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。

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.

Evolution of Diagenetic Fluid of the Dawsonite-Bearing Sandstone in the Jiyang Depression,Eastern China

Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.

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.

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.

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.

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.

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...

Preparation of (Ti, Sn)O_2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (Ti, Sn)O2 were investigated and its catalytic mechanism was proposed. The photo-catalytic particles prepared using SCFD combination technology exhibited small particle size, large surface area and high activity.

Degumming of Silk Fibers by CO₂Supercritical Fluid

This paper is to study a new method to remove sericin from raw silk fiber. This new process is done using an organic acid as a pretreatment and then using CO2 supercritical fluid to remove sericin from silk fiber. This method would be a huge break from the traditional environmentally unsustainable methods used today. This new processing method keeps the removed sericin in a clean state that can be used as a highly marketable silk protein in the medical and cosmetic industries.

Supercritical Fluid Carbon Dioxide in the Extraction of Lanolin and Its Alcohol

The use of supercritical fluid carbon dioxide (SFCO2) in extraction of lanolin and its alcohol is superior to the conventional solvent extraction method. Its distinctive advantages include high extractive ratio, nontoxic and nonflammable solvents, and minimal by -product pollution. The resulting refined lanolin and its alcohol have light color and little odor, and can be used as raw materials for high grade cosmetic products.

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.

Micro-mechanical properties of shale due to water/supercritical carbon dioxide-rock interaction

To investigate the impacts of water/supercritical CO_(2)-rock interaction on the micro-mechanical properties of shale,a series of high-temperature and high-pressure immersion experiments were performed on the calcareous laminated shale samples mined from the lower submember of the third member of Paleogene Shahejie Formation in the Jiyang Depression,Bohai Bay Basin.After that,grid nanoindentation tests were conducted to analyze the influence of immersion time,pressure,and temperature on micro-mechanical parameters.Experimental results show that the damage of shale caused by the water/supercritical CO_(2)-rock interaction was mainly featured by the generation of induced fractures in the clay-rich laminae.In the case of soaking with supercritical CO_(2),the aperture of induced fracture was smaller.Due to the existence of induced fractures,the statistical averages of elastic modulus and hardness both decreased.Meanwhile,compaction and stress-induced tensile fractures could be observed around the laminae.Generally,the longer the soaking time,the higher the soaking pressure and temperature,the more significant the degradation of micro-mechanical parameters is.Compared with water-rock interaction,the supercritical CO_(2)-rock interaction caused a lower degree of mechanical damage on the shale surface.Thus,supercritical CO_(2)can be used as a fracturing fluid to prevent the surface softening of induced fractures in shale reservoirs.

Characteristics and mechanism of smart fluid for sweep-controlling during CO_(2) flooding

A smart response fluid was designed and developed to overcome the challenges of gas channeling during CO_(2)flooding in low-permeability,tight oil reservoirs.The fluid is based on Gemini surfactant with self-assembly capabilities,and the tertiary amine group serves as the response component.The responsive characteristics and corresponding mechanism of the smart fluid during the interaction with CO_(2)/oil were studied,followed by the shear characteristics of the thickened aggregates obtained by the smart fluid responding to CO_(2).The temperature and salt resistance of the smart fluid and the aggregates were evaluated,and their feasibility and effectiveness in sweep-controlling during the CO_(2)flooding were confirmed.This research reveals:(1)Thickened aggregates could be assembled since the smart fluid interacted with CO_(2).When the mass fraction of the smart fluid ranged from 0.05%to 2.50%,the thickening ratio changed from 9 to 246,with viscosity reaching 13 to 3100 mPas.As a result,the sweep efficiency in low-permeability core models could be increased in our experiments.(2)When the smart fluid(0.5%to 1.0%)was exposed to simulated oil,the oil/fluid interfacial tension decreased to the level of 1×10^(-2)mN/m.Furthermore,the vesicle-like micelles in the smart fluid completely transformed into spherical micelles when the fluid was exposed to simulated oil with the saturation greater than 10%.As a result,the smart fluid could maintain low oil/fluid interfacial tension,and would not be thickened after oil exposure.(3)When the smart fluid interacted with CO_(2),the aggregates showed self-healing properties in terms of shear-thinning,static-thickening,and structural integrity after several shear-static cycles.Therefore,this fluid is safe to be placed in deep reservoirs.(4)The long-term temperature and salt resistance of the smart fluid and thickened aggregates have been confirmed.

