Study of the High‐Pressure Vapour‐Liquid Equilibria for Strongly Non‐ideal Binary and Ternary Mixtures

High‐pressure vapour‐liquid equilibria for binary and ternary high polar and asymmetric systems are calculated using the Peng‐Robinson‐Stryjek‐Vera equation of state coupled with the Twu‐Coon (TWMR), the Orbey‐Sandler (OSMR) and the Wong‐Sandler (WSMR) mixing rules. Modified UNIFAC model is used for determining the activity coefficient and excess Gibbs free energy. The calculated results are compared with the experimental data and good agreement is observed. The average absolute deviation percents (AAD%)s indicated that the WSMR has less AAD% than other mixing rules in most of cases.     

超临界流体CO_2提取虎杖中的有效成分

以大黄素为指标对虎杖中的有效成分进行超临界流体CO2萃取。用正交设计法考察了最优萃取条件。影响超临界流体萃取率的主要因素依次是:动态流量、温度、压力、时间;确定了大黄素的最佳萃取条件是:萃取压力25 MPa,萃取温度55℃,动态流量8 kg/h,萃取时间30 m in。超临界流体萃取大黄素的提取率达0.36%。     

Phase behavior and density of polysulfone in binary fluid mixtures of tetrahydrofuran and carbon dioxide under high pressure: Miscibility windows

Mixtures of tetrahydrofuran (THF) and carbon dioxide (CO₂) were identified as new solvent systems for polysulfone. The miscibility and density of polysulfone in binary fluid mixtures of THF and CO₂ were investigated from 300 to 425 K at pressures up to 70 MPa. The influence of the CO₂ and polysulfone concentrations was studied, with the concentrations of the other two components kept constant. At a 4.5 wt % polymer concentration, the demixing pressures in a 10 wt % CO₂ and 90 wt % THF mixture increased with temperature (310–425 K) from 15 to 40 MPa. With increasing CO₂ concentration (from ca. 10 to 14 wt %), a significant increase (from 15 to 70 MPa at 310 K) was observed in the demixing pressures. Furthermore, with an increasing amount of CO₂, the nature of the phase boundary shifted from lower critical solution temperature behavior to upper critical solution temperature behavior. The influence of the polymer concentration was studied in the 0–5 wt % range at two CO₂ levels, with solvent compositions of 10 wt % CO₂ and 90 wt % THF and 13 wt % CO₂ and 87 wt % THF. The system with a higher level of CO₂ (13 wt %) showed highly unusual phase behavior: on pressure–composition and temperature–composition diagrams, the system displayed two distinct regions of miscibility. In the system with 10 wt % CO₂, the distinct regions of miscibility that were observed in the system with 13 wt % CO₂ partially overlapped and led to a W‐shape phase boundary. The densities of the polymer solutions were measured from the one‐phase region through the demixing point into the two‐phase region at a constant temperature. No significant change in density was found around the phase boundary; this indicated that the coexisting phases had similar densities, as is often the case with liquid–liquid phase separation in polymer solutions under high pressure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2357–2362, 2002     

Environmentally benign precipitation copolymerization of methacrylate ester and styrene to make polymeric microspheres in supercritical carbon dioxide

The polymeric microspheres were synthesized by the precipitation copolymerization of glycidyl methacrylate (GMA) with methacrylic acid(MAA) or 2‐hydoxyethyl methacrylate (2‐HEMA) containing styrene (ST) in SC‐CO₂. Scanning electron microscopy (SEM) showed that the products were spherical microparticles, with the addition of MAA and/or 2‐HEMA as the monomer, with diameter of 0.2–2 μm. The effects of copolymerization pressure, temperature, and ratios of GMA/MAA, ST, and/or GMA/2‐HEMA, on the particle size and morphology were investigated in detail. A new experiment setup is proposed for the large amount of production, based on the rule of lower monomer concentration, more stable system, and better use of the present polymerization apparatus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2425–2431, 2007     

Processing of polypropylene–clay nanocomposites: Single‐screw extrusion with in‐line supercritical carbon dioxide feed versus twin‐screw extrusion

