Élimination de métaux par adsorption en réacteur à membranes à lit mobile de particules et en réacteur lit fixe continu - Approche cinétique

Ce travail propose un nouveau procédé d'élimination du Cu2+ par adsorption sur des résines échangeuses d'ions poreuses, mises en œuvre dans un réacteur à membrane à lit mobile de particules. Ce procédé a été étudié sur le plan cinétique pour des solutions synthétiques de Cu(II) dans de l'eau. L'application visée à moyen terme est l'intégration de cette opération unitaire dans une filière de traitement complète des effluents industriels liquides.L'étude cinétique a été réalisée avec une résine cationique forte Mono C-350H en réacteur agité fermé et thermostaté. Les isothermes d'adsorption ont été établies à 21°C et les paramètres de Langmuir et de Freundlich ont été calculés. Une étude de l'influence de la vitesse d'agitation et de la température sur la vitesse réactionnelle apparente a permis de déterminer la zone opératoire correspondant à un régime cinétique. Ce régime est obtenu pour un Reynolds d'agitation supérieur à 4700 et une température inférieure à 60°C. Dans ces conditions, l'ordre de la réaction par rapport au Cu2+ est de un et la constante cinétique exprimée par unité de masse de particules est kwapp=0,03721 lgrés-1min-1 à 21°C. L'énergie d'activation de la réaction a également été déterminée.Par ailleurs, en s'appuyant sur les résultats de l'étude cinétique, les premiers éléments de comparaison d'un réacteur classique à lit fixe et d'un réacteur original à membranes à lit de particules sont présentés. Pour le même débit à traiter, en fixant dans les deux cas un taux de conversion objectif de 95 %, le nouveau procédé permettant d'utiliser des particules de plus faible diamètre conduit à une réduction du volume de particules réactives d'un facteur 4, de la puissance énergétique à fournir au système d'un facteur 3 à 5. Les performances prometteuses de ce procédé restent à valider lors d'une étude pilote.Legislation in France and in Europe is becoming more rigorous for industrial fluid wastes, which is encouraging many industries to find a proper solution to their effluent problems and to include a complete wastewater treatment plant in their process. This paper focuses on effluents containing metallic compounds, which can be toxic. For Cu(II) the maximal allowed concentration is 1 mg/l. Many unit operations can be used to remove metal compounds from industrial waste waters, but the most widely used are scaling followed by settling and/or filtration, adsorption, solvent extraction and incineration. The main drawbacks encountered with these processes are:1. a low yield, 2. high operating and investment costs, 3. sludge production. This paper deals with a new unit operation to be included in a complete treatment line in place of adsorption, for removing metallic compounds. This new operation consists of a membrane moving bed reactor, which uses very fine dispersed adsorbent particles, so as to increase the particles' specific area. The particles are circulated with the water and separated from the treated water by an ultrafiltration hollow fibre or tubular membrane. The potential advantages of the process are the following: use of high specific area particles, production of a permeate without particles or suspended matter, no bed fouling (in comparison with fixed bed adsorption), continuous separation of metallic compounds and particles by the membrane. Moreover, we have chosen porous ion exchange resins as adsorbent particles, thus allowing a further continuous regeneration and recycling of the particles.The aim of this first paper on this new reactor is to introduce a comparison between the performances of a conventional fixed bed reactor and those of the moving bed membrane reactor, for the removal of Cu(II) from pure water. The first step for this study consists of a characterization of the particles/metallic compounds interactions in terms of kinetic rates and adsorption isotherms. Ion exchange is here considered with a chemical engineering approach, as a heterogeneous liquid/solid reaction.Experiments have been carried out in a thermostatted 1 litre stirred batch reactor. The solutions are prepared with CuSO4 . 5H20 in demineralised water. Cu(II) concentrations are measured by spectro-colorimetry using the regulation T90022 from AFNOR. Particles are cationic ion exchange resins referenced as Mono C-350H. Their mean diameter (315 mm) is higher than the membrane pore diameter (0.01 mm). No membrane internal fouling will then occur during particle filtration. Moreover the particle diameter is lower than the inner diameter of the fibres to prevent plugging of the hollow fibre.The adsorption isotherms have been determined at 21°C and the relevant Langmuir and Freundlich parameters are given in Table 2. The influence of stirring velocity and temperature in the reactor on the reaction rate has been studied. For stirring velocities above 100 rpm, the apparent reaction rate is independent of the stirring velocity. That means that the kinetic regime is obtained for stirring Reynolds numbers higher than 4700. The plot of Lnkwapp against T-1, at a constant and high enough stirring velocity to prevent external diffusion limitations, shows two linear areas :- under 60°C, the kinetic regime is obtained, thus allowing the determination of the reaction activation energy (given in Table 3); - above 60°C, the internal diffusion is limiting. In the kinetic controlled area, the reaction was found to be first-order and the rate constant expressed by mass of particles is kwapp=0.03721 lgrés-1 min-1 at 21 °C.Using the kinetic data, it is possible to design and to compare the characteristics of a fixed bed reactor and a moving bed reactor, which would have the same conversion rate (95 %), for the same effluent flow rate to treat (5 m3/h). As a first approximation, we consider operating conditions inducing a kinetic regime. We also consider that the reaction mostly takes place at the particle surface. This assumption allows one to obtain the reaction rate expressed by particle's area for any particle size. At 21 °C, the previously defined reaction rate is ks=4.43x10-5 m3/s.m2. The expression of the conversion rate as a function of ks, the reaction volume and the particle diameter is obtained for each reactor from the mass balance written in terms of Cu(II). The pressure drop expression is also given for the reactors. In the case of the moving bed reactor the increase of dynamic viscosity induced by the presence of particles has been taken into account. For each reactor, a solid retention, particle diameter and fluid velocity corresponding to values widely used industrially have been chosen (see Table 4). For the membrane reactor, we consider hollow fibres with 0.93 mm inner diameter, 1.2 m length and a total filtration area of 50 m2 per module. Calculations have been done for two limit values of the permeation flux: 50 and 100 l/h.m2.A comparison of the two reactors is given in Table 5, which demonstrates the interest of the moving-bed reactor, as it allows one to reduce the volume of adsorbent particles by a factor 4. This result is linked to the high specific surface of the fine dispersed particles. The membrane reactor also induces a high reduction of the pressure drop (by a factor 40) and of the energy consumption (from 4.7 for a one- module plant to 2.6 for a two-module plant). These promising results are encouraging to continue the research on this process with the aim to optimize it. Further studies will include:- comparison of different adsorbent particles and choice of the best available; - validation of this preliminary simulation by experiments on a pilot plant, with synthetic and then industrial waters; - integration of this unit operation in a complete treatment plant

