MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO_2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the similar...

Polymerization of Styrene in Supercritical CO_2-swollenPoly(ethylene terephthlate)

Polystyrene/Poly(ethylene terephthlate) (PET) blends have been prepared by theheterogeneous free-radical polymerization of styrene within supercritical carbon dioxide-swollenPET substrates. Composition of the blends and the average molecular weight of polystyrene inthe blends can be controlled by equilibration time and reaction condition.

Pressure Effect on the Local Composition SurroundingEthyl Acetoacetate in Supercritical CO_2 - Ethanol Mixture

The keto-enol tautomerization of ethyl acetoacetate (EAA) in supercritical CO2-ethanol mixture has been investigated at 308.15 K and at different pressures using UV-Visspectroscopy. A method for calculating the local composition about EAA has been developed based on the relationship between the equilibrium constant and dielectric property of the mixing solvent. The results indicate that the local concentration of ethanol surrounding EAA is much higher than that in the bulk.

Effect of Co-solvent and Pressure on the Thermal Decomposition of 2,2′Azobis-(isobutyronitrile) in Supercritical CO_2

The thermal decomposition of 2, 2'-azobis (isobutyronitrile) (AIBN) in supercritical CO2 with cosolvent methanol or cyclohexane has been studied by using UV/Vis spectroscopic method at 335.15 K and at 12.0 MPa and 14.0 MPa. Both of the cosolvents can accelerate the decomposition rate, and the effect of methanol is more significant than that of the cyclohexane.

Effect of Co-solvent on the Palladium Catalyzed Alkoxycarbonylation of Allyl Bromide in Supercritical CO_2

The effect of cosolvent on the palladium catalyst which catalyze alkoxycarbonylation of allyl bromide in supercritical CO2 has been investigated. It was found that a small amount of cosolvent such as ethanol, CH2Cl2 and cyclohexane can affect both reaction yields and selectivities largely. Ethanol was the most favorable cosolvent for increasing the total yield of unsaturated esters and the selectivity of 3-butenoic acid ester. Using cosolvent ethanol and cocatalyst FeCl2 simultaneously can lead to better reaction results.

Cosolvent Effect on the Tautomerism of Ethyl Acetoacetate in Supercritical CO_2

The effect of cosolvent cyclohexane, chloroform, and acetonitrile on the keto-enol tautomeric equilibrium of ethyl acetoacetate in supercritical CO2 was studied by UV-Vis spectroscopy over the pressure range from 76 to 110 bar at 308.15 K. It was found that the equilibrium constant decreases with increasing polarity of the cosolvents.

SOLID PHASE TRANSITION OF SYNDIOTACTIC POLYSTYRENE IN SUPERCRITICAL CO_2

Solid phase transition of the a form crystals to the 3 form crystals in syndiotactic polystyrene (sPS) samples has occurred in supercritical CO2. This transformation is different from those detected under other conditions. The effects of some factors (e.g. time, temperature, and pressure) on the solid phase transformation of sPS in supercritical CO2 were analyzed in detail. Experimental results show that longer time, higher temperature or higher pressure favors the transformation of the a form crystals to the beta form crystals.

Extraction of Heavy Metals from Solid Material by Supercritical CO_2

Extraction of heavy metal ions from solid matrix by means of an incorporation of chelating agents with supercritical carbon dioxide（scCO2） was investigated experimentally. Four commercially available chelating agents, diethylammonium diethyldithiocarbamate（Et2NH2DDC）, trifluoroacetylacetone（TFA）, hexafluoroacetylacetone（HFA） and thenoyltrifluoroacetone（TTA） were tested. The extraction experiments were conducted at 50 °C and 1.39×107― 2.80×107 Pa. According to the experimental results, for the extraction of Cu2＋, all the chelating agents investigated here are effective. For other metal ions, such as Pb2＋, Ni2＋ and Cd2＋, Et2NH2DDC exhibited a better extraction result, while other chelating agents were less effective. This investigation is expected to provide a tentative evaluation on the scCO2-based metal extraction from solid media.

