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.

Proppant transport in rough fracture networks using supercritical CO_(2)

Proppant transport within fractures is one of the most critical tasks in oil,gas and geothermal reservoir stimulation,as it largely determines the ultimate performance of the operating well.Proppant transport in rough fracture networks is still a relatively new area of research and the associated transport mechanisms are still unclear.In this study,representative parameters of rough fracture surfaces formed by supercritical CO_(2) fracturing were used to generate a rough fracture network model based on a spectral synthesis method.Computational fluid dynamics(CFD)coupled with the discrete element method(DEM)was used to study proppant transport in this rough fracture network.To reveal the turning transport mechanism of proppants into branching fractures at the intersections of rough fracture networks,a comparison was made with the behavior within smooth fracture networks,and the effect of key pumping parameters on the proppant placement in a secondary fracture was analyzed.The results show that the transport behavior of proppant in rough fracture networks is very different from that of the one in the smooth fracture networks.The turning transport mechanisms of proppant into secondary fractures in rough fracture networks are gravity-driven sliding,high velocity fluid suspension,and fracture structure induction.Under the same injection conditions,supercritical CO_(2)with high flow Reynolds number still has a weaker ability to transport proppant into secondary fractures than water.Thickening of the supercritical CO_(2)needs to be increased beyond a certain value to have a significant effect on proppant carrying,and under the temperature and pressure conditions of this paper,it needs to be increased more than 20 times(about 0.94 m Pa s).Increasing the injection velocity and decreasing the proppant concentration facilitates the entry of proppant into the branching fractures,which in turn results in a larger stimulated reservoir volume.The results help to understand the proppant transport and placement process in rough fracture networks formed by reservoir stimulation,and provide a theoretical reference for the optimization of proppant pumping parameters in hydraulic fracturing.

Effect of Allelochemicals of Chinese-fir root extracted by supercritical CO_2 extraction on Chinese fir

Allelochemicals of Chinese-fir root was extracted by technology ofsupercritical CO_2 extraction under orthogonal experiment design, and it was used to analyzeallelopathic activity of Chinese-fir through bioassay of seed germination. The results showed thatas to the available rate of allelochemicals, the pressure and temperature of extraction were themost important factors. The allelochemicals of Chinese-fir root extracted by pure CO_2 and ethanolmixed with CO_2 have different allelopathic activities to seed germination, and the allelochemicalsextracted by ethanol mixed with CO_2 had stronger inhibitory effects on seed germination than thatextracted by pure CO_2.

Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn_2O_4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide （LiMn2O4） by supercritical hydrothermal （SH） accelerated solid state reaction （SSR） route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn2O4 materials were studied. The experimental results show that after 15 min reaction in SH route at 400 ℃ and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 ℃, compared with the conventional solid state reaction method. The prepared LiMn2O4 material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA.h/g at a rate of 0.1C （1C=148 mA/g） and a good rate capability at high rates, even up to 50C.

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.

Effect of Allelochemicals of Chinese-fir root extracted by supercritical CO2 extraction on Chinese fir

Allelochemicals of Chinese-fir root was extracted by technology of supercritical CO2 extraction under orthogonal experiment design, and it was used to analyze allelopathic activity of Chinese-fir through bioassay of seed germination. The results showed that as to the available rate of allelochemicals, the pressure and temperature of extraction were the most important factors. The allelochemicals of Chinese-fir root extracted by pure CO2 and ethanol mixed with CO2 have different allelopathic activities to seed germination, and the allelochemicals extracted by ethanol mixed with CO2 had stronger inhibitory effects on seed germination than that extracted by pure CO2.

