PC／PET共混物的非等温结晶动力学

采用等速变温ＤＳＣ法对ＰＣ／ＰＥＴ共混体系的非等温结晶动力学进行了研究，结果表明，从玻璃态结晶时，随着ＰＣ含量的增加，ＰＥＴ组分的结晶速率先增加后降低。耐从熔体结晶时，体系的结晶速率随着ＰＣ含量的增加而增加，讨论了ＰＣ对ＰＥＴ组分结晶过程的影响。     

Kinetic model for water/oil absorption of mesquite gum (Prosopis juliflora) and gum arabic (Acacia senegal)

The water and oil uptake of mesquite and arabic gums in powdered form was studied at temperatures of 23, 35 and 45°C. A previously proposed equation to predict osmotic equilibrium was tested using the experimental data with both gums and a good statistical fit was obtained. Mesquite gum showed the highest water and oil absorption at all temperatures studied. Temperature dependence of the reciprocal of the S₁ and WL_∞ were determined using an Arrhenius equation. The activation energy for water and oil absorption for gum arabic was 21.98 and 39.57 kJ mol⁻¹, compared to that of mesquite gum having values of 15.79 and 46.16 kJ mol⁻¹, respectively. A second order kinetic model was obtained for water and oil absorption for both gums.     

Development and simulation studies of an unsteady state biofilter model for the treatment of cyclic air emissions of an α‐pinene gas stream

This paper describes the development and simulation of an unsteady state biofilter model used to predict dynamic behaviour of cyclically‐operated biofilters and compares it with experimental results obtained from three, parallel, bench‐scale biofilters treating both periodically fluctuating concentrations and constant concentrations of an α‐pinene‐laden gas stream. The dynamic model, using kinetic parameters estimated from the constant concentration biofilter, was able to predict the performance of cyclic biofilters operating at short cycle periods (ie, in the order of minutes and hours). Steady state kinetic data from a constant concentration biofilter can be used to predict unsteady state biofilter operation. At a 24 h cycle period, the dynamic model compared well with experimental results. For long cycle periods (ie, hours and days), removal efficiency decreased after periods of non‐loading: the longer the period of non‐loading, the poorer the biofilter's performance at the re‐commencement of pollutant loading. At longer time scales the model did not effectively predict transient behaviour, as adsorption and changes in kinetic parameters were not accounted for. Modelling results showed that similar biofiltration performance for the cyclic and constant concentration biofiltration of α‐pinene is expected for biofilters operating solely in the first order kinetics regime. Poorer performance for cyclic biofilters following Monod kinetics spanning the entire kinetics range is expected as the cycle amplitude increases. The most important parameters affecting the performance of a cyclically‐operated biofilter with short cycle periods are: amplitude of cyclic fluctuations, C_{g, max}/C_g, relative value of the half‐saturation constant in the Monod expression, K_s, and effective diffusivity of α‐pinene in the biofilm, D_e. Copyright © 2005 Society of Chemical Industry     

DO浓度对SUFR系统同步硝化反硝化的影响

采用螺旋升流式反应器（SUFR）处理生活污水，考察了好氧反应池中DO浓度对其同步硝化反硝化的影响。结果表明，在好氧反应池上部溶解氧浓度为3．0～3．5mg／L时，发生了明显的同步硝化反硝化现象，其对TN的去除量占SUFR系统对TN去除总量的16％左右；好氧反应池中的同步硝化反硝化反应只发生在池的下部，其中、上部只进行了好氧硝化反应；SUFR系统中好氧反应池上部的最佳溶解氧浓度范围为3．0～3．5mg／L，此时系统的硝化和反硝化效果最佳，好氧反应池中的脱氮效果也较好，系统对TN的去除率〉84％。     

Mass transfer kinetics of neodymium(III) extraction by calix[4]arene carboxylic acid using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamics and kinetics data are both important to explain the extraction property. In order to develop a novel separation technology superior to current extraction systems, many promising extractants have been developed including calixarene carboxylic acids. The extraction thermodynamics behavior of calix[4]arene carboxylic acids has been reported extensively. In this study, the mass transfer kinetics of neodymium(III) and the interfacial behavior of calix[4]arene carboxylic acid were investigated. RESULTS: The rate constant (K_ao) becomes constant when the stirring speed was controlled between 250 rpm and 400 rpm. The activation energy (E_a) was calculated to be 21·41 kJ mol^?1 or 88·17 kJ mol^?1 (dependent on temperature) from the slope of log K_ao against 1000/T. The linear relationship between the specific area and the extraction rate is the characteristic of an interfacial reaction control. The minimum bulk concentration of the extractant necessary to saturate the interface (C_min) is lower than 4·19 × 10^?4 mol L^?1. CONCLUSION: The effect of stirring speed, temperature, and species concentration on the extraction rate demonstrates that the extraction regime depends on the extraction conditions. The chemical reaction control governs the extraction regime at temperatures below 303 K and a mixed control regime occurs when the temperature is between 303 K and 318 K. The probable locale for the chemical reaction is at the liquid–liquid interface and the rate equation is deduced to be: ? d[Nd³⁺]_(a)/dt = k_f[Nd³⁺]_(a)[H₄A]_(o)^0·727[H⁺]_(a)^?0·978. The rate‐controlling step was suggested by the analysis of the experimental results. Copyright © 2008 Society of Chemical Industry     

