Synthesis of manganese oxide particles in supercritical water

The synthesis of manganese oxide and LiMn₂O₄ particles in supercritical water has been investigated with a residence time of 10–40 seconds. It was suggested that the reaction temperature for SCW process should be relatively higher than the critical temperature of water, to synthesize the particles of uniform size and shape. It was observed that the selective synthesis of LiMn₂O₄ was mainly dependent of the amount of OH^- ion in the reactants. We concluded that the size, shape and structure of particles were strongly influenced by a change in the reaction temperature, reactant composition and OH^- ion amount, and thus enabling to synthesize a specific metal oxide particles. The reaction mechanisms for manganese oxides and LiMn₂O₄ have been proposed with the oxidation, hydrolysis and dehydration steps.     

基于多变量摄动的超临界CO2干气密封动态特性

超临界CO₂压缩机进口端干气密封工况处于临界点附近,强非线性物性及高Reynolds数流动使其密封特性异于常规介质干气密封。在综合考虑四种实际流体效应的稳态膜压求解模型基础上,基于摄动法推导了包括膜压、密度、黏度、Reynolds数、湍流系数和惯性系数在内的多变量摄动干气密封动特性数值模型。对比分析了超临界CO₂和N₂干气密封的动态特性,研究了不同频率比下各实际流体效应和变量摄动形式对超临界CO₂干气密封动特性系数的影响规律,获得了不同条件下动态特性的关键影响因素。结果表明：高频下超临界CO₂干气密封的刚度和阻尼系数较N₂干气密封降幅超过50%,湍流效应和实际气体效应对干气密封动态特性影响显著,低频下采用经典变量摄动和忽略湍流系数摄动会使动特性系数计算偏差很大,而高频下经典变量摄动模型对刚度系数的预测精度可接受。     

圆管内超临界CO2的阻力特性

对超临界二氧化碳在圆管内流动时的压降和摩擦系数进行了实验研究。实验段长为2000 mm,内径为10 mm。该实验压力范围为8～16 MPa,质量流量范围为1000～1525 kg·m^-2·s^-1,内壁热通量范围为96.5～283.2 kW·m^-2。得到了不同工况下竖直圆管内流动阻力的变化规律,分析了压力、质量流速、主流焓值和热通量对圆管内摩擦阻力的影响。实验结果表明摩擦压降随着质量流量和压力的增加而显著增加,特别是当主流焓值超过拟临界焓值后,其增加的速度变得更加剧烈,同时发现热通量对摩擦压降的影响较小。对于预测常物性摩擦因子的经验关联式并不能预测超临界CO₂的摩擦因子。因此提出了一个新的经验关联式,其实验数据在±20%误差范围内占83.31%。     

Low temperature deposition of titanium oxide containing thin films in trench features from titanium diisopropoxide bis(dipivaloylmethanate) in supercritical CO2

We studied supercritical carbon dioxide fluid deposition of titanium oxide (TiO₂) in trench features on Si substrates using a flow-type deposition apparatus from titanium diisopropoxide bis(dipivaloylmethanate), aiming at fabricating conformal films at a relatively low temperature. We investigated the deposition rate and step coverage under a fluid temperature from 40 to 60 °C, a pressure from 8.0 to 10.0 MPa, and a substrate temperature from 80 to 120 °C. They were dependent on the fluid density, indicating that the solubility difference between the bulk fluid and the neighborhood of the substrate surface plays a decisive role for the deposition. An excellent conformal filling of the trench features was achieved from the fluid of 60 °C under 8 MPa on the substrate kept at 80–100 °C. The XPS spectra of the deposited film suggested partial formation of TiO₂, and the XRD spectra showed the existence of some crystalline TiO₂ (anatase).     