Preparation of TiO_2-MoO_3 nano-composite photo-catalyst by supercritical fluid dry method

A series of TiO 2-MoO 3 nano-composite photocatalysts were prepared by supercritical fluid dry method(SCFD) and an impregnation technique with TiCl 4 and (NH 4) 6Mo 7O 24 ·4H 2O as the starting materials. The catalysts were characterized by the means of XRD, TEM and UV-Vis. Methyl orange was used as model compound for the evaluation of their catalytic activities. The results indicated that the photo-catalyst prepared by SCFD had the advantages of small size(12.84 nm), narrow distribution and good dispersivity. The presence of small amount of Mo in composite catalyst gives rise to the red shift of its absorbance wavelength, decrease of its energy gap and increase of the utility of visible light. Furthermore, higher surface acidity of the photo-catalyst was obtained as the result of the addition of MoO 3. Compared with pure TiO 2, the catalytic activity of the TiO 2-MoO 3 nano-composite photo-catalyst was improved significantly. As the doping concentration of the composite catalysts was controlled at 0.6%(molar percentage), 100% degradation of methyl orange was achieved with in 1.2 h irradiation time.

Supercritical water syntheses of transition metal-doped CeO_2 nano-catalysts for selective catalytic reduction of NO by CO:An in situ diffuse reflectance Fourier transform infrared spectroscopy study

In the present study,we synthesized CeO2 catalysts doped with various transition metals(M=Co,Fe,or Cu)using a supercritical water hydrothermal route,which led to the incorporation of the metal ions in the CeO2 lattice,forming solid solutions.The catalysts were then used for the selective catalytic reduction(SCR)of NO by CO.The Cu‐doped catalyst exhibited the highest SCR activity;it had a T50(i.e.,50%NO conversion)of only 83°C and a T90(i.e.,90%NO conversion)of 126°C.Such an activity was also higher than in many state‐of‐the‐art catalysts.In situ diffuse reflectance Fourier transform infrared spectroscopy suggested that the MOx‐CeO2 catalysts(M=Co and Fe)mainly followed an Eley‐Rideal reaction mechanism for CO‐SCR.In contrast,a Langmuir‐Hinshelwood SCR reaction mechanism occurred in CuO‐CeO2 owing to the presence of Cu+species,which ensured effective adsorption of CO.This explains why CuO‐CeO2 exhibited the highest activity with regard to the SCR of NO by CO.

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.

Current research into the use of supercritical CO2 technology in shale gas exploitation

The use of supercritical CO2 for shale gas extraction is a promising new technology.This paper explores current research into this process,looking at analysis of the mechanism of CH4 displacement in nanoporous shale,the positive and negative effects accompanying its use for sequestration as well as organic extraction,the migration of elements and the swelling process,and the macro and micro control mechanisms involved in permeability enhancement in reservoirs.Fruitful directions for future research are also considered through comparison with hydraulic fracturing.The research findings indicate that ScCO2 fluid replacement can be used to increase gas production and seal up greenhouse gases as an effective,clean and safe method of shale gas exploitation.It is particularly effective for promoting the desorption of CH4 in shale reservoirs that have developed fine neck-wide body pores,and the subtle structural changes effected by ScCO2 fluid in sensitive minerals in reservoirs with a high brittle mineral content also have a positive effect on permeability and storage capacity.The adsorption process has been characterized as consisting of three stages:short-term shrinkage,slow swelling,and stability;an expansion equation has been proposed for CO2/CH4 that incorporates competitive adsorption,collision desorption,and impingement re-adsorption.ScCO2 fracturing has been found to be more effective than hydraulic fracturing for dense reservoirs and more effective at linking up pore-micro-fissure-fracture systems.

Characteristics and mechanisms of supercritical CO_(2) flooding under different factors in low-permeability reservoirs

In recent years,supercritical CO_(2)flooding has become an effective method for developing lowpermeability reservoirs.In supercritical CO_(2)flooding different factors influence the mechanism of its displacement process for oil recovery.Asynchronous injection-production modes can use supercritical CO_(2)to enhance oil recovery but may also worsen the injection capacity.Cores with high permeability have higher oil recovery rates and better injection capacity,however,gas channeling occurs.Supercritical CO_(2)flooding has a higher oil recovery at high pressure levels,which delays the occurrence of gas channeling.Conversely,gas injection has lower displacement efficiency but better injection capacity at the high water cut stage.This study analyzes the displacement characteristics of supercritical CO_(2)flooding with a series of experiments under different injection and production parameters.Experimental results show that the gas breakthrough stage has the fastest oil production and the supercritical CO_(2)injection capacity variation tendency is closely related to the gas-oil ratio.Further experiments show that higher injection rates represent significant ultimate oil recovery and injection index,providing a good reference for developing low-permeability reservoirs.

