23-Mar-'16

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.
 23-Mar-16

Glassification of Solid Gatalysts

&unsupported (bulk) catalysts
@ supported catalysts
6 hybrid catalysts

l:'
4.

Unsupported (Bulk) Gatalysts

c" Metal Oxides
q, Metals & MetalAlloys
{, Carbons
(, lon-Exchange Resins & lonomers
u Molecularly lmprinted Catalysts
t' Metal- Organic Frameworks
q, Metal Salts

Platinum Black

2
 23-Mar-16

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)
.\lutrtinuDr ( )\id( i,\li( ), )

lror ()\idr al:!.O,,

( rlriorl ( )\rdr (('ti())
:(!lruilr ( )\xir ( Nx-())
ll,lx:\i!Dt ( )\il. (K-()r
IlnngrN!r ( )\rlr (\,1[())
I ilrrilnl ()\iJ! r'l rO.)
Ilnirrrri,nir ( )\{1. \l!())
1

l'ho\th('rr\ {)\il. {1,.().)

nsupported (Bulk) Gatalysts

Metals & Metal Alloys
Metals & metal alloys are used as bulk, un-supported catalysts in
only a few cases.

Metal gauzes or grids are used as bulk catalysts in

strongly exothermic reactions which require
catalyst beds of small height.

Examples:
Platinum.-1[oc|ium grids used
for ammonia o
nitric acid process, & silver grid
for the dehydrogenation of
methaneto formaldehyde.
 23-Mar-16

6, supported catalysts play a significant role in many industriar

processes.

&The-support provides high surface area & stabilizes the

dispersion of the active component (e.g., metals supported
on oxides).
& Active phase - support interactions which are dictated by the
surface chemistry of the support for a given active phase, are
responsible for the dispersion & the chemical state of the
latter.
$eAlthough supports are often considered to be inert, this is not
generally the case. Supports may actively interfere with the
catalytic process.

6, Typical examples for the active interplay between support &

active phase are bifunctional catalysts such as highly
dispersed noble metals supported on the surface of an acidic
carrier.

& To achieve the high surface areas & stabilize the highly
disperse active phase, supports are typically porous
materials having high thermostability.

fu For application in industrial processes they must also be

stable towards the feed and they must have a sufficient
mechanical strength.
 23-Mar-16

Supports
Many of the bulk materials may also function as supports.

The most frequently used supports are binary oxides

including transitional aluminas, alpah-AlrO3, SiO2, MCM-41,
TiO, (anatase), ZrO (tetragonal), MgO etc., and ternary
oxides including amorphous SiOr-AlrO. & zeolites.

Additional potential catalyst supports are auminophosphates,

calcium aluminate.
Carbons in various forms (charcoal, activated carbon) can
be applied as supports unless oxygen is required in the feed
at high temperatures.

Supports
{t Monolithic supports with unidirectional macrochannels are
used in automotive emission control catalysts where the
pressure drop has to be minimized.

The channelwalls are nonporous or may contain

macropores. For the above application the monoliths must
have high mechanical strength & low thermal expansion
coefficients give sufficient thermal shock resistance.

Therefore, the preferred materials of

monolith structures are ceramics
(cordierite) or high quality corrosion-
resistant steel.
 23-Mar-1:

ii;rll
l:,ti:r '
-*a@
I
Supports
'Isbh 7. ltolfnics ol t|pi!.d dilillil luplxrl!

SupFnl ('r)'l.rll,):ft,11n. |h.r... l':,,ttrtr.'i.ril,ir..,1r,,n.

AI:O1 nhsll! q rtrd 1

SiOr .iil!rPh,){\ S \ Lrii i,' Li{x, lI.ll.rll\ .t.rirl.. h!dl,,r:.il,rllinl,ln(l (illr'r trlr.
Cartxn rr)!rpl,)rl S \ lri, :1, lLr!r Iir'l.rhla il1,,\rd c|\il,)rlrI. h\rlr\,!!'trilli(rl r,tls.
TiO-r .ilrl:ric nrl!]. S\ 1 i, j,, li') ijriirl.ij ttr.rnr.ti.rrhilitli S('R.rl\
i!t*O t.. \ \ rrir r,' .:li) r.h)lirrir,rn r)t;r) it lrobl.ntJi.: \t.rrn r.l,)rilirn! !f,1
7rrrlitcs rril.*s tliujNrtrs- ZS\l it I Ir;:ltlr ,lrtircrl l\r. \\{.rrl: .ll.tl! \rlffli\.: hilun.ti,rnrl .r15.
Silic{./$}umiil{ Nrrrphous S.\ rJl) ilr s{x): [).Jilril) \tf,'rt! .tr i(l rit'si d0htrlrr\!arrli,rr (r!\.: hitrilalrorrrl crtrl: stt.

