Impregnation of metals on
supports
This is the most important method for preparation of industrial catalysts, and
there are different methodologies, however, the most important is the
impregnation over frame-shaped solids, like pellet or extruded.
The solution with specified metal concentration, varying time, temperature, and
pH transfers the active phase to the support, and after drying and calcination, it is
fixed and stable. The support is in general an inert material or can be partially
active; however, the main properties must be well defined. In this case, the
volume of solution must be sufficient to fill all pores, known as dry impregnation.
When the support is in powder form, the volume of solution needed is higher than
the pore volume of the support, and the impregnation is known as wet
impregnation.
The impregnation method involves three steps: (1) contacting the support with the
impregnating solution for a certain period of time, (2) drying the support to remove the
imbibed liquid and (3) activating the catalyst by calcination, reduction or other
appropriate treatment.
Two methods of contacting may be distinguished, depending on the total amount of
solution.
(1) With excess of solution. The support is placed on a screen (vessel) and dipped into
an excess quantity of solution for the time necessary for total impregnation. The solid
is then drained and dried. This operation can be done continuously as shown in Fig. 1a.
In such an operation, the composition of the batch solution will change and the release
of debris can form a mud, which makes it difficult to completely utilize the solution.
a
Fig. 1. Support impregnation processes: (a) with excess of solution
(2) With repeated application of solution. A more precise control is achieved by
this technique, termed dry impregnation or incipient wetness impregnation. The
support is contacted with a solution of appropriate concentration, corresponding
in quantity to the total known pore volume or slightly less.
This operation can be performed continuously as shown in Fig. 1b. The catalyst is
kept in motion in a rotating cylinder or drum, and is sprinkled as required with a
solution of salt by sprayers. The disadvantage is the poorer distribution of the
precursors.
For both techniques the main operating variable is the temperature which affects
both the precursor solubility and the solution viscosity and, as a consequence, the
wetting time. A proper control of the operating conditions during impregnation
and drying determines the impregnation profile of the final catalyst.
b
Fig. 1. Support impregnation processes:
(b) impregnation to incipient wetness.
Incipient Wetness Impregnation - YouTube
Decantation, filtration, centrifugation and washing
Decantation, filtration and centrifugation are well known unit operations, the aim of which
is the separation of the solid phase from the mother liquor.
Washing of the solids is then required to remove the mother liquor completely and to
eliminate impurities. The separation of the mother liquor is quite easy for crystalline
precipitates, difficult for flocculates and of no use for hydrogels.
The selection of the separation method will also depend on the particle size of the solids. A
satisfactory but time-consuming method is decantation. Washing is carried out
simultaneously with it. The slurry is added to a large volume of distilled water and the
suspension is thoroughly mixed. Upon standing, particles settle down.
When a definite interface is visible, water is removed by decantation and the
process repeated until the desired purity is reached.
When washing flocculates, problems may arise, as the purified flocculate takes
longer to settle with each washing, since removal of counter-ions reverts the
flocculate to sol. This is the well known phenomenon called peptization. Care
must be taken not to wash too much or allow settling times to become too long.
When washing is completed the solid is filtered.
If the particles are too small and the settling time too high, filtration or
centrifugation must be used. Again, care must be taken not to wash too much with
water, otherwise the flocculates peptize and pass through the filter.
Drying
Drying is described as the elimination of the solvent (usually water) from the
pores of a solid. This is a routine procedure for crystalline solids but becomes
critical for flocculates and even more for hydrogels that can contain up to 90% of
water. Therefore, we will discuss only the drying of such gels.
The removal of water can result in a certain collapse of the structure. Care must
be taken to properly control the drying operations if high porosity is desired.
Initially drying occurs through evaporation of moisture from the outside surface
of hydrogel.
The water loss rate is constant and the mass transfer is controlled by temperature,
relative humidity, flow rate of air over the surface and size of the gel particles.
This process continues until the moisture content is reduced to about 50%. Then
the gel mass begins to shrink. The material so obtained is called xerogel.
The subsequent moisture loss occurs with a declining rate, in which evaporation
is controlled by capillary forces. The saturation point decreases as pores become
smaller and evaporation slows until water is forced into larger pores by
concentration gradients.
If evaporation occurs but removal of moisture is blocked by smaller pores, an
internal pressure of steam develops and the structure collapses, with loss of pore
volume and surface area. The pore volume loss on drying of a silica hydrogel is
reported in Fig. 2.
Fig. 2. Pore volume reduction on drying a silica hydrogel.
High temperature gradients should be avoided in order to reduce such
effects. The effect of temperature is shown in Fig. 3. Gel breakage is
reduced by lowering the drying temperature, increasing the relative
humidity of the drying medium or reducing air flow through the gel
bed. Vacuum drying at lower temperatures is an advisable laboratory
procedure.
