Impregnation and Drying

Supported catalysts: catalytically active phase dispersed over a support

Requirements for supported catalysts preparation :
1. The precursor of the active phase should be distributed uniformly.
2. the number of operations needed for the precursor introduction should be limited.
3. Complete deposition of precursors should be ensured.

Impregnation and drying method :

Precursor is dissolved in a liquid. The solution is then introduced into the voids of
the support, after which the solvent is eliminated.

Important parameters in impregnation

1. During impregnation, the dissolved precursor migrates in the pores of the support, on which
it may adsorb.
2. The support can be used as a powder but most often in industry it appears in the form of
extrudates or pellets of specific size and shape, implying a transport of matter in the solid at a
macroscopic scale and a distribution that might not be homogeneous.
3. The impregnation solution contains several chemical species: the metal precursor of the
active phase, its counterions, coimpregnants; precursors are also selected according to their
physicochemical properties and cost.
4. Choice of parameters such as concentration and temperature is critical. Depending on these,
different physicochemical phenomena may lead to different types of deposited phases and
ultimately to more or less active catalysts.
Drying and calcination
Drying is thermally activated step during which the solvent is able to
influence the transport of its chemical partners or to react with them.

Calcination concerns a system in which the solid/solvent interface has

been replaced by a solid/gas interface, on which new transformations
take place (decomposition of ligands, ion diffusion, etc.).

Methods of Impregnation
according to the volume of solution added, impregnations can be
classified in two categories
1. Dry or incipient wetness impregnation: proper wetting ,no excess
of solution remains outside pore space of support. Solution
containing the precursor of the active phase is drawn into the pores
of supports.
2. Wet impregnation : Impregnation is carried out in diffusional
conditions, that is, by immersing a water-filled support in the
precursor solution.
 Physical Models for Impregnation
Figure 4.1 Phenomena of transport in
(a) wet impregnation and (b) dry impregnation.
The solute migrates into the pore from the left
to the right of the figures
In wet impregnation, the distribution of the solute inside
the wet porosity of the pellet is assumed to be governed by
two phenomena :
the diffusion of the solute into the pores of the pellet,
described by Ficks law.
the adsorption of the solute onto the support, which
depends on the adsorption capacity of the surface and on
the adsorption equilibrium constant.
The distribution of the precursor along the pellet depends
on the balance between diffusion and adsorption. Wet
impregnation takes several hours.
In dry impregnation equation based on Poiseuille steady
states or on the related Darcys law is added to represent
the pressure-driven capillary flow of the solution inside the
empty pores.
For low concentrations, strong adsorption of the solute or short
times, egg-shell distributions are expected . If the adsorption
of the solute is weak and time is long enough, distribution
should tend to uniformity.
For powders, equilibrium is reached within a few minutes, but it can
take a few hours to reach a uniform distribution of the
precursor inside a pellet. A blockage of the pores by bulky
species has been invoked in some cases.
 Drying
Heating the impregnated system in an oven up
to the boiling point of the solvent or at a lower
temperature for gentle drying in static conditions
or under a flow of gas with the aim of solvent
elimination

Phenomena of transport involved in:

a. Constant-rate period (Slow drying): The
distribution of the precursor phase in the pellet
at the outer surface, results from the balance
between adsorption, convection.
b. Falling-rate period (fast drying): the solvent
front recedes inside the pores and evaporation
occurs inside the pellet. fast drying is usually
associated with high heating rate and drying
temperature.

Figure 4.3 Phenomena of transport involved

in (a) the constant-rate period of drying
(b) the falling-rate period of drying.
The solvent migrates from the left
to the right of the figures.
The various conditions of impregnation and drying leading to different types of precursor
distributions: egg-shell, uniform, or egg-yolk.
 The impregnated system is heavily determined by concentrations, pH, viscosity, choice of
counterions and competitors, use of water as a solvent.
Improving the quality of impregnation requires investigation of the chemistry of the system
such as: adjusting the pH, introducing ligands or organic additives, using time as a variable
influencing Chemistry
Parameters can be varied in the drying step (temperature,heating rate, gas flow and
pressure, time). In order to optimize drying for a given system, dual studies should be
undertaken on powders and on extrudates,
END