Dry impregnation in fluidized bed: Drying and calcination effect on nanoparticles dispersion and location in a porous support

The synthesis of metal nanoparticles dispersed inside the grains of a porous inorganic support was carried out by ‘‘dry impregnation’’ in a fluidized bed. The principle of this technique consists in the spraying of a solution containing a metal source into a hot fluidized bed of porous particles. The metal source can be of different nature such as metal salts, organometallic precursors or colloidal solutions. The experimental results obtained from iron oxide deposition on a porous silica gel as support, constitute the core of this article but others results concerning the deposition of rhodium from a colloidal suspension containing preformed rhodium nanoparticles are also described. More precisely, this study aims to understand the effect of the bed temperature during the impregnation step, the initial particle porosity and the calcination operating protocol on the metallic nanoparticles dispersion and location in the silica porous particles. The so-obtained products were characterized by various techniques in order to determine their morphology, their surface properties and the dispersion of the nanoparticles inside the support. The results showed that, under the chosen operating conditions, the deposit efficiency is close to 100% and the competition between the drying rate, depending on the process-related variables, and the capillary penetration rate, depending on the physicochemical-related variables, controls the deposit location. A quasi uniform deposit inside the support particles is observed for soft drying. The metal nanoparticles size is controlled by the pore mean diameter of the support as well as the calcination operating protocol

Synthesis of Supported Catalysts by Dry Impregnation in Fluidized Bed

The synthesis of catalytic or not composite materials by dry impregnation in fluidized bed is described. This process can be carried out under mild conditions from solutions of organometallic precursors or colloidal solutions of preformed nanoparticles giving rise to reproducible metallic nanoparticles containing composite materials with a high reproducibility. The adequate choice of the reaction conditions makes possible to deposit uniformly the metal precursor within the porous matrix or on the support surface. When the ratio between the drying time and the capillary penetration time (tsec/tcap) is higher than 10, the impregnation under soft drying conditions leads to a homogeneous deposit inside the pores of the particles of support. The efficiency of the metal deposition is close to 100%, and the size of the formed metal nanoparticles is controlled by the pores diameter. Finally, some of the presented composite materials have been tested as catalysts: iron-based materials were used in carbon-nanotubes synthesis, while Pd and Rh composite materials have been investigated in hydrogenation reactions

Effect of operating conditions and physico–chemical properties on the wet granulation kinetics in high shear mixer

The wet granulation process is sensitive to changes in product properties and process variables. The optimal process and formulation are based on the knowledge of the granule growth mechanisms and of the effects of product properties and process variables. This paper presents the study of wet granulation of microcrystalline cellulose powder, MCC (Avicel PH101) using high-shear mixer granulator. It aims at understanding the effect of operating parameters (impeller rotational speed, liquid binder flow ate) and of physicochemical properties (viscosity, wettability) of a binder solution on solid particles surfaces, on the agglomeration kinetics. The experiments are carried out with water, aqueous solutions of sodium carboxymethylcellulose, polyvinylpyrrolidone, hydroxypropylméthylcellulose or a non ionic surfactant oxo-C10C6 at a critical micellar concentration. Concerning the process variables the experimental results show that an optimal interval of impeller speed operation exists ranging from 150 to 200 rpm for granule growth. Below, an uncontrollable agglomerate size and localised over-wetting occur, and above granule breakage occurs. Increasing the liquid binder flow rate reduces the extension of the non growth regime, but does not affect the granule mean size. The effect of the physicochemical properties is evaluated using a modified capillary viscous number, Ca′, that we define as the ratio between the viscous forces (μLU) and the work of adhesion Wa=γL(1+cosθ). For Ca′b1, the viscosity of the solution does not significantly affect the granulation process. The dominant forces in the granulation process are the interfacial forces since increasing the work of adhesion enhances the growth kinetics. For Ca′N1.6, the viscous forces predominate and control the granule growth

Biomass steam gasification in fluidized bed of inert or catalytic particles: Comparison between experimental results and thermodynamic equilibrium predictions

In order to improve the understanding of biomass gasification in a bed fluidized by steam, the thermochemical equilibrium of the reactive system was studied. The equilibrium results were compared to LGC experimental results, obtained by the gasification of oak and fir in a laboratory-scale fluidized bed of different catalysts: sand, alumina, and alumina impregnated with nickel. The research was completed by a study of the influence on the equilibrium of additional parameters such as the quantity of steam, the pressure or the kind of biomass. Those results of simulation may be used for evaluating the limits of actual reactors.The following conclusion may be drawn from all the results: The thermodynamic equilibrium state calculated is far away from the experimental results obtained on sand particles. The steam to biomass ratio, between 0.4 and 1 kgsteam/kgdry biomass, has a strong influence on the gas mixture composition. The temperature increase and the use of catalyst allow producing a gas mixture with a high content of hydrogen and carbon monoxide. The H2:CO ratio may reach values greater than 3. The use of catalyst allows the system to get closer from the equilibrium, especially for the nickel based catalyst

Wet granulation in laboratory scale high shear mixers: Effect of binder properties

The effect of binder properties on torque curves, granule growth kinetics, wet mass consistency and dry granule strength has been investigated in this study. Granulation runs have been performed on a fine cohesive microcrystalline cellulose powder (Avicel 105, d50 = 20 μm) in two types of laboratory high shear mixers: a Mi-Pro high shear mixer using a 1.9 L bowl and a 6 L Diosna high shear mixer. Binders used included ultra-pure water and solutions of varying concentrations of PVP and HPMC allowing us to cover different values for parameters like viscosity and work of adhesion. Torque curves recorded during granulation are found to allow good control of the process. Optimum liquid requirement for granulation has been found to vary with binder type and decrease with increasing viscosity while granule growth kinetics has been found to be to be related to the work of adhesion for low viscosity binders. Granule strength has been evaluated for wet granules by the means of wet mass consistency measurements on a mixer torque rheometer and for dried granules by means of uniaxial compression tests on a Texture Analyser mechanical testing machine. For low viscosity binders both wet mass consistency and dry granule strength have been found to depend on the work of adhesion. For high viscosity bindershigherwet mass consistencies but lower dry granule strengths have been observed. Granulating on the larger 6 L scale has shown that constant impeller tip speed offers good agreement in terms of mean granule size however granule size distribution seems to be scale dependan

Wet granulation in laboratory-scale high shear mixers: Effect of chopper presence, design and impeller speed

The effect of the main means of agitation in a high shear mixer has been investigated in this study. Granulation runs have been performed on a fine cohesive microcrystalline cellulose powder (Avicel 105, d50 = 20 μm) often used as a pharmaceutical excipient in tablet formulations in two bowls of a Mi-Pro® laboratory high shearmixer with a capacity of 0.9 and 1.9 L, respectively. Torque curves recorded during granulation are found to allow good control of the process while increasing impeller speed is found to generally reduce granule size and the onset of breakage seems to occur for similar values of impeller tip speed. As a general rule, the chopper allows for better binder distribution in the Mi-Pro® and is found to be necessary for successful granulation at low to moderate impeller speeds. For high impeller speeds in excess of 4.4 m/s with or without a chopper, similar granule sizes and growth mechanisms are observed. Granule roundness was found to increase with impeller speed up to a certain speed after which granule roundness has been found to decrease with increasing impeller speed most probably because of increased breakage of the granules. Dry granule strength has been found to increase with increasing impeller speed, presenting only a slight decrease at the highest impeller speed studied