Enhanced equivalent model algorithm for solar mirrors

The SolarPACES Reflectance Guideline provides an essential tool to obtain comparable reflectance measurements, but because of the lack of adequate commercial instrumentation, till now the exhaustive characterization of reflectance behaviour versus incidence ¿i and (half) acceptance angle ¿ is unachieved. An expert group in Task III has been working to outline some practicable solutions. The Equivalent Model Algorithm (EMA) was found quite promising: with few input data, EMA allows to predict any reflectance feature by computation. The recent availability of reliable reflectance measurements at oblique incidence made possible the refinement of EMA by analysing a representative set of commercial solar mirrors. This paper describes the new EMA for solar mirror, named EMA4SM, and reports its validation

Stratigraphy, Structural Geology and Thermochronology of the Northern Berkshire Massif and Southern Green Mountains

Guidebook for field trips in southwestern New Hampshire, southeastern Vermont, and north-central Massachusetts: New England Intercollegiate Geological Conference, 80th annual meeting, October 14, 15 and 16, 1988, Keene, New Hampshire: Trip A-

Stratigraphy, Structural, Geology and Thermochronology of the Northern Berkshire Massif and Southern Green Mountains

Guidebook for field trips in southwestern New Hampshire, southeastern Vermont, and north-central Massachusetts: New England Intercollegiate Geological Conference, 80th annual meeting, October 14, 15 and 16, 1988, Keene, New Hampshire: Trip B-