Preparation of Semi-interpenetrating Polymer Network of Silicon Rubber and Poly(methyl methylacrylate) Using Supercritical CO_2

The heterogeneous free-radical polymerization of methyl methylacrylate (MMA) and divinylbenzene (DVB) as cross-linker within supercritical carbon dioxide-swollen silicon rubber (SR) has been studied as an approach to preparing semi-interpenetrating polymer network (semi-IPN) of SR and poly(methyl methylacrylate) (PMMA). The SR/PMMA semi-IPNs were characterized by scanning electron microscopy (SEM) and dynamic mechanical analyzer (DMA).

A supercritical CO_2 fluid technique for the preparation and evaluation of rhBMP-2-loaded PLLA microspheres

Introduction The use of supercritical fluids such as supercritical CO2（scCO2） has provided a ’clean’ and effective alternative to traditional methods of protein delivery systems.Here。

Experimental Study on Performance of Supercritical CO_2 Heat Exchanger with Four Different Inner Tubes

The experiment was conducted to investigate the heat transfer performance of supercritical CO_2 in a casing heat exchanger by comparing their heat transfer,entropy production unit number,non-dimensional entropy production rate and field synergy factor.The results show that both heat transfer and entropy production unit number in four tubes decrease with water temperature increasing.Heat transfer and entropy production unit number in multiple tubes( i. e.,triple straight tube and double helix tube) is higher than their single counterparts; the non-dimensional entropy production rate increases with water temperature. Non-dimensional entropy production rate of triple straight tube and double helix tube is far below the single tube. Field synergy factor of double helix tube is much higher than that of the triple straight tube under the same condition. Further experiment was carried out in double helix tube,under various CO_2 pressure and inlet water temperature,the results are analyzed and reported in this paper.

Demonstration of a small‐scale power generator using supercritical CO_(2)

The supercritical CO_(2)(sCO_(2))power cycle could improve efficiencies for a wide range of thermal power plants.The sCO_(2)turbine generator plays an important role in the sCO_(2)power cycle by directly converting thermal energy into mechanical work and electric power.The operation of the generator encounters challenges,including high temperature,high pressure,high rotational speed,and other engineering problems,such as leakage.Experimental studies of sCO_(2)turbines are insufficient because of the significant difficulties in turbine manufacturing and system construction.Unlike most experimental investigations that primarily focus on 100 kW‐or MW‐scale power generation systems,we consider,for the first time,a small‐scale power generator using sCO_(2).A partial admission axial turbine was designed and manufactured with a rated rotational speed of 40,000 rpm,and a CO_(2)transcritical power cycle test loop was constructed to validate the performance of our manufactured generator.A resistant gas was proposed in the constructed turbine expander to solve the leakage issue.Both dynamic and steady performances were investigated.The results indicated that a peak electric power of 11.55 kW was achieved at 29,369 rpm.The maximum total efficiency of the turbo‐generator was 58.98%,which was affected by both the turbine rotational speed and pressure ratio,according to the proposed performance map.

Multi-objective optimization and evaluation of supercritical CO_(2) Brayton cycle for nuclear power generation

The supercritical CO_(2) Brayton cycle is considered a promising energy conversion system for Generation IV reactors for its simple layout,compact structure,and high cycle efficiency.Mathematical models of four Brayton cycle layouts are developed in this study for different reactors to reduce the cost and increase the thermohydraulic performance of nuclear power generation to promote the commercialization of nuclear energy.Parametric analysis,multi-objective optimizations,and four decision-making methods are applied to obtain each Brayton scheme’s optimal thermohydraulic and economic indexes.Results show that for the same design thermal power scale of reactors,the higher the core’s exit temperature,the better the Brayton cycle’s thermo-economic performance.Among the four-cycle layouts,the recompression cycle(RC)has the best overall performance,followed by the simple recuperation cycle(SR)and the intercooling cycle(IC),and the worst is the reheating cycle(RH).However,RH has the lowest total cost of investment(C_(tot))of$1619.85 million,and IC has the lowest levelized cost of energy(LCOE)of 0.012$/(kWh).The nuclear Brayton cycle system’s overall performance has been improved due to optimization.The performance of the molten salt reactor combined with the intercooling cycle(MSR-IC)scheme has the greatest improvement,with the net output power(W_(net)),thermal efficiencyη_(t),and exergy efficiency(η_(e))improved by 8.58%,8.58%,and 11.21%,respectively.The performance of the lead-cooled fast reactor combined with the simple recuperation cycle scheme was optimized to increase C_(tot) by 27.78%.In comparison,the internal rate of return(IRR)increased by only 7.8%,which is not friendly to investors with limited funds.For the nuclear Brayton cycle,the molten salt reactor combined with the recompression cycle scheme should receive priority,and the gas-cooled fast reactor combined with the reheating cycle scheme should be considered carefully.

