Design of a reactor operating in supercritical water conditions using CFD simulations. Examples of synthesized nanomaterials

International audience; Direct information about fluids under supercritical water conditions is unfeasible due to the engineering restrictions at high pressure and high temperature. Numerical investigations based on computational fluid dynamics (CFD) calculations are widely used in order to get extensive information on the fluid behavior, particularly to help the design of a new reactor. This paper presents the numerical investigations performed on an original supercritical water device, especially in the level of the reactor. CFD calculations allow to design and optimize the present reactor described in this study. Currently, this process produces some nanometric oxide powders in continuou…

Corrigendum to “Development of a combined solver to model transport and chemical reactions in catalytic wall-flow filters” [Chem. Eng. Res. Des. 117 (2016) 681–687]

Spark Plasma Sintering tool design for preparing alumina-based Functionally Graded Materials

Abstract A way to produce Functionally Graded Materials (FGM) is by means of Spark Plasma Sintering (SPS) and specifically designated tools. These new tools permit a current density modulation and therefore a temperature variation along the z-axis. The key feature relies on a varying die section. FEM modelling has given the suitable range of die dimensions between the top and the bottom to obtain a given temperature gradient (around 300 °C) out of roughly a 15 mm height. Experiments conducted in different configurations (with or without samples) and the measurement of the associated thermal gradient led to improvements of the mould (in particular the introduction of a counter-piston). By th…

Development of a combined solver to model transport and chemical reactions in catalytic wall-flow filters

Abstract In this work, we develop a non-isothermal model for diesel particulate filters including exothermic and competing chemical reactions. We begin with an isothermal, single-reaction model and we gradually increase its complexity. By comparing various models, we aim at establishing the minimum degree of complexity required to effectively model the system under investigation. Based on the numerical simulations, we conclude that isothermal models are adequate only if the temperature of the catalyst is, at all times, completely below or completely above a critical temperature. However, if the goal is to predict the critical temperature, only non-isothermal models should be used. The resul…

Influence of the pH on the ZnO nanoparticle growth in supercritical water: Experimental and simulation approaches

Abstract In order to improve the knowledge on the nucleation and the growth mechanisms of metal oxides nanoparticles produced in supercritical water domain, ZnO was used as a “model” material. A continuous process of hydrothermal synthesis was employed to synthesize ZnO nanopowders ( T  = 410 °C and P  = 305 bar) from Zn(NO 3 ) 2 and KOH solutions with different values of [KOH]/[Zn(II)] ratio from 0 to 8 in order to investigate the pH effect on the growth of ZnO nanocrystallite in terms of size and morphology. The samples were characterized by X-Ray Diffraction and Transmission Electronic Microscopy. ZnO crystal was considered as a cylindrical crystallite with a diameter D and height H . Es…

Thermodynamics of Nanoparticles: Experimental Protocol Based on a Comprehensive Ginzburg-Landau Interpretation

MATERIAUX+SMR:SDA; The effects of surface and interface on the thermodynamics of small particles require a deeper understanding. This step is crucial for the development of models that can be used for decision-making support to design nanomaterials with original properties. On the basis of experimental results for phase transitions in compressed ZnO nanoparticles, we show the limitations of classical thermodynamics approaches (Gibbs and Landau). We develop a new model based on the Ginzburg-Landau theory that requires the consideration of several terms, such as the interaction between nanoparticles, pressure gradients, defect density, and so on. This phenomenological approach sheds light on …

CFD simulation of ZnO nanoparticle precipitation in a supercritical water synthesis reactor

International audience; Continuous hydrothermal flow synthesis process has shown great advantages concerning the control of particle size and morphology through the optimization of supercritical water processing parameters. In particular, micromixing is a key issue of the process for controlling the nucleation mechanism. A Computational Fluid Dynamics (CFD) model is suggested for nanoparticle size determination using a population balance approach. Models for reaction kinetics, thermodynamics, nucleation and growth are presented. The effects of base concentration and hydrodynamics are investigated. Results show that the CFD may be valuable simulation tool for controlling the size and the sha…

Wall collision and drug-carrier detachment in dry powder inhalers: Using DEM to devise a sub-scale model for CFD calculations

Abstract In this work, the Discrete Element Method (DEM) is used to simulate the dispersion process of Active Pharmaceutical Ingredients (API) after a wall collision in dry powders inhaler used for lung delivery. Any fluid dynamic effects are neglected in this analysis at the moment. A three-dimensional model is implemented with one carrier particle (diameter 100 μm) and 882 drug particles (diameter 5 μm). The effect of the impact velocity (varied between 1 and 20 m s−1), angle of impact (between 5° and 90°) and the carrier rotation (±100,000 rad s−1) are investigated for both elastic and sticky walls. The dispersion process shows a preferential area of drug detachment located in the southe…

Fast and continuous synthesis of nanostructured iron spinel in supercritical water: influence of cations and citrates

International audience; Spinel iron oxide nanoparticles were obtained under supercritical water conditions in a continuous and fast (less than 10s) way by modifying the initial stoichiometric Fe II /Fe III molar ratio from (1/2) to (3/0), without base solution, and using citrates directly with iron precursors. This result opens the way of an economical and environmentally benign approach to synthesize superparamagnetic iron oxide nanoparticles (SPIONs) in important yields.

Quasi-free nanoparticle vibrations in a highly-compressed ZrO2 nanopowder

Several-nanometer-size mechanical oscillators, or nanoresonators, may complement electronic and optical technologies in future terahertz devices, but they can be useful only if they can be made to ...

Original Supercritical Water Device for Continuous Production of Nanopowders

Well-crystallized ZnO, ZrO2, TiO2, CeO2, Y2O3 and La2O3 nanoparticles are synthesized under supercritical water conditions (T > 647 K and P > 22.1 MPa) using a home-made continuous process. At room temperature, metallic salts with or without aqueous hydroxide solution (KOH or NaOH) are pressurized to 25–30 MPa. Then, the reactant(s) is/are rapidly heated to 673–773 K by mixing with the supercritical water in a patented reactor. Residence time is in the range from 2 to 8 s. XRD, TEM and surface area analyses highlight the production of pure and well-crystallized nanoparticles with a uniform size distribution.

Acoustic vibrations of monoclinic zirconia nanocrystals

International audience; Polarized low-frequency Raman spectra originating from confined acoustic vibrations are reported for monoclinic ZrO2 nanoparticles with a narrow size distribution synthesized from a continuous supercritical water process. The monoclinic lattice structure is taken into account for the interpretation of the spectra by comparing with isotropic and anisotropic continuum elasticity calculations for monodomain nanocrystals. The various mechanisms leading to the broadening of the Raman peaks are discussed. We demonstrate that an accurate determination of the size distribution of the nanoparticles is possible using the Raman peak due to the fundamental breathing vibration wh…

Coupling between oxidation kinetics and anisothermal oil flow during deep-fat frying

Deep-fat frying is a cooking technique that has been used continuously since prehistoric times. A domestic deep-fryer heated from the bottom develops significant convection inside the bath cavity. It is responsible for very high heat transfer coefficients and the exposure of the deep-frying oil to the atmospheric oxygen. The continuous conversion of gaseous dioxygen into unstable and reactive hydroperoxides and their subsequent advection throughout the bulk volume is at the origin of the main complaints made of frying which includes issues such as odors, fouling, and generation of several toxic compounds. This study analyzes the coupling between natural convection of triacylglycerols and th…