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     

酸催化二甘醇脱水环化反应研究

以硫酸、磷钨酸、ZRP-5分子筛为催化剂,研究了二甘醇(DEG)脱水环化的反应规律。结果表明,DEG发生分子内脱水环化反应,生成1,4-二氧六环(DOX),DEG分子间脱水不仅可以生成四甘醇、六甘醇等,同时可生成三甘醇、五甘醇等一系列的多甘醇(PEG)。不仅DEG可以脱水环化生成DOX,在反应中生成的PEG也同样可以进行生成DOX的反应。对于二甘醇(DEG)脱水环化反应,硫酸是性能优良的催化剂,反应可以在较低的温度下进行,馏出产物中DOX选择性大于95％。     

Nature and Growth of Interaction Layers Formed during the Reaction between Solid Ni and Liquid Al

The nature and growth of the interaction layers between solid Nb and liquid Al has been studied by carrying out the tests on Nb(s)-Al(l)and Nb(s)-Al(l)-Ni(s) reaction couples isothermally reacted between 700℃and 900℃for different time intervals.It has been found that the interaction layer between Nb and Al contains two parts:a thin continuous layer of NbAl3 adjacent to the Nb surface and a two-phase zone constituted of NbAl3 particles dispersed in an Al matrix.Although the nature and growth of interaction layers follows the sour-stage mechanism,a typical cruciform pattern does not occur in Nb(s)-Al(l) reaction couples.However,a cruciform pattern was observed in Nb(s)-Al(l)-Ni(s)reaction couples.The movement of NbAl3 particles is important to the production of cruciform pattern in the reaction couples.     

Thermal Expansion Behavior of La1—xSrxMn1—yCoyO3—δ Perovskites

The thermal expansion behavior of La1-xSrxMn1-yCoyO3-δ (x=0.2-0.4, y=0.1-0.3) perovskites in air has been investigated. The average linear thermal expansion coefficients increased with increasing Sr content up to 40 mole fraction or Co content up to 30 mole fraction. The expansion is generally attributed to an increase in the average cation radius as some of the cations in the perovskite are reduced in valence when oxygen ions are removed from the structure.     

Effect of Cu concentration on the reactions between Sn-Ag-Cu solders and Ni

The reaction between the Sn-Ag-Cu solders and Ni at 250°C for 10 min and 25 h was studied. Nine different Sn-Ag-Cu solders, with the Ag concentration fixed at 3.9 wt.% and Cu concentrations varied between 0.0–3.0 wt.%, were used. When the reaction time was 10 min, the reactions strongly depended on the Cu concentration. At low-Cu concentrations (≦0.2 wt.%), only a continuous (Ni_1−xCu_x)₃Sn₄ layer formed at the interface. When the Cu concentration increased to 0.4 wt.%, a continuous (Ni_1−xCu_x)₃Sn₄ layer and a small amount of discontinuous (Cu_1−yNi_y)₆Sn₅ particles formed at the interface. When the Cu concentration increased to 0.5 wt.%, the amount of (Cu_1−yNi_y)₆Sn₅ increased and (Cu_1−yNi₆)₆Sn₅ became a continuous layer. Beneath this (Cu_1−yNi_y)₆Sn₅ layer was a very thin but continuous layer of (Ni_1−xCu_x)₃Sn₄. At higher Cu concentrations (0.6–3.0 wt.%), (Ni_1−xCu_x)₃Sn₄ disappeared, and only (Cu_1−yNi_y)₆Sn₅ was present. The reactions at 25 h also depended strongly on the Cu concentration, proving that the strong concentration dependence was not a transient phenomenon limited to a short reaction time. The findings of this study were rationalized using the Cu-Ni-Sn isotherm. This study shows that precise control over the Cu concentration in solders is needed to produce consistent results.     

Al-Cu-Fe QUASICRYSTALLINE PHASE FORMATION BY MECHANICAL ALLOYING

Al-Cu-Fe alloys were prepared from elemental powders in a high-energy planetary ball mill. A sequence of solid state reactions resulting in quasicrystal (QC) phase formation takes place during heating of the as-milled powder. These reactions were studied by both differential scanning calorimetry and x-ray diffraction methods. Mechanically alloyed powders were consolidated by cold and hot pressing, as well as by explosive compaction. After annealing at sufficiently high temperatures, the consolidated samples are single-phase QC, except the ones consolidated by explosion. The high reactivity of the as-milled alloys causes the appearance of high porosity of the consolidated samples after the annealing.     

Thermodynamic Aspects of Aromatic Hydrogenation

Aromatic hydrogenation is one of the important classes of hydrotreating reactions and its thermodynamics play a significant role in achieving the product specifications. This article comprehensively reviews the available experimental thermodynamic data as well as the methods to estimate the data for aromatic hydrogenation. The data indicate that aromatic hydrogenation reactions are thermodynamically more favorable at about 200°C-250°C and moderate pressures (3-5 MPa). Industrially, however, these reactions are carried out at 300°C-375°C to have reasonable kinetics. Hence there is a need for highly active catalysts, which can facilitate significant kinetics of hydrotreating reactions at around 200°C-250°C.     

Pu(OH)4(am)与碳酸根的配位行为研究

为了解在惰气环境Pu(OH)_4(am)与碳酸盐溶液中HCO^-₃，CO^2-₃的配位行为，考察了放置时间对Pu总浓度的影响；同时也考察了pH值、碳酸根总浓度变化对碳酸盐溶液中Pu的主要存在形态及溶解总浓度的影响。实验结果表明，HCO^-₃离子与Pu(OH)_4(am)生成[Pu(OH)₄(HCO₃)₂]^2-（lg K=-2.61±0.18, lgβ=54.25±0.18）或[Pu(OH)₂(CO₃)₂]^2-（lgK=-2.61±0.18, lgβ=46.91±0.18）；CO^2-₃离子与Pu(OH)_4(am）生成[Pu(OH)₄(CO₃)₂]^4-（lgK=-3.52±0.11, lgβ=53.33±0.11）。可能的配位反应方程式为： Pu(OH)_4(am)+2HCO^-₃ = [Pu(OH)₄(HCO₃)₂]^2-, Pu(OH)_4(am)+2HCO^-₃ =[Pu(OH)₂(CO₃)₂]^2-+2H₂O, Pu(OH)_4(am)+2CO^2-₃=[Pu(OH)₄(CO₃)₂]^4-。     

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.