Application of Supercritical CO2 Gas Turbine for the Fossil Fired Thermal Plant

A supercritical CO2 gas turbine cycle can produce power at high efficiency and the gas turbine is compact compared with the steam turbine. Therefore, it is very advantageous power cycle for the medium temperature range less than 650 ℃. The purpose of this paper is to show how it can be effectively applied not only to the nuclear power but also to the fossil fired power plant. A design of 300 MWe plant has been carried out, where thermal energy of flue gas leaving a CO2 heater is utilized effectively by means of economizer and a high cycle thermal efficiency of 43.4 % has been achieved. Since the temperature and the pressure difference of the CO2 heater are very high, the structural design becomes very difficult. It is revealed that this problem can be effectively solved by introducing a double expansion turbine cycle. The component designs of the CO2 heater, the economizer, supercritical CO2 turbines, compressors and the recuperators are given and it is shown that these components have good performances and compact sizes.

Oxidation of n-Butanol and 2-Pentanol with Molecular Oxygen in Supercritical CO2

Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried out in SC CO2. It has been observed that co-solvent affects conversion and selectivity of the reaction considerably.

Porosity of polystyrene membranes prepared by supercritical CO2-induced phase inversion

Microporous asymmetric polystyrene （PS） membranes were prepared by supercritical CO2-induced phase inversion. The effects of different process parameters, such as temperature, COe pressure and PS concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes were experimentally investigated. The porosity showed a tendency of increasing to a maximum and then decreasing with an increase of temperature, CO2 pressure or PS concentration. The effects of process parameters on the membrane porosity were explained based on the properties of supercritical fluids.

Effect of Mucuna Defatted Bran Extracted with Supercritical CO2 on Soybean Seed Germination

In the present work, we investigated the effect of Mucuna deeringiana defatted bran on seed germination of soybean （Glycine max L. Merrill）. For this, the defatted bran was obtained from different operational conditions using CO2 under pressurized conditions as solvent. Oil extractions were carried out in a laboratorial scale unit at temperatures ranging from 310 to 330 K, pressure from 15 to 25 MPa and solvent flow set in 3 mL min^-1. The experiment was conducted in a germination chamber （25℃, 12：12 h light：dark photoperiod）, and the germination rate and germination speed index （GSI） were evaluated for seven days. The results showed that the oil extraction with supercritical CO2 concentrates the allelochemical L-3,4-dihydroxyphenylalanine （L-DOPA） in bran with levels from 1.86% to 4.65%. Subsequent experiments revealed that the rate of soybean seed germination was not affected by defatted bran whereas the GSI increased significantly after treatment. In brief, we concluded that the extraction process with supercritical CO2 is efficient to obtain L-DOPA of Mucuna, which influences the soybean seed germination.

Orthogonal array design for the optimization of stripping Sr(Ⅱ) from ionic liquids using supercritical CO2

The strontium ions extracted from the aqueous phase into 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(C_2mimNTf2) with dicyclohexyl-18-crown-6(DCH18C6) was stripped effectively by supercritical CO_2(sc-CO_2).Hexafluoroacetylacetone(HFAA)-acetonitrile was found to be an excellent modifier of sc-CO_2 to enhance the stripping efficiency.In the orthogonal array design(OAD),OA_(25)(5~5)matrix was employed to optimize the stripping of Sr(Ⅱ) from the DCH 18C6-C_2mimNTf_2 system.Effects of five experimental factors:temperature,pressure,concentration of HFAA,static and dynamic extraction times as well as each factor at five-levels on the stripping of Sr(Ⅱ) were optimized.The effects of these parameters were treated by the analysis of variance(ANOVA).The results showed that Sr(II) could be nearly 100%extracted from the IL phase at 308 K,30 MPa,40 min of dynamic extraction and 60 mmol·L^(-1) HFAA in acetonitrile,respectively.Finally,the stripping mechanism was studied by ESI-MS.

Supercritical CO2 produces the visible-light-responsive TiO2/COF heterojunction with enhanced electron-hole separation for highperformance hydrogen evolution

To construct the heterojunctions of TiO2 with other compounds is of great importance for overcoming its inherent shortages and improving the visible-light photocatalytic performance.Here we propose the construction of TiO2/covalent organic framework(COF)heterojunction with tight connection by a supercritical CO2(SC CO2)method,which helps bridging the transformation paths for photo-induced charge between T i02 and COF.The produced T i02/COF heterojunction performs a H2 evolution of 3,962 nmol·g^-1·h^-1 under visible-light irradiation,which is-25 times higher than that of pure TiO2 and 4.5 folds higher than that of TiO2/COF synthesized by the conventional solvothermal method.This study opens up new possibilities for constructing heterojunctions for solar energy utilization.