This work investigates two different melt‐blending strategies for preparing compatibilized polypropylene‐clay nanocomposites, specifically: (1) conventional twin‐screw extrusion, and (2) single‐screw extrusion capable of direct supercritical carbon dioxide (scCO₂) feed to the extruder barrel. Proportional amounts (3 : 1) of maleic anhydride functionalized polypropylene compatibilizer and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt % are melt‐blended with a polypropylene homopolymer using the two approaches. The basal spacing, degree of exfoliation, and dispersion of organoclay is assessed using X‐ray diffraction, transmission electron microscopy, and rheology. In terms of the latter, both steady shear and small‐amplitude oscillatory shear provide information about the apparent yield stress and solid‐like terminal behavior respectively. Finally, nanoindentation is performed to determine the room temperature modulus of each melt‐blended nanocomposite. The results reveal unequivocally that the high shear of the twin‐screw process is vastly superior to the single‐screw with in‐line scCO₂ addition in generating well‐exfoliated, percolated polypropylene‐clay nanocomposites. It is likely that increased contact time between clay and scCO₂ is necessary for scCO₂ to positively affect exfoliation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 884–892, 2007     

Study of different effect on foaming process of biodegradable bionolle in supercritical carbon dioxide

Microcellular foaming of biodegradable Bionolle in supercritical CO₂ has been produced. The effects of a series of variable factors, such as saturation temperature, saturation pressure, and depressurization time and step on the foam structures and density, were studied through measurement of density and SEM observation. The experimental results show that higher saturation temperatures lead to an increase in bulk densities; and different depressurization time and step result in different product cell morphology. In addition, at some saturation temperature, the orientation of the cells can be found in the product morphology. XRD experimental results show that the foaming treatment with SC CO₂ increased the crystallinity of Bionolle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2901–2906, 2006     

600MW超临界燃煤机组SCR烟气脱硝工程实例

介绍了国电铜陵600 MW超临界燃煤机组安装脱硝装置项目的前期研究、主要设计特点、系统设计、调试运行,以及投产运行后的经济情况,得出了一系列火电项目加装脱硝设施建设与运行方面的参考意见.     

某支线飞机超临界机翼设计研究

文章在翼身组合体构形下,采用面向机翼的精细修形设计方法针对某支线飞机进行了超临界机翼设计.由于支线飞机机翼面积较小,在满足气动性能的前提下,能否满足结构设计的要求就成为本次修形设计所考虑的主要因素.设计实践表明,在合理的设计思想指导下,当初始外形与设计目标相差较大时,采用渐近修形设计技术仍然可以得到比较满意的结果.     

强化两相混合的超临界技术制备聚乳酸微粒

针对商品化聚乳酸微球粒径分布较宽难于适用气溶胶给药要求的不足,采用水力空化混合强化超临界流体辅助雾化技术(SAA-HCM)制备聚乳酸(PLA)超细微粒.该技术主要特点是通过在超临界流体和液相进料处引入水力空化混合器,强化两相间的混合.考察SAA-HCM过程混合器压力、温度、沉淀器温度、进料中CO2与液体溶液质量流量比和溶液质量浓度等操作参数对微粒形态和粒径分布的影响,成功制备出球形度较好,粒径分布较窄(1～3μm)的PLA微球.经X射线衍射(XRD)分析和差示扫描量热(DSC)分析显示,与原料PLA相比,微球晶型及热曲线变化不大,但结晶度下降.同时把操作参数与相行为进行关联,探讨了影响颗粒形貌的机理.对比超临界流体辅助雾化法(SAA)的实验结果表明:水力空化的引入能有效强化混合器内的两相传质,混合更好,能制备出适用于气溶胶给药要求的超细微粒.     

琥珀酰亚胺酯基类偶氮染料的制备及其超临界CO2羊毛清洁化染色

以对氨基苯甲酸和4-氨基-2-氯苯甲酸、苯胺和间甲苯胺为原料,采用重氮偶合反应制备染料前驱体,通过在前驱体上引入琥珀酰亚胺酯获得4例活性分散染料Ⅰ～Ⅳ.对染料的紫外-可见吸收光谱、光热稳定性、超临界二氧化碳(scCO2)中羊毛纤维的染色工艺等进行了测试.结果表明,4例染料均具有良好的光热稳定性,染料Ⅰ、Ⅲ和Ⅳ最大吸收波长集中在360～370 nm,染料Ⅱ的最大吸收波长红移到379～452 nm,染料均具备scCO2染色的条件.染料Ⅰ和Ⅲ的最佳染色条件为2 h、80℃和15 MPa,染料Ⅱ的最佳染色条件为1.5 h、80℃和15 MPa,染料Ⅳ的最佳染色条件为2 h、80℃和24 MPa.染色后的羊毛纤维的耐皂洗和耐光色牢度都可达4～5级,固色率最高可达86％,相比于未活化的前驱体,耐皂洗色牢度能提高2～3级,固色率最高能提升63％.SEM和显微镜成像证明4例染料具有良好的透染性,且能均匀附着于纤维的表面和内部.力学性能测试表明,染色后的羊毛纤维能基本保持原有的力学性能.