超临界流体技术在有机电合成中应用可能性探讨

阐述了超临界流体技术与有机电合成的优势和不足，探讨了在有机电合成中应用超临界技术的可能性，并指出其应用前景。     

Catalytic hydrodechlorination of 1-chlorooctadecane, 9,10-dichlorostearic acid, and 12,14-dichlorodehydroabietic acid in supercritical carbon dioxide

Kinetic and thermodynamic analyses of catalytic hydrodechlorinations in supercritical carbon dioxide (SC-CO₂) were performed using 5% Pd supported on γ-Al₂O₃. The selected standard compounds used for the study represented chlorinated wood resins commonly found in pitch deposits; 1-chlorooctadecane (C₁₈-Cl), 9,10-dichlorostearic acid (Stearic-Cl₂), and 12,14-dichlorodehydroabietic acid (DHA-Cl₂). The reaction utilized isopropanol as a hydrogen donor. Pressure, temperature, and the concentrations of isopropanol and palladium were varied to study the effect of each parameter and to optimize the dechlorination yield. The reaction in SC-CO₂ was compared to the one in liquid solvents at atmospheric pressure. By applying a Langmuir–Hinshelwood kinetic model, the rate-determining step of the reaction was deduced to be adsorption of the chlorinated molecules on the palladium surface. The apparent activation energies of the reactions for C₁₈-Cl, Stearic-Cl₂, DHA-Cl₂ were 43±5, 40±7, and 135±7 kJ mol⁻¹, respectively, in SC-CO₂. The relatively high activation energy for DHA-Cl₂ was apparently due to structural differences from the other two compounds. The apparent activation energy of dechlorination of C₁₈-Cl in liquid isopropanol at atmospheric pressure was determined to be 35±3 kJ mol⁻¹, leading to the conclusion that the rate-determining step is the same for this compound in both fluid systems. The enthalpies of desorption of stearic acid and dehydroabietic acid were determined to be 18±2 and 12±2 kJ mol⁻¹, respectively. These values being less than half of the apparent activation energies of dechlorination of their corresponding chlorinated compounds indicates that desorption of the dechlorinated products is not the rate-determining step of the reaction. This was consistent with the conclusion that the rate-determining step is adsorption, on the understanding that the reaction mechanism is same in both fluid systems.     

600MW超临界机组凝泵变频控制及效果分析

节能减排是电力行业的一项基本要求,属于考核范围的重要项目之一。在大型发电企业中,各企业都在寻找各种节能减排的方式,凝泵变频控制受到更多的电厂重视和应用推广。本文介绍了浙能乐清电厂在#1机大修过程中对凝泵控制进行了改造,采用变频器控制。根据凝泵变频器的特点和除氧器两个调节阀的特性,对除氧器水位控制策略进行了完善和改进。现场的实际应用表明,改进后的凝泵变频器控制能有效的降低凝泵的耗电量,减小阻力损失,降低企业生产成本,凝泵变频器的控制和除氧器水位调节阀配合在一起能很好的对除氧器水位进行控制。     

超临界直流炉蒸汽发生器的建模与仿真分析

研究以某600MW机组超临界直流炉的蒸汽发生器为对象,从过程基本方程出发,建立单相及两相受热管动态特性的动力学方程.采用随体导数法建立了关于在亚临界及超临界工况的非线件分布参数动态数学模型.针对蒸汽发生器在两种典型工况下的动态特性进行了仿真研究,所得结果,对进一步研究超临界直流锅炉的安全运行中全工况动态仿真提供有意义的设计参考.     

Effect of NaOH on the decomposition of halogenated hydrocarbon by supercritical water oxidation

To protect alloys from corrosion phenomena in the supercritical water oxidation (SCWO) process, the effects of neutralizer on the conversion and corrosion were investigated. The surface morphologies of all the alloy coupons exposed to 2,4-Dichlorophenol (2,4-DCP) in the SCWO were significantly changed in microscopic images. The theoretical amount of NaOH as a neutralizer was calculated under the assumption of complete oxidation of 2,4-DCP. The pre-dosed NaOH in the range of 100% to 300% stoichiometric amount could not affect significantly the pH value in the SCWO. Moreover, the pH = 7 was not achieved until 700% stoichiometric amount of NaOH was pre-dosed to the reactor. It is noted that the conversion rate recorded over 99% without oxidant when 800% of NaOH was pre-dosed into the reactor. In addition, under the addition of H₂O₂ as an oxidant, the increased amount of NaOH led to the improvement of conversion rate. The pre-dosed NaOH may contribute to the conversion rate of 2,4-DCP in the SCWO. However, due to low solubility of salt in the SCWO, the fouling problem should be solved in the SCWO process.     