Performance Analysis and Evaluation of a Supercritical CO2 Rankine Cycle Coupled with an Absorption Refrigeration Cycle

The utilization of sensible waste heat such as flue gas and industrial surplus heat is essential for energy saving. Supercritical CO2 power generation cycle is a promising way to be used in this field. In this paper, a new supercritical CO2 Rankine cycle coupled with an absorption refrigeration cycle is proposed, which consists of a reheating supercritical CO2 cycle, a mixed-effect Li Br-H2O absorption refrigeration cycle and solar subsystem including evacuated-tube collector and a hot water storage tank. The system has four variants according to the presence or absence of solar subsystem and net cooling energy output. The thermodynamic model of the proposed system was established and its performance was evaluated. The proposed system is able to realize cascade utilization of flue gas waste heat and efficient conversion of solar energy. It has much higher thermodynamic efficiency than the reference system(i.e., the conventional supercritical CO2 Brayton cycle). Taking combined power and cooling system driven by flue gas waste heat and solar energy as an example, its thermal efficiency and exergy efficiency are 20.37% and 54.18% respectively, compared with the 14.74% and 35.96% of the reference system. Energy Utilization Diagrams(EUD) are implemented to investigate the irreversible losses and variation of the exergy destruction in the energy conversion process. Parametric analysis in two key parameters is conducted to provide guidance for the system optimal design.

Key problems and solutions in supercritical CO2 fracturing technology

Supercritical CO2 fracturing is considered to be a new method for efficient exploitation of unconventional reservoirs,such as shale gas,coal bed methane,and tight sand stone gas.Supercritical CO2 has many special properties including low viscosity,high diffusion coefficient,and lack of surface tension,which brings about great advantages for fracturing.However,these properties also cause several problems,such as difficulty in proppant transportation,high friction loss,and high pump displacement.In this paper,the above problems were analyzed by combining field test with laboratory study and specific solutions to these problems are given.The high frictionloss in the pipeline could be reduced by developing a new drag reducing agent and selecting large-size casing.Besides,for the problem of poor capacity in proppant carrying and sand plug,the methods of adding tackifier into supercritical CO2,increasing pump displacement and selecting ultralow density proppants are proposed.Moreover,for the problem of fast leak-off and high requirement for pump displacement,the displacement can be increased or the pad fluid can be injected into the reservoir.After solving the above three problems,the field test of supercritical CO2 fracturing can be conducted.The research results can promote the industrialization process of supercritical CO2 fracturing.

Preliminary experimental study of a supercritical CO2 power cycle test loop with a high-speed turbo-generator using R134a under similarity conditions

Research on applying a supercritical carbon dioxide power cycle （S-CO2） to concentrating solar power （CSP） instead of a steam Rankine cycle or an air Brayton cycle has been recently conducted. An S-CO2 system is suitable for CSP owing to its compactness, higher efficiency, and dry-cooling capability. At the Korea Institute of Energy Research （KIER）, to implement an S-CO2 system, a 10 kWe class test loop with a turbine- alternator-compressor （TAC） using gas foil bearings was developed. A basic sub-kWe class test loop with a high- speed radial type turbo-generator and a test loop with a capability of tens of kWe with an axial type turbo- generator were then developed. To solve the technical bottleneck of S-CO2 turbomachinery, a partial admission nozzle and oil-lubrication bearings were used in the turbo- generators. To experience the closed-power cycle and develop an operational strategy of S-CO2 operated at high pressure, an organic Rankine cycle （ORC） operating test using a refrigerant as the working fluid was conducted owing to its operational capability at relatively low- pressure conditions of approximately 30 to 40 bar. By operating the sub-kWe class test loop using R134a as the working fluid instead of CO2, an average turbine power of 400 W was obtained.

Effects of Various Factors on the Modification of Carbon Nanotubes with Polyvinyl Alcohol in Supercritical CO2 and Their Application in Electrospun Fibers

Supercritical（SC） CO2 anti-solvent induced polymer epitaxy（SAIPE） method was used to help prepare nanohybrid carbon nanotubes（CNTs） wrapped with polyvinyl alcohol（PVA） nanocrystals.With the variation of a series of experimental conditions or peripheral effects,such as PVA concentration,CNTs concentration,and SC CO2 pressure,the optimal experimental variables for PVA-nanocrystals growing on CNTs have been found.The adsorption of polymer on CNTs via multiple weak molecular interactions has been studied by Fourier transform infrared（FTIR） spectroscopy and Raman spectroscopy.The mechanism about the formation of PVA nanocrystals on CNTs can be suggested through the experimental phenomena.These CNTs wrapped with PVA nanocrystals can be directly used as nanofillers to fabricate PVA composite fibers reinforced with CNTs by electrospinning.

