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     

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     

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     

Measuring and modeling the rheological data of diglycidylether of bisphenol‐A during polymerization for finite element analyses

Finite element analyses (FEA) of thermosets are often performed on the basis of rheological data for fully cured resin. For the FEA of thermosets during curing, a material model is established and a technique is demonstrated, which allows the rheological data of the linear viscoelastic material to be derived. As the moduli are sensitive to conversion, all measured properties are related to temperature and conversion. Therefore the basis for the rheological data has to be a suitable reaction kinetic. Based on the kinetics shear and compression properties are measured independently and modeled mathematically with the focus to gain a formulation, which is suitable for FEA. The considered time constants are in the range between one second and one month as these times are relevant for the investigated relaxation times. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1868–1872, 2003     

The process window for diamond deposition from the vapor phase with sulfur in the C–H–O feed gas mixtures

Theoretical predictions using a modified radical species ternary diagram for C–H–O system indicate that addition of sulfur expands the C–H–O gas phase compositional window for diamond deposition. Sulfur addition to no-growth domain increases the carbon super-saturation by binding the oxygen and the addition of sulfur to the non-diamond domain reduces the heavy carbon super-saturation by decreasing C_nH_m species concentration in the gas phase. The overall effect of sulfur addition to gas phase mixtures is characterized as that of oxygen addition to the C–H system, i.e. expansion of the compositional window over which diamond can be deposited from the gas phase. In addition, the increasing sulfur concentration to diamond domain feed gases beyond 2000 ppm did not affect the steady state gas phase composition but the quality of diamond was reduced.     

高分子材料辐射接枝苯乙烯的研究进展

对各高分子材料辐射接枝苯乙烯的动力学，接枝方法及接枝材料的应用进行了综述，讨论限辐射剂量，剂量率，温度，后效应，溶剂，添加剂和高分子材料厚度及结晶性等方面对接枝反应的影响。     

Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

Significance of fluid regime in biological filtration

A dispersed flow model previously developed to study substrate utilization in unsaturated media was experimentally verified and its practical application was considered. For this purpose, measurements were made using tap water and a synthetic feed solution. The importance of the change in fluid regime as regards to the simultaneous transport and reaction within biological filters were demonstrated. The effect of drop formation and the breakage of liquid jets inside the filters on substrate utilization was also shown.