方形微通道内超临界CO2流动换热特性研究

采用SST k-ω湍流模型对加热条件下超临界CO₂在方形微通道内的流动换热特性进行了数值模拟。通过对比三种壁面平均传热系数、浮升力参数和二次流强度的沿程变化研究了管型、热通量、质量流量和倾斜角度对微通道内流动换热性能的影响。结果表明：水平方形微通道的整体换热性能优于相同水力直径的半圆形微通道。流体域典型截面的温度分布、速度分布和湍动能分布等信息可以很好地解释水平方向流动时上、下壁面传热差异的现象。减小热通量、增大质量流量或减小流体流动方向与重力方向之间的夹角,可提高方形微通道的整体换热水平。该模拟结果对以超临界CO₂为工质的微通道换热器的设计和优化具有一定的理论指导意义。     

Research progress on leakage characteristics of supercritical CO2 pipeline

Leakage of supercritical CO₂ long-distance pipelines may cause significant accidents such as pipeline fracture propagation, human injury and medium loss. Therefore, it is of great significance to further study the variation of thermodynamic parameters in the process of pipeline leakage. At present, there is insufficient research on the leakage characteristics of supercritical CO₂ pipelines, and it is necessary to conduct a detailed literature review and analysis. This paper introduces the research background and significance of CO₂ pipeline leakage characteristics. The experimental, theoretical analysis and numerical simulation of the decompression process, near-field jet expansion and far-field diffusion of CO₂ pipeline at home and abroad are reviewed in detail. Finally, this paper summarizes the current research deficiencies of supercritical CO₂ pipeline leakage characteristics, and prospects the future research direction.     

超临界CO2管道泄漏特性研究进展

超临界CO₂输运管道泄漏可能造成断裂扩展、人员伤害和输运介质损失等重大事故,因此对泄漏过程中热力学参数变化规律的深入研究具有重要意义。目前对超临界CO₂管道泄漏特性研究不够,有必要进行详细的文献综述分析。介绍了CO₂管道泄漏特性研究背景及意义,综述了国内外CO₂管道泄漏过程中减压过程、近场射流膨胀及远场扩散规律实验、理论分析和数值模拟方面的研究现状,分析了目前超临界CO₂管道泄漏特性的研究不足,并对将来的研究方向进行了展望。     

压力瞬态下超临界压力CO2的传热特性

在均匀加热条件下,开展超临界压力二氧化碳在压力瞬态下的传热特性实验研究。实验段内径为10.0mm,实验参数范围：压力P=7.58~9.97MPa,热流密度q _w=64~256kW/m²,质量流速G=660~893kg/(m²·s)。分析了正常传热和传热恶化条件下,瞬间泄压过程对传热的影响规律。实验结果表明,正常传热工况下,壁温随着压力的减小有降低的趋势,传热系数明显增大;传热恶化发生后壁温迅速上升,对应的传热系数减小传热恶化更加严重,且恶化壁温峰值点向着入口方向移动。最后对实验现象进行了解释,正常传热下壁温降低是由于压力的降低增大了比热容,从而改善了传热。传热恶化发生后,压力的降低减小了拟临界焓值i _pc,从而增大了超临界沸腾数SBO,更大的SBO表明膨胀动量力占主导,靠近壁面低密度的vapor-like fluid在不断向外膨胀,从而使得低密度层流体的厚度增加,从而加大了传热热阻,这时壁温升高或者出现更大的恶化。     

Effect of dispersion method and process variables on the properties of supercritical CO2 foamed polystyrene/graphite nanocomposite foam

In this study, polystyrene/nanographite nanocomposite foams were made by different compounding methods, such as direct compounding, pulverized sonication compounding, and in situ polymerization, to understand the effect of the process variables on the morphology of the nanocomposites and their foam. The foam was made by batch foaming using CO₂ as the blowing agent. Various foaming pressures and temperatures were studied. The results indicated that the cell size decreased and the cell morphology was improved with the advanced dispersion of the nanoparticles. Among the three methods, the in situ polymerization method provided the best dispersion and the resulting nanocomposite foam had the finest cell size and the highest cell density. In addition, adding nanoparticles as a nucleating agent can make foams of similar cell size and cell density at a much lower foaming pressure. This result can be explained by the classical nucleation theory. This discovery could open up a newroute to produce microcellular foams at a low foaming pressure. POLYM. ENG. SCI., 53:2061–2072, 2013. © 2013 Society of Plastics Engineers     

