-CO_(2) decreases and the jet temperature difference increases.The SC-CO_(2) jet is higher in pressure than the nitrogen jet and differs little from the water jet.Temperature difference of SC-CO_(2) jet is 5 times that of water jet and more than 2.5 ti mes that of nitrogen jet when the jet standoff distance is larger than 10.The tem-perature stress is the main reason why SC-CO_(2) jet is superior to water and nitrogen jets in rock-breaking.The rock under the SC-CO_(2) jet has greater rock stress,effective rock-breaking jet standoff distance and rock-breaking area.The jet pressure plays a major role in rock-breaking when the jet standoff distance is small,while the jet temperature difference plays a major role in rock-breaking when the jet standoff distance is large.The SC-CO_(2) jet is an efficient volume rock-breaking method,which results in tensile and shear failure on the rock surface under short time jet and large area tensile failure inside the rock simultaneously under long time jet.

New CO_2-philic Compounds: Design, Synthesis and Solubility in Supercritical Carbon Dioxide

A series of gluscose derivatives were designed, synthesized, and their structures were confirmed by IR, NMR and elementary analysis. All new compounds are highly soluble in liquid or supercritical carbon dioxide. The compound with electron-withdrawing substituent on benzene ring had even better solubility than the compounds with electron-donating substituent.

Reduction of Aldehydes by Fe-H_2O-CO_2 System in Supercritical Carbon Dioxide

1 Introduction Nowadays, green chemistry has received increased attention. The use of water and scCO2 as a solvent or reagent is an important field for organic reactions and green chemistry both in laboratory and industry.

The Magnetic Field Effect on the Polymerization of Styrene in Supercritical Carbon Dioxide

Styrene was polymerized in supercritical （sc） CO2 with benzoyl peroxide （BPO） as initiator. It was found that the polymerization was accelerated by the external magnetic field.