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Ghapter 5
Gatalysts Materials & Preparations
arning outcome
At the end of the chapter, you should be able to:
w Understand catalyst preparation methods of
unsupported, supported and metal catalysts.
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l:'
4.
Platinum Black
2
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supported (Bul
Metal Oxides
@ Simple Binary Oxides
(Aluminas, Silicas, [Iagnesium oxide, Transition
metal oxides (Titania TiO2, Zirconia, iron oxide,
chromium oxide)
6i Complex Multicomponent Oxides
(Aluminum silicates, Amorphous
silica-alumina Zeolites, Aluminum
phosphates, Clqys, Mixed metal
oxides, Va nadi u m-Fhqpphates)
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Examples:
Platinum.-1[oc|ium grids used
for ammonia o
nitric acid process, & silver grid
for the dehydrogenation of
methaneto formaldehyde.
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& To achieve the high surface areas & stabilize the highly
disperse active phase, supports are typically porous
materials having high thermostability.
Supports
Many of the bulk materials may also function as supports.
Supports
{t Monolithic supports with unidirectional macrochannels are
used in automotive emission control catalysts where the
pressure drop has to be minimized.
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Supports
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Surface-Modified Oxides
The surface properties, that is acidity & basicity, of oxides
can be significantly altered by deposition of modifiers. The
acid strength of aluminas is strongly enhanced by
incorporation of Cl- into or on the surface.
calm
Supported $ulfide Catalyst
Coated catalysts are catalytically active layers applied on inert
structured surfaces. These active layers consist of bulk or
supported catalysts.
Examples:
Egg-shell catalysts deposited on an inert carrier
Monolithic honeycombs for environmental applications
or for multiphase reactions
Structured packings
L Foams & sponges
Fibers & cloths
L Catalytic-wal I reactors
catalytic filters for flue gas treatment & diesel exhaust after-treatment
*,, Membrane - electrode assemblies for fuel cells
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reparation of Heterogeneous Gatalysts
Catalysts applied in several industrial processes can be
subdivided into the following categories:
nsupported Gatalysts
Mechanical treatment
For example, mixing, milling, or kneading of catalytic active
materials or their precursors with promoters structure
stabilizers, or pore-forming agents, one of the simplest
preparation methods.
nsupported Gatalysts
Mechanical treatment
'Ihble 8. Urtsup;xrrted cltuly'sts prtlpflrcil bl mtrchuniqal trertrr)cnr
tiv{l't or by lusiorr (F)
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hsupported Gatalysts
Precipitation & co-precipitation
& Precipitation & co-precipitation are the most frequently
applied methods for the preparation of unsupported
catalysts or catalyst supports.
6supported GatatYsts
Precipitation & co-precipitation
6, co-precipitation of two or more metal cations is a suitable
operation for the homogeneous dispersion of the
corresponding oxides, especially if the catalyst precursors
have a defined crystalline structure, for example,
Ni6Al2(OH)roCOs. After thermal treatment, binary oxides
such as NiO-Al2O. is formed.
nsupported Gatalysts
Precipitation & co-precipitation
Example: Preparation of Au/ceo, catalysts for selective
catalytic oxidation of CO in the presence of H,
Co-precipitation method :
@ An aqueous solution of NarCO. (1 M) is added into an
aqueous mixture of gold(lll) chloride trihydrate HAuClo:xHrO
& cerium(lll) nitrate hexahydrate Ce(NO.).:6HrO & is kepfat
_ room temperature & constant pH of 8.0.
@ fne precipitate is aged for an hour &
.3,; Tnen is washed several times with distilled water untit there
are no excess anions.
O rrre catalysts are dried overnight at 3g3 K & calcin ed atr73
Kfor5h.
Miil
Weighing
machines Catalyst pellets
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/
_ _=_ /
6-supported Gatalysts
Precipitation & co-precipitation
The industrial production of precipitated catalysts usually
involves the following stePs:
g( Preparation of metal salt solution & of precipitating
agent (dissolution, filtration)
6 Precipitation
91 Ageing of the PreciPitate
g,' Washing of the precipitate by decantation
M Filtration
M Washing of the filter cake (spray drying)
s( Drying
n6' Calcining
M Shaping
M Activation
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Catalysts
Hydrogenation Ni1Ai
hsupported Gatalysts
The sol - gel process
6i The sol - gel process involves the formation of a sol,
followed by the creation of a gel.