Tandem Staudinger-Aza-Wittig reaction in supercritical CO2: Synthesis of a pharmaceutical interest compound

The aim of this research was to investigate the capability of using supercritical CO₂ (scCO₂) as reagent and solvent in the synthesis of pharmaceutical cyclodextrinyl derivatives in smooth reaction conditions. In this way we have followed the kinetics of a synthesis which was previously realized in DMF, by using tandem Staudinger-Aza-Wittig (S.A.W.) reaction in scCO₂ at 200 bars pressure in a 100 mL reactor. The results show that the reaction in scCO₂ showed a second order kinetics with the yield of 92%.     

垂直上升管内超临界CO2 流动传热特性研究

在压力为7.5～21 MPa，热通量为50～413 kW·m^-2，质量流速为519～1500 kg·m^-2·s^-1的实验参数范围内，对超临界CO₂在内径为10.0 mm的垂直上升管内的流动传热特性进行了均匀加热条件实验研究。分析了热通量、压力和浮升力对圆管内传热特性的影响规律。实验结果表明：随着热通量的增加，传热出现恶化现象，并且随着热通量的增加壁温峰值点向入口段移动。传热恶化发生在流体温度小于拟临界温度而壁面温度大于拟临界温度附近。增大压力时由于物性的变化趋于平缓，传热恶化被抑制。当传热恶化发生时，浮升力对传热恶化有明显的影响。基于实验数据，综合考虑物性变化和浮升力对传热的影响，建立了新的超临界二氧化碳传热关联式，在实验工况范围内，预测值与实验值的平均偏差和标准差分别为1.2%和16.29%。     

Synthesis of barium titanate using supercritical CO2 drying of gels

BaTiO₃ powders from sol-gel derived gels were prepared using two different drying methods. In addition to the conventional drying of gels in air at 90°C the supercritical CO₂ drying method was also used. Results showed that the properties of BaTiO₃ powder produced by supercritical drying with CO₂ are better. The grain surface is less contaminated as a result of the supercritical drying and the microstructure development during sintering leads to a homogeneous fine-grained microstructure.     

Effect of cations and anions on properties of zinc oxide particles synthesized in supercritical water

Hydrothermal synthesis of zinc oxide fine particles from zinc salt (Zn(CH₃COO)₂, ZnSO₄, Zn(NO₃)₂) and alkali metal hydroxide (LiOH, KOH) aqueous solution was carried out with a Ti alloy batch reactor in supercritical water. Particle size synthesized in LiOH solution was relatively smaller than that in KOH. Emission spectra of the particle produced from ZnSO₄ and LiOH aqueous solution shows the highest intensity among these systems. Hydrothermal synthesis of zinc oxide fine particles from Zn(NO₃)₂ and LiOH solution was also carried out with a flow-through apparatus for continuous production and rapid heating of the starting solution to supercritical states. Nanoparticles having an average particle diameter of 16 nm was produced at 659 K and 30 MPa.     

氧化物气凝胶催化剂的超临界CO2干燥法制备及其应用

超临界CO2干燥技术是一项绿色安全,制品结构可控的新的制备特殊材料的技术,综述了国内外探索其工艺和干燥机理的研究现状,阐述了利用其制备超细ZrO2气凝胶的工艺实验研究,并展望了氧化物气凝胶催化剂的应用前景.     