Effect of pH on the Crystallization of Homogeneously Precipitated Nanosized PZT Powder

Nanosized lead zirconate titanate (PZT) powder with Zr:Ti ratio in the morphotropic phase boundary region was synthesized by homogeneous precipitation of metal ions. The powder precipitated at 90°C and at pH 6.7 resulted single-phase perovskite lead zirconate titanate powder when calcined at 550°C and above for 4 hours in air. The solution pH and the precipitation temperature strongly affect the composition of the calcined powder. The results obtained by structural characterization of homogeneously precipitated powder were compared with that obtained from the conventional precipitation method using ammonia in terms of crystallization, homogeneity, and microstructure. The homogeneously precipitated powder showed smaller particle size, minimum agglomeration and uniform shape on calcination and annealing. Powdered samples that precipitated by homogeneous precipitation crystallized directly to perovskite PZT, without any intermediate pyrochlore phase formation. In contrast, the NH₃ precipitated powder converted to perovskite PZT via metastable pyrochlore and it showed phase segregation upon annealing at higher temperatures. The reaction kinetics has been studied by X-ray diffraction, differential thermal analysis, and differential scanning calorimetry.     

Identification and modelling of aerobic hydrolysis – application of optimal experimental design

Hydrolysis mechanism plays a dominant role in the delicate balance of electron donor/electron acceptor ratios in BNR and EBPR systems as an important carbon source. In this study, the surface‐saturation‐type hydrolysis kinetics was investigated based on respirometric measurements, within the context of the theoretical and the practical identifiability of mathematical models. The identifiable parameters of a selected model were derived from respirograms. In addition, the information from the experiments was evaluated on the basis of Optimal Experimental Design (OED) methodology for different initial conditions of the batch respirometric experiment. © 2003 Society of Chemical Industry     

环己酮肟液相重排反应机理及动力学研究

研究了环己酮肟重排反应生成己内酰胺的机理及反应动力学方程。在建立用分光光度法测定环己酮肟浓度方法的基础上,实验研究了反应温度为20~45℃范围内的液相重排反应动力学。提出了此反应的化学反应动力学速率方程式: -r肟= k0exp (-E/RT)Ca肟Cb硫酸,其中环己酮肟反应级数a为2,硫酸反应级数b为1,活化能为-E/R = -19.86 kJmol-1, 频率因子k0为1.35×1027。通过实验研究证实了作为催化剂的硫酸参与重排反应的机理,认为重排反应过程中游离SO3不参与反应,仅作为水的吸收剂,此结论对环己酮肟液相重排反应的生产技术改造提供了有力依据,并在生产中得到了应用。     

Sorption of Acid Green 25 on chitosan: Influence of experimental parameters on uptake kinetics and sorption isotherms

Acid Green 25, which is a diazoic dye bearing two sulfonic groups, is efficiently sorbed on chitosan. The protonation of chitosan may explain the electrostatic attraction of this anionic dye and that its optimum pH is close to 3. Preliminary protonation of amine groups (obtained by contact with a sulfuric acid solution) reduced the variation of solution pH following sorbent addition but significantly reduced sorption performance: the maximum sorption capacity of raw chitosan, 525 mg dye/g (0.84 mmol dye/g), was halved by acidic preconditioning. The acidic conditioning also reduced the kinetic rate—the time necessary to reach equilibrium increased up to threefold depending on the experimental conditions. The size of sorbent particles influenced sorption kinetics and equilibrium because of resistance to intraparticle diffusion, but the sorption appeared to occur not only at the surface of the sorbent but also in the intraparticle network of the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1073–1080, 2003     

含两种不同共聚组分改性聚酯的结晶速率

添加己二酸、间苯二甲酸,聚乙二醇对PET进行改性,合成样品。用DSC法研究合成共聚物的等温结晶动力学。结果表明,在所选择的温度范围内,共聚物很好的符合Avrami方程。随温度的升高,共聚物的结晶速度常数K和Avrami指数n逐渐减小,结晶速度G逐渐降低。含2种柔性组分的共聚酯随着一种柔性组分含量的增加,结晶速率G上升;含一种刚性一种柔性组分的共聚酯随刚性组分含量的增加,结晶速率G下降。