Fundamental study and utilization on supercritical CO_(2) fracturing developing unconventional resources:Current status,challenge and future perspectives

Under the fact that considerable explo ration and production of unconventional re sources and wo rsening global climate,reducing carbon emission and rationally utilizing carbon resources have been drawn increasing attention.Supercritical CO_(2)(SC-CO_(2)) has been proposed as anhydrous fracturing fluid to develop unconventional reservoirs,since its advantages of reducing water consumption,reservoir contamination etc.Well understanding of SC-CO_(2)fracturing mechanism and key influencing factors will exert significant impact on the application of this technology in the field.In this paper,the fundamental studies on SC-CO_(2)fracturing from the aspects of laboratory experiment and simulation are reviewed.The fracturing experimental setups,fracture monitoring and characterizing methods,unconventional formation categories,numerical simulation approaches,fracturing mechanism and field application etc.,are analyzed.The fundamental study results indicate that compared with conventional hydraulic fracturing,SC-CO_(2)fracturing can reduce fracture initiation pressure and easily induce complex fracture networks with multiple branches.The field test further verifies the application prospect and the possibility of carbon storage.However,due to the limitation of reservoir complexity and attributes of SC-CO_(2),massive challenges will be encountered in SC-CO_(2)fracturing.According to the current research status,the limitations in basic research and field application are summarized,and the future development direction of this technology and relevant suggestions are proposed.

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.

Isolation of Organochlorine Pesticide from Ginseng with Supercritical CO_2

The feasibility of removal of the organochlorine pesticides residues of hexachlorocyclohexane(BHC) from radix ginseng with supercritical CO2 was explored. Some factors, such as extraction pressure, extraction temperature, and kinds of co-solvents were investigated. The experimental results indicate that it is possible to reduce BHC residues in radix ginseng to the level of 0.1 × 10^-6 with supercritical CO2 in the presence of suitable amount of co-solvent, such as water.

Experimental and Simulating Study of Supercritical CO_2 Extraction of Ginger Essential Oil

An experimental setup for separating ginger essential oil by supercritical fluid extraction is established. The effects of the extraction pressure, temperature, CO2 flow rate and particle size of raw material on the extraction rate are investigated, and the optimum process conditions of supercritical CO2 extraction are determined. A mathematical simulation model is established based on the mass conservation in differential units of extraction bed. The total mass transfer driving force and the equilibrium absorption constant are evaluated by the linear driving force theory. The results from numerical simulation agree well with the experimental data.

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...

Effect of proppant pumping schedule on the proppant placement for supercritical CO_(2) fracturing

Supercritical CO_(2)fracturing is a potential waterless fracturing technique which shows great merits in eliminating reservoir damage,improving shale gas recovery and storing CO_(2)underground.Deep insight into the proppant-transport behavior of CO_(2)is required to better apply this technique in the engineering field.In the present paper,we adopted a coupled Computational Fluid Dynamics and Discrete Element Method(CFD-DEM)approach to simulate the proppant transport in a fracking fracture with multiple perforation tunnels.Previous experiments were first simulated to benchmark the CFD-EDM approach,and then various pumping schedules and injection parameters(injection location,multi-concentration injection order,multi-density injection order and injection temperature)were investigated to determine the placement characteristics of proppant.Results indicate that the swirling vortex below the injection tunnels dominates the proppant diffusion in the fracture.The velocity of fluid flow across the proppant bank surface in multi-concentration injection shows a positive correlation with the proppant concentration.Injecting high-density proppant first can promote the transportation of low-density proppant injected later in the fracture to a certain extent.Decreasing the initial injection temperature of supercritical CO_(2)slurry helps enhance the particle-driving effect of fluid and improve the performance of supercritical CO_(2)in carrying proppant.

Hydrogen production by glycerol reforming in supercritical water over Ni/MgO-ZrO_2 catalyst

Nano ZrO2 and MgO-ZrO2 were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water （SCW）. The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600-800 ℃. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO2 catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H2/mol of glycerol could be obtained.

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.