Polydimethylsiloxane assisted supercritical CO2 foaming behavior of high melt strength polypropylene grafted with styrene

Foamable high melt strength polypropylene （HMSPP） was prepared by grafting styrene （St） onto polypropylene （PP） and simultaneously introducing poly- dimethylsiloxane （PDMS） through a one-step melt extru- sion process. The effect of PDMS viscosity on the foaming behavior of HMSPP was systematically investigated using supercritical CO2 as the foaming agent. The results show that the addition of PDMS has little effect on the grafting reaction of St and HMSPP exhibits enhanced elastic response and obvious strain hardening effect. Though the CO2 solubility of HMSPP with PDMS （PDMS-HMSPP） is lower than that of HMSPP without PDMS, especially for PDMS with low viscosity, the PDMS-HMSPP foams exhibit narrow cell size distribution and high cell density. The fracture morphology of PDMS-HMSPP shows that PDMS with low viscosity disperses more easily and uniformly in HMSPP matrix, leading to form small domains during the extrusion process. These small domains act as bubble nucleation sites and thus may be responsible for the improved foaming performance of HMSPP.

Extraction of selected rare earth elements from anthracite acid mine drainage using supercritical CO2 via coagulation and complexation

Rare earth elements(REEs)are valuable raw materials which are in great demand in modern high technology industries.Developing methods to produce/recover REEs from waste is significant to the national security of any developed country.This study was focused on investigating the use of supercritical CO2(sCO2)to extract REEs from anthracite acid mine drainage(AMD).Four different mine drainage water source locations at Blaschak Coal Corp.in Pennsylvania,USA were selected for sample collection.An extraction process was developed and demonstrated for two of those water sources containing the highest concentration of REEs.A method involving metal ion coagulation,their dissolution from the sludge into a concentrated aqueous HNO3 solution,complexation with organic ligands and sCO2 extraction was developed to recover REEs from AMD.Specifically,sodium aluminate(NaAlO2)was used as the coagulant to concentrate REEs from the AMD into a solid precipitate.Consequently,over 99%of the REEs in AMD is concentrated in the remaining sludge.During the coagulation process,the effects of pH and NaAlO2 concentration on REE precipitation were investigated.Fuming nitric acid(HNO3)was used to digest the pre-concentrated sludge and tributyl phosphate(TBP)was used to form REE/TBP/HNO3,a non-polar complex with selected REEs,specifically,cerium(Ce),lanthanum(La)and neodymium(Nd).HNO3 concentration and organic/aqueous phase ratio were considered as the variables to improve complexation efficiency.Dynamic extraction experiments using sCO2 and REE/TBP/HNO3 solutions were then conducted at optimal conditions of 60℃and 20 MPa.The overall REE extraction efficiencies are found to increase with the atomic number of the REE.As a result,the average overall REE extraction efficiencies of 41.8%,40.1%and 58.2%for Ce,La and Nd,respectively,are obtained.The potential improvements in the overall extraction efficiency are also discussed.

Pine Needle-like Nanocomposite： Supercritical CO2 Assisted Polythiophene Synthesis on Carbon Nanotubes

A facile method was succcssfidly developed to prepare a ＂pine needle-like＂ nanocompositc of carbon nanotubcs/polylhiophenc（CNTs/PTh） in ethanol with the assistance of supercritical CO2（SC CO2）. The experiment conditions such as mass ratio of thiophene monomer to carbon nanotubes, reaction temperature, and reaction time wcrc optimized, and the morphology and thickness of PTh layers on CNTs were hence effectively controlled. The results of Fourier translbrm infrared（FTIR） spectra, X-ray photoelectron spectra（XPS） and Raman spectra indicate the π-π interactions between PTh and CNT. A possible formation mechanism about the unique microstructure was suggested by virtue of the morphological evolution of the nanocomposite. As a facile, environment benign, and adjustable method, the proposed method holds great potential in the preparation of functional hybrid nanocomposites with the help of SC CO2, which will be promising in the tields of nanofabrication and electrochemical device preparation.