Microscopic Model for High-spin vs. Low-spin ground state in [Ni2M(CN)8][Ni_2{M(CN)_8]} (M=MoV,WV,NbIVM=Mo^V, W^V, Nb^{IV}) magnetic clusters

Conventional superexchange rules predict ferromagnetic exchange interaction between Ni(II) and M (M=Mo(V), W(V), Nb(IV)). Recent experiments show that in some systems this superexchange is antiferromagnetic. To understand this feature, in this paper we develop a microscopic model for Ni(II)-M systems and solve it exactly using a valence bond approach. We identify the direct exchange coupling, the splitting of the magnetic orbitals and the inter-orbital electron repulsions, on the M site as the parameters which control the ground state spin of various clusters of the Ni(II)-M system. We present quantum phase diagrams which delineate the high-spin and low-spin ground states in the parameter space. We fit the spin gap to a spin Hamiltonian and extract the effective exchange constant within the experimentally observed range, for reasonable parameter values. We also find a region in the parameter space where an intermediate spin state is the ground state. These results indicate that the spin spectrum of the microscopic model cannot be reproduced by a simple Heisenberg exchange Hamiltonian.Comment: 8 pages including 7 figure

Response to ranibizumab therapy in neovascular AMD - an evaluation of good and bad responders

Background: Treatment of neovascular age-related macular degeneration (AMD) with Lucentis® shows a broad spectrum regarding the course of visual acuity (VA). While some patients show a good response (increase in VA), others disclose much less promising results. Patients and Methods: A retrospective data analysis of all eyes treated for neovascular AMD at the University Hospital of Zurich, Switzerland for at least 12 months was carried out. The courses of VA between the 90th (good responders, GR) and the 10th (bad responders, BR) percentiles were compared at 3, 12 and 24 months from baseline. An analysis regarding demographic data, lesion type and size as well as injection frequency and visits was done and predictive factors for GR and BR were evaluated. Results: Marked differences in the course of VA between GR (n = 30) and BR (n = 30) are already observed 3 months from baseline. In GR the gains in VA after 3, 12 and 24 were 15.7 ± 9 letters ETDRS, 25.3 ± 7 and 14.0 ± 14. BR showed a deterioration of 8.3 ± 11 letters ETDRS after 3, 22.1 ± 8 after 12 and 23.6 ± 13 after 24 months. The gender distribution was equal with a higher percentage of female patients (64 % in BR and 66 % in GR). The baseline VA was statistically significantly lower in GR (45.7 ± 10 vs. 55.4 ± 11, p < 0.05) than in BR. No other significant differences in baseline data were found, and no predictor for group membership could be identified. Conclusions: Only the course of VA in the first three months seems to be of value for an estimation of the response to treatment. In the future the response to treatment in the early phase may influence the treatment algorithm and the injection frequency

MVA-based H5N1 vaccine affords cross-clade protection in mice against influenza A/H5N1 viruses at low doses and after single immunization.

Human infections with highly pathogenic avian influenza viruses of the H5N1 subtype, frequently reported since 2003, result in high morbidity and mortality. It is feared that these viruses become pandemic, therefore the development of safe and effective vaccines is desirable. MVA-based H5N1 vaccines already proved to be effective when two immunizations with high doses were used. Dose-sparing strategies would increase the number of people that can be vaccinated when the amount of vaccine preparations that can be produced is limited. Furthermore, protective immunity is induced ideally after a single immunization. Therefore the minimal requirements for induction of protective immunity with a MVA-based H5N1 vaccine were assessed in mice. To this end, mice were vaccinated once or twice with descending doses of a recombinant MVA expressing the HA gene of influenza virus A/Vietnam/1194/04. The protective efficacy was determined after challenge infection with the homologous clade 1 virus and a heterologous virus derived from clade 2.1, A/Indonesia/5/05 by assessing weight loss, virus replication and histopathological changes. It was concluded that MVA-based vaccines allowed significant dose-sparing and afford cross-clade protection, also after a single immunization, which are favorable properties for an H5N1 vaccine candidate