Dried xerogels contain 25-30% of water, encapsulated in fine pores or
chemically bound to the oxide. In this moist state it is sometimes easier
to form the material into pellets or extrudates.
Fig. 3. Effect of drying temperature on the surface area of a silica hydrogel.
This is sometimes done for convenience, provided subsequent calcination does
not weaken or damage the particles.
Large capillary stresses can be avoided by operating at temperatures higher than
the critical temperature of water or by vaporizing the water under vacuum at
temperatures ranging from -50 to - 5°C.
The solid structure undergoes only a small modification by retaining the textural
properties of the wet gel and leading to a highly porous dry solid called aerogel.
Calcination
Calcination is a further heat-treatment beyond drying.
As with drying, this unit operation can be located before or after the forming operation,
depending on the case.
We will refer in the following to calcination in air, typically at temperatures higher than
those used in the catalytic reaction and catalyst regeneration.
Other thermal treatments, such as reductions or sulfidations, are performed in special
atmospheres, so they will be designated as activation operations. The latter are usually
performed in the industrial reactor at the start-up of the unit. Therefore, they are not
considered to be preparation procedures.
Several processes occur during calcination: loss of the chemically bonded water or CO2,
modification of the texture through sintering (small crystals or particles which turn into
bigger ones), modification of the structure, active phase generation and stabilization of
mechanical properties.
Alumina is a good example with which to demonstrate all these features. Fig. 4 outlines
the principal decomposition sequences that occur upon heating the aluminum hydroxide.
Upon calcination of bohemite above 300 °C, a series of phase changes occur,
simultaneously with loss of hydroxyl groups and hence of water. These result in
the formation of a series of oxides (ƞ -, γ- and δ-phases), known as pseudo y-
alumina, good for binder and catalysts support, and therefore useful ingredients in
catalyst preparation.
Above 1000 °C monoclinic θ-Al2O3 forms, transforming into hexagonal ϭ- Al2O3
at 1200 °C. These are anhydrous, low surface area oxides and are not suitable for
porous supports.
They are used in applications where mechanical strength is required. Changing
the calcination temperature, even when phase transitions are avoided, can affect
the pore size distribution.
Fig. 4. Alumina modification upon calcination.
In Fig. 5 is reported the effect of the calcination temperature on a γ -alumina: increasing
the temperature results in a collapse of micropores and in the increase of the mean pore
size.
Fig. 5. Effect of calcination temperature on
the pore size of γ - Al2O3.
Forming operations
Forming operations are applied to obtain suitably sized particles of catalyst to be
used in the reactor.
Therefore, forming and shaping of supports and catalysts is an important step in
the preparation procedure of a catalyst. A catalyst particle shape and dimension
should promote catalytic activity, strengthen the particle resistance to crushing
and abrasion, minimize bed pressure drop, lessen fabrication cost and distribute
dust build-up uniformly.
Unfortunately, these objectives are not easily achieved. Indeed, several are
mutually exclusive. For instance, a smaller particle size increases activity but also
increases bed pressure drop.
The best operational catalyst, therefore, has the shape and size that, in the end,
represent the optimum economic trade-off. The selection of the shape and size is
driven by the type of reactor.
Table 1 gives a rough survey of the different shapes and the reactors in which
they are used. For a given reactor the shape and the size of the catalytic particles
will depend on the hydrodynamic and on heat and mass transfer limitations.
Here we will describe the different techniques for shaping the catalysts into the
shape mentioned in Table 1.
Two extreme types of shaping can be distinguished, depending on whether the
desired products are powder micro-granules or grains of the size order of one to
several millimeters.
Table 1 Different types of catalyst shapes
Extrusion and wet pressing
Extrusion is the most commonly applied shaping technique for catalysts and catalyst
supports. A wet paste is forced through a die. As the ribbon of the extrudate paste emerges
from the die it is cut to the desired length by a proper device.
Usually catalyst mixes of powdered oxides made by precipitation do not by themselves have
the necessary mouldability and plasticity even when the optimum water content is added.
They behave rather like sand. Besides, quite a number of such materials need a binder to
produce extrudates with good mechanical behavior.
So in the formulation of the paste different additives can be used: compounds for
improving the rheological behavior of the paste (clays or starch); binders
(aluminas, clays); peptizing agents to deagglomerate the particles (acetic acid,
nitric acid); combustible materials to increase the macroporosity (the so called
pore formers like carbon black, starch).
Extruding equipment can be classed in one of two categories: press extruders (for
wet pressing) and screw extruders. The operating variables include: mixing time,
additives content, water content, paste aging, extrusion temperature.
The quality of the extrudates will also depend on the drying and calcining
procedure.
Special shapes such as rings, and hollow cylinders can be obtained by using
proper dies.
Monolith or honeycomb supports are also manufactured by extrusion of a thick
inorganic dough through a special die. Such unusual support form is used in
automobile catalytic converters, where a very low pressure drop is required to
minimize power loss from the engine.