Extraction of betulin from bark of Betula platyphylla by supercritical carbon dioxide extraction

Betulin, which is a medicinal pentacyclic triterpene, is abundant in the bark of white birch (Betula platyphlly). The bark of birch was collected at Tayuan Forest Farm of Jiagedaqi, Heilongjiang Province in September 2000. Supercritical fluid extraction (SFE) that is a new separation technology has been used for the processing pharmaceutical and natural products. In this paper, the extraction of betulin from the bark of birch by supercritical CO2 extraction was studied. The authors investigated and analyzed a few parameters such as modifier dosage, extraction pressure and extraction temperature. The optimal extrac-tion conditions showed that the modifier dosage used for per gram bark powder was 1.5 mL, the extraction pressure was at 20 Mpa, and the extraction temperature was at 55 C. The velocity of flow of liquid CO2 was at 10 kg/h. The pressure and tem-perature in separation vessel were at 5.5 Mpa and 50 C, respectively.

A Comparative Study on Chemical Composition of Supercritical CO_2 Extraction Products in Peels of Trichosanthes kirilowii Maxim. from Changqing District

[Objective] This study aimed to investigate the differences in chemical composition of supercritical CO2 extraction products in peels of Trichosanthes kirilowii Maxim. from Changqing district. [Method] Supercritical fluidextraction （SFE） and GCMS method were applied to determine and analyze the chemical components of the extracts in peels of three strains of Trichosanthes kirilowii Maxim. [Result] The chemical components of supercritical CO2 extraction products in peels of three strains of Trichosanthes kirilowii Maxim. varied., and the number of chemical components with normalized percentage content higher than 1% was 5, 7 and 8, respectively. There are 14 kinds of common components, and the relative content of hexadecanoic acid was the highest. [Conclusion] Supercritical CO2 extracts in peels of different strains of Trichosanthes kirilowii Maxim. contain different chemical components, providing scientific basis for breeding excellent varieties and the development and utilization of Trichosanthes kirilowii Maxim.

Measurement and Correlation of the Solubility of Ligusticum Chuanxiong oil in Supercritical CO_2

Extraction of the Ligusticum Chuanxiong oil with supercritical CO2 （SC-CO2） was investigated at the temperatures ranging from 55℃ to 70℃ and pressure from 25 MPa to 35 MPa. The mass of Ligusticum Chuanxiong oil extracted increased with pressure at constant temperature. The initial slope of the extraction was considered as the solubility of oil in SC-CO2. Chrastil equation was used to correlate the solubility data of Ligusticum Chuanxiong oil. An improved Chrastil equation was also presented and was employed to correlate the solubility data, The correlation results show that the values of the average absolute relative deviation are 5.94% and 3.33% respectively, indicating the improved version has better correlation accuracy than that of Chrastil equation.

Measurement and Correlation of Solubilities of C.I. Disperse Red 73,C.I. Disperse Blue 183 and Their Mixture in Supercritical Carbon Dioxide

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology.In this study,solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method.Under the experimental conditions for the binary(C.I.Disperse Red 73+CO2 or C.I.Disperse Blue 183+CO2) and ternary(C.I.Disperse Red 73+C.I.Disperse Blue 183+CO2) systems,the solubilities increase with pressure.The solubility of C.I.Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa,and the trend is opposite when the pressure is higher than 16 MPa.However,there is no crossover pressure for C.I.Disperse Red 73.The solubilities are also affected by molecular polarity of dyes.The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their dissolution in supercritical CO2.The experimental data of solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183,and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.

Solubility of Paclitaxel in Mixtures of Dichloromethane and Supercritical Carbon Dioxide

Phase behavior of paclitaxel in solvent mixtures of dichloromethane and supercritical carbon dioxide was investigated using a supercritical phase monitor.Cloud point pressures were determined as a function of temperature,pressure and paclitaxel content from 313.1 to 343.1K and pressures up to 33.52 MPa.The ternary mixtures exhibit a typical lower critical solution temperature behavior.When paclitaxel content increases,the single-phase region shrinks in size.Three cubic equations of state(Redlich-Kworng,Soave-Redlich-Kwong and Peng-Robinson equation of state) coupled with the van der Waals one-fluid mixing rules were selected to correlate the experimental data.The results indicate that SRK EOS coupled with two binary interaction parameters kij and lij can predict paclitaxel solubility for the best fit of experimental data.

Dynamic Supercritical Fluid Devolatilization of Polymers

A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercritical fluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercritical fluid devolatilization of spherical polymer particles. The rate of supercritical fluid devolailization for styrene/polystyrene system is measured at 343 K and 18 MPa and at CO2 flow rate of 1.93, 3.27 and 5.62 L·min^-1, respectively. The model analysis, which is consistent with experimental results, indicates that the supercritical fluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min^-1.