纳米SiO_(2)强化CO_(2)地质封存页岩盖层封堵能力机制试验

页岩为CO_(2)盐水层地质封存常见盖层岩石类型,强化盖层封堵能力有利于提高CO_(2)地质埋存量和安全性。为探究随CO_(2)混注纳米SiO_(2)(SNPs)强化盖层封堵能力的有效性和可行性,对CO_(2)地质封存页岩盖层样品开展原地条件下的超临界CO_(2)酸蚀反应试验,基础组为页岩样品-地层水、对照组为页岩样品-地层水+超临界CO_(2)、优化组为页岩样品-地层水+SNPs+超临界CO_(2),并采用核磁共振测试、场发射扫描电镜可视化观测、X射线衍射测试和岩石力学试验,探究CO_(2)酸蚀反应前后的页岩孔隙结构、表面形貌、矿物成分及力学性质特征。结果表明:优化组的大孔孔隙分量及孔隙度和渗透率增大幅度低于对照组;与对照组相比,优化组黏土矿物与碳酸盐岩矿物相对含量损失少,表明随CO_(2)混注SNPs可使岩样内部酸蚀作用减弱;SNPs在岩石端面吸附聚集或进入岩心孔喉,可使优化组页岩样品力学性能损伤程度降低;随CO_(2)混注SNPs有利于强化CO_(2)盐水层地质封存盖层封堵能力。

适合致密油藏的超临界CO_(2)-气溶性表面活性剂复合吞吐技术

为了进一步提高致密油储层超临界CO_(2)吞吐的开发效果,探索适合致密油藏的超临界CO_(2)-气溶性表面活性剂复合吞吐技术,通过原油黏度实验、油气界面张力实验、最小混相压力实验、原油膨胀系数实验以及超临界CO_(2)-气溶性表面活性剂复合吞吐模拟实验,评价了不同类型气溶性表面活性剂的性能及其对吞吐采收率的影响。结果表明:气溶性表面活性剂GRS⁃1的综合性能更加突出,随着气溶性表面活性剂质量分数的不断增大,原油黏度、油气界面张力和最小混相压力均呈现出逐渐降低的趋势,而原油体积膨胀系数则逐渐增大,并且岩心的吞吐采收率和入口端压力也呈现出逐渐增大的趋势;随着混合流体注入量的增加以及闷井时间的延长,岩心吞吐采收率和入口端压力均逐渐增大,并且岩心的渗透率越大,吞吐采收率就越高;超临界CO_(2)-气溶性表面活性剂复合吞吐的最佳实验参数为气溶性表面活性剂GRS⁃1的质量分数0.6%、混合流体注入量0.5 PV、闷井时间3 h、吞吐轮次3次。该复合吞吐技术能够显著提高致密油藏的采收率,对高效开发致密油藏具有指导意义。

页岩油藏注CO_(2)驱孔隙动用特征研究

CO_(2)在页岩油藏驱油时的孔隙动用特征是评价其应用于提高页岩油藏采收率效果的一项重要指标。因此,开展了超临界CO_(2)驱替页岩岩心室内实验,并以核磁共振(NMR)在线岩心扫描技术为手段对CO_(2)驱页岩油藏的孔隙动用特征和规律进行研究。结果表明,超临界CO_(2)非混相驱油主要动用页岩中孔隙半径在0.1~3.0µm范围内的油,而此过程中小于0.008µm孔隙半径内的油量反而增加,分析原因主要是CO_(2)在页岩层中通过压差和扩散作用将大孔隙内页岩油带入小孔隙中并发生吸附滞留,在驱替时间5 h后,CO_(2)驱替页岩油采收率达到35.7%,驱油效果较好。