超临界CO2在水平螺旋管内的冷却换热特性

采用数值模拟和实验结合的方法研究超临界CO₂在水平冷却螺旋管内的换热特性。研究了质量流量、热通量及压力对传热系数的影响,并比较了直管和螺旋管在加热和冷却条件下的换热特性。结果表明,与直管相比,螺旋管对换热的强化作用随着质量流量的减小和压力的增加而增加。在相同热通量条件下,螺旋管的冷却换热的传热系数比加热的传热系数高,且由于浮升力的影响,加热条件下传热系数存在较大的振荡。     

低质量流速下超临界CO2在管内冷却换热特性

开展了低质量流速下超临界CO₂在水平直管内冷却过程的换热特性的实验研究。实验压力为p=7.5~9.0 MPa,质量流速为G=79.6~358.1 kg·m^-2·s^-1,流体温度为25.0~50.0℃。分析了质量流速、压力、流体温度对换热的影响,并引入Richardson数阐述浮升力对超临界CO₂在水平直管内冷却换热影响。实验结果表明: 传热系数随着质量流速的增加而增大。传热系数峰值点随压力的升高向高温区偏移。当质量流速较小时,传热系数峰值点出现在准临界温度之前,且浮升力作用加大,流体处于混合对流状态。将传热系数的实验值和已有的换热关联式计算值作对比后发现在低质量流速下误差较大,拟合了低质量流速工况的超临界CO₂在水平直管内冷却换热的关联式,94%的实验值和拟合关联式误差在±20%范围内。     

超临界CO2/R41小通道内的换热特性

对R41和混合工质CO₂/R41 (20.5/79.5)、CO₂/R41(51.4/48.6)在直径为2 mm的水平光滑圆管中的超临界冷却流动换热特性进行了实验研究。质量流速范围为400～800 kg·m^-2·s^-1,压力为6.0～8.0 MPa,热通量为12～48 kW·m^-2,流体温度为20～80℃。3种工质的对流传热系数的极值随CO₂含量的增加而增大,在相同条件下R41的传热系数小于CO₂/R41的传热系数。混合物的超临界传热系数变化规律与纯R41相同。实验条件下,3种流体的传热系数在2～25 kW·m^-2·K^-1之间,压力的影响显著,越接近临界压力对应压力条件下的传热系数极值越高。在远离准临界点的区域传热系数随热通量变化不明显,而在准临界点附近对流传热系数的极值随热通量的增加而小幅减小。将实验结果与经验关联式计算结果进行了比较,有4个关联式的预测效果较好,误差均在±30%以内,预测误差随CO₂含量的增加而下降。     

超临界CO2染色技术

主要对超临界CO2染色技术进行了研究。运用超临界CO2特性,研制了无水染色装置,对该装置的基本结构及工作原理加以说明,并实现了计算机自动控制。使用无水染色装置,在超临界CO2状态下对纤维织物用分散染料进行染色,并采用扫描电镜和红外光谱仪测定分析改性和染色的效果。对染色工艺参数,如压强、温度和CO2的流量进行了分析,结果表明这些参数对染色效果影响较大。对天然纤维的改性,可以达到改善染色牢度和匀染度,通过合理控制染色压强、温度和CO2的流量等影响因素就可以取得较好的染色效果。     

Effect of albumin on physical characteristics of drug particles produced by supercritical fluid technology

In this study, two drugs, terbutaline sulphate (TS) and ipratropium bromide (IB), were micronized by means of a CO₂-based aerosol solvent extraction system (ASES). TS and IB particles with albumin as additive were also precipitated in order to improve the powder flow behavior in an accelerating air flow. Albumin is considered an inactive ingredient for FDA-approved drugs and is endogenous to the lung. The addition of albumin affected the particle morphology resulting in improved aerosolization properties. In the present study, ASES experiments were conducted using a mixed solvent of ethanol/dimethylformamide (EtOH/DMF) for the micronization of TS and pure DMF was used as solvent for IB. For the respirable TS, optimum processing conditions were at about 100 bar and 50 °C. For the IB particles, the conditions were at 200 bar and 40 °C. The aerosol characteristics of all precipitated drug particles in this work were analyzed by comparing the particle size distribution (PSD) and the associated mass median aerodynamic diameter (MMAD) measured by scanning electron microscopy (SEM) to those obtained from Aerodynamic Particle Sizer (APS) and from the Micro-orifice Uniform Deposit Impactor (MOUDI). The results indicate that the TS and IB particles with albumin are less cohesive and less agglomerated in air flow, thus leading to more effective and consistent lung deposition.