Extraction of rare earth elements from their oxides using organophosphorus reagent complexes with HNO_3 and H_2O in supercritical CO_2

Direct extraction of metals from solids with complexing agents in supercritical CO2(SC-CO2) has recently attracted interests in separation,purification,recovery,and analysis of metals.In the present study,the static/dynamic extraction of rare earth elements(Nd,Ce) from their oxides(Nd2O3,CeO2) with organophosphorus complexes with HNO3 and H2O in SC-CO2 was investigated.The static extraction efficiency of Nd from Nd2O3 with the tri-n-butylphosphate(TBP)-HNO3 complex could reach 95% under optimized experiment...

Experimental and numerical simulations of bottom hole temperature and pressure distributions of supercritical CO_2 jet for well-drilling

The supercritical carbon dioxide （SC-CO2） drilling is a novel drilling technique developed in recent years. A detailed study of temperature and pressure distributions of the SC-CO2 jet on the bottom of a well is essensial to the SC-CO2 drilling. In this paper, the distributions of pressure and temperature on the bottom of the hole during the SC-CO2 jet drilling are simulated experimentally and numerically, and the impacts of the nozzle diameter, the jet length, and the inlet pressure of the SC-CO2 jet are analyzed. It is shown that, the bottom hole temperature and pressure increase with the increase of the nozzle diameter, and the bottom hole temperature reduces and the pressure increases first and then decreases with the increase of the jet length, indicating that the jet length has an optimum value. The increase of the inlet pressure can increase the temperature and pressure on the bottom, which has a positive effect on the drilling rate.

Phase equilibria of supercritical CO_2-ethanol-stearic acid ternary system and hydrogen bonding between ethanol and stearic acid

Solubility of stearic acid in supercritical CO 2 with ethanol cosolvent was determined at 308.15 K in the pressure range from 8 to 16 MPa, and the cosolvent concentration ranges from 0 mol% to 4 mol%. The corresponding densities of the fluid phases were also measured. It was observed that ethanol enhances the solubility significantly. The solubility increases with pressure noticeably at lower pressure, especially at lower cosolvent concentrations. The effect of pressure on the solubility is very limited at higher pressures or higher cosolvent concentrations. The hydrogen bonding between ethanol and stearic acid in supercritical CO 2 was also studied using FTIR in order to understand the mechanism of the solubility enhancement by ethanol.

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.

Numerical Investigation of Heat Transfer Characteristics of Supercritical CO_2 Tube in Combustion Chamber of Coal-Fired Boiler

To achieve compact structure, light weight, and high thermal efficiency for the coal-fired boiler, the supercritical CO_2 power cycle has been considered as one of the promising alternatives in the coal-fired power conversion system. One of the major problems concerning fossil fuel powered plants is the safety of the water wall in boiler design. In this work, the heat transfer characteristics of the supercritical CO_2 tube in the combustion chamber were determined through the low Reynolds number k-ε model, the gas real model and the P-1 radiation model. The study covered the supercritical CO_2 tube and the fins, and the annulus flue gas passage was also included. The wall temperature and the heat transfer coefficient were compared against those obtained from the experiments. Based on the examinations of the calculated flow and turbulence fields, the distributions of the velocity and the temperature inside the supercritical CO_2 tube in the combustion chamber were resolved numerically. Moreover, the effects of the heat transfer coefficient on the heat transfer characteristics were also discussed. And it was numerically focused on the influence of the inclined angle on the flow and the heat transfer of the supercritical CO_2 tube. The results show that the heat transfer coefficient keeps namely constant as the increasing inclined angle. It would help to better understand the heat transfer mechanism of unique characteristics of supercritical CO_2 above the pseudo-critical temperature, which may provide the corresponding theoretical basis on the optimization design of the coal-fired boiler.