Foaming of polymers with supercritical CO2: An experimental and theoretical study

Microcellular polystyrene (PS) foams and porous structures of the biodegradable poly(d,l-lactic acid) (P_d,lLA) were prepared with the batch foaming technique (pressure quench) using supercritical CO₂ as blowing agent. The effect of pressure, temperature and depressurization rate on the final porous structure was investigated. The results revealed that the size of the pores decreases and their population density increases with pressure increase, or decrease of temperature, and/or increase of the depressurization rate. The results were correlated by combining nucleation theory with NRHB model in order to account for and emphasize the physical mechanism related to nucleation of bubbles inside the supersaturated polymer matrix. A satisfactory agreement between correlations and experimental data was obtained indicating that the nucleation theory yields quantitative correlations when variables such as sorption, degree of plasticization, and surface tension of the system polymer-supercritical fluid are accurately described.     

超临界水的辐化反应研究

It is known that water exists in supercritical state above 374C and 22.1MPa, where gas phase and liquid phase are merged into a single phase. In the supercritical state, the density is controllable by changing the pressure. The properties such as the ionic product, solubilities of salts, gas and organic compounds, and dielectric constant of supercritical water are very different from those of water at room temperature.Recently much attention has been paid to supercritical water because many possible applications such as synthesis of functional materials, waste oxidation, and biomass conversion have been proposed by using above peculiar properties of the supercritical water. Thus, much intensive work is in progress all over the world. In addition, a new concept of nuclear reactor using the supercritical water as a coolant has been proposed, which has been chosen by DOE, USA as one of the forth generation nuclear reactors.Therefore, radiation chemistry study of the supercritical water seems inevitably important, yet little work has been done so far. We started radiation chemistry study of supercritieal water by pulse radiolysis and γ radiolysis five years ago. We have observed hydrated electrons as a first target. We also measured inorganic radicals, metal ions, organic radicals in high temperature and supercritical water by a pulse radiolysis technique. It was found that absorption spectra of the transient species are dependent on temperature. Some transients show red-shift, and some bands are blue-shifted, with increasing temperatures. A G-value evaluation of water decomposition products was also done by using methyl viologen as a scavenger and it was revealed that the values are significantly dependent not only on temperature but also on density in supercritical water. An extended study on the behavior of solvated eleclions in different alcohols at high temperatures and super critical state is also in progress.     

沙轻和沙中减压渣油的分离、组成与性质

利用超临界流体萃取分馏技术,对沙轻和沙中减压渣油进行了分离;分析测定了窄馏分的密度、折光率、残炭、平均分子质量、元素(C、H、N、S)、含镍、钒质量分数、族组成(饱和分、芳香分、胶质、沥青质);计算了窄馏分的平均结构参数;对窄馏分的平均沸点进行了预测,其最后一个馏分的平均沸点可达1050K,残渣的平均沸点接近1500K。研究表明,沙轻和沙中减渣窄馏分的性质、组成和平均结构随收率的增加基本呈现有规律的变化;超临界流体萃取分馏所得重馏分和残渣性质低劣,氢碳原子比小,N、S和金属元素质量分数高,含胶质、沥青质质量分数高;分析了两种渣油萃取分馏窄馏分、残渣的性质组成对加工过程的影响。     

二次再热超临界机组热力系统经济性定量分析方法

该文针对二次再热超临界机组采用了二次再热和高低压加热器回热抽汽均设有外置蒸汽冷却器进行过热度跨级利用的特点，基于等效热降理论，经过严格的理论分析和数学推导，得出了各加热器名义和真实抽汽等效热降及抽汽效率的计算方法，给出了二次再热超临界机组热力系统经济性的局部定量分析法则，形成了一套完整的经济性定量计算方法。利用该模型仅用3个公式即可以方便、快捷、准确地计算出热力系统发生局部调整和变化时机组经济性指标的变化，为此类机组的经济性分析和节能诊断提供了一种简捷、准确的定量方法。并通过实例计算验证了该模型的可行性和准确性。