-nsupported Gatalysts
The sol - gel process
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hsupported Gatalysts
The sol - gel process
Example: Preparation of Au/CeOrcatalysts for selective
catalytic oxidation of CO in the presence of H,
upported Gatalysts
& The main feature of supported catalysts is that the active
material forms only a minor part & is deposited on the surface
of the support.
& ln some cases, the support is more or less inert, e.9., a-
alumina, porous glass, ceramics.
& ln other cases the support takes part in the catalytic reaction,
as in the case of bifunctional catalytic systems, e.9., alumina,
aluminosilicate, zeolites, etc.
{talyst Gomponents
& Active phase
e, Where the reaction occurs (mostly metal/metal
oxide)
& Promoter
.. Textual Promoter
for NH. Production)
'. Electric or structural
(e g. Al - Fe
modifier
/t"'\
(*. -*,,,,,"{
- Poison resistant Promoters
..1,) Support / carrier
L lncrease mechanical strength
- lncrease surface area (98% sudace area is supplled
within the Porous structure)
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Example:
1-2 wt % alumina is added to the iron ammonia synthesis
catalyst to facilitate preparation of a high surface area iron
phase & thereafter maintain its high surface area during
reaction.
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lmpregnation
lmpregnated catalysts are prepared by impregnating a metal
salt on a porous support. The metal loading in the finished
catalysts typicallyl -5%.
pellets
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Schematic of steps in the preparation of supported catalysts
by impregnation to incipient wetness
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inlcraelion ir illt lhe sttppot ls
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repar n
:.:'a'-: : r'
Suplort to b:
imp egna:ed
lnl)ltgritli! bi5 n
:"
rted Gat
xample: Preparation of NiMo/Al;O3 catalyst
Metals: Ni & Mo
Support: Alumina (125-250 pm, S.A. 263 mzlg)
Procedure:
(1) The support is dried overnight at 3g5 K before impregnation.
(2) The catalyst is prepared by co-impregnation using
ammonium heptamolybdate and nickel nitrate solution in
ammonia.
(3) After impregnation, the catalyst is dried in air for 16 h
at 3g5
K and calcined in static air for 2h atz2s Kafter heating to
this temperature in t h.
Disadvantages include:
@sometime material is nonuniformly deposited along pores
& through the pellet
I The tendency for deposited base metal precursors to be
oxidized in the aqueous solution to oxides that interact
strongly with alumina or silica supports and which are
difficult to reduce.
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Adsorption
r-. Adsorption of PdCl2 from aqueous solution on different aluminas is
very fast, & a high equilibrium concentration (2 wt %) can be
obtained. The Pd deposition takes place mainly in an outer shell
(egg shell profile) of shaped particles. With H2(PtClr) only I wt %
Pt loading on alumina is possible owing to from the flat adsorption
isotherm.
& ln general, with increasing acid strength the metal ions are forced
deeper into the support particles.
Support
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Concentration l.^.*l
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--===-=--
reparation of Supported Gatalysts
lon Exchange
L lt is very similar to ionic adsorption but involves exchange of
ions other than protons. Lower valence ions, such as
Na* or NHo* can be exchanged with higher valence ions, for
example, Ni2* or Pta*.
-ffiS
High load supported catalYst
sinter at T = 100 oC
Supported catalyst
F S--s---m ^
s o .rroon-"Ew -X-
(PUA|2O3)does not
usually sinter under
450-500"c.
Low load supported catalyst
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SuPPort -@-
r_l @\ \ ru","t
Support
Support
Effect of catalyst particle size & the strength of the metal support
interaction on the metal: support contact area
ac ir--
LJ-l\ =
ng & Galcination:DF
Drying is described as the elimination of water or solvent from
the pores of the precipitate or gel. lt can be done in two ways:
Solvent evaporation
This type of drying is done in a conventional oven at 100-200
oC & is generally accompanied by a contraction of the
structure.
Super criticaldrying
It is aimed at eliminating the liquid vapor interface and the
accompanying capillary pressure responsible for structure
collapse during conventional drying particularly for gels.
inationl..]calcinat
Often the heating is done in the presence of flowing air or oxygen to
burn any residual organics or to oxidize the sample. Multiple
changes occur during this process including:
,$ Active phase generation The hydroxide form is converted to oxide form.
:ri Loss of chemically bound water: The chemically bound water is removed at
higher temperature.
$Changes in pore size distribution & surface area due to sintering: Exposing
the sample to high temperature over an extended period of time leads to
sintering & consequently decreases the surface area.