SA surluc rr.r ir nri/!

Supported Metal Oxide Gatalysts

Supported metal oxide catalysts consist of at least one active
metal oxide component dispersed on the surface of an oxide
support.
The active oxides are often transition metal oxides, while the
support oxides typically include transitional aluminas
(preferentially g-AlrO3), SiO2, TiO, (anatase), ZtO2
(tetragonal), & carbons.
Supported vanadia catalysts are extremely versatile
oxidation catalysts. V2C.sffio2 is used for the selective
oxidation of o-xylene to phthalic anhydride & for the
ammoxidation of alkyl aromatics to aromatic nitriles.
 23-Mar-'16

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.

This may occur during impregnation with solutions

containing chloride precursors of an active component
or by deposition of AlCl..

Chlorinated aluminas are also obtained by surface reaction

with CClo. The presence of chlorine plays an important role
in catalytic reforming with Pt -Al2O3 catalysts.

Supported Sulfide Gatalyst

& Sulfided catalysts of Mo & W supported on y-Atzo3 or active
carbons are obtained by sulfidation of oxide precursors in a
stream of HrlHrS.

They are typically promoted with Co or Ni & serve for

hydrotreating processes of crude oil, including
hyd rodesu lfu rization ( H DS), hyd roden itrogenation
HDN, & hydrodemetalation HDM.
 23-Mar-i e

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

t Microstructured reactors with coated channels

:;+"<-.:'-
reparation of Heterogeneous Gatalysts
Catalysts applied in several industrial processes can be
subdivided into the following categories:

$ Unsupported (bulk) catalysts

V Supported catalysts
 zJ-tvtar- to

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.

An important advantage of these methods is that formation of

wastewater is avoided.

nsupported Gatalysts
Mechanical treatment
'Ihble 8. Urtsup;xrrted cltuly'sts prtlpflrcil bl mtrchuniqal trertrr)cnr
tiv{l't or by lusiorr (F)

K. Cr.
Fr:..0 ,t llT cthvlhcnzcne tle hr tlrogt'naliorr
('c,
\'lo1 (sl'rc,e llr'(xlu(tir)t))
I:c:0.{K) Ill' Fischcr * 'l-r'oPsch s1'nlhcsis
ZnO _. L-r-,(), \11' lrvdrogcnlrliorr ol culhonr,l
e()t1 )l]t ,u [(lt
liri(J.i{K. .\1. I: :\-}l r sYnlhesis
Cl. \1g i
V"Or .. K.-S,[). F S[). oriduliorr lH_.-SL)r

I:triluction )
irlil{ir i:r.iii I; Nllr urirjlliol ill\Or
prrrtltrLtirirt )

l.r"l c nl!' rl ts irt ltarr: nlhcse s iu c Ir olt)(rl.,t.\.

 nsupported Gatalysts
Fusion of components or precursors
Used for the production a small group of unsupported
catalysts. The fusion process permits the synthesis of alloys
consisting of elements which do not mix in solution or in the
solid state.
However, preparation of unsupported catalysts by fusion is an
energy-consuming & quite expensive process.

The most important application of this method is the

production of ammonia synthesis catalysts based on the
fusion of magnetite (FerOo) with promoters such as oxides of
K,Al, Ca, & Mg.

liiril, '

hsupported Gatalysts
Precipitation & co-precipitation
& Precipitation & co-precipitation are the most frequently
applied methods for the preparation of unsupported
catalysts or catalyst supports.

& However, both methods have the major disadvantage of

forming large volumes of salt-containing solutions in the
precipitation stage & in washing the precipitate.

& Source materials are mainly metal salts, such as sulfates,

chlorides, & nitrates. Basic precipitation agents on an
industrial scale are hydroxides, carbonates, &
hydroxocarbonates of sodium, potassium, or ammonium.
 23-Mar-'16

Precipitation & co'precipitation

L To precipitate the catalyst precursor in the form of a hydroxide

or carbonate by adjusting the pH of the metal salt solution-
support slurry through addition of a base such as NaOH or
NH4OH.
For example, preparation of alumina is done by precipitating
aluminium hydroxide from aluminium nitrate solution by
addition of ammonium hYdroxide:
,\l(\o.). rNIl,()l! + 'Nll,NO,
'.'\li()11i.

supporl & catalyst precursor can be co-precipitated together,

such as co-precipitation of Ni hydroxide on silica by pouring
together aqueous solutions of sodium silicate & nickel nitrate.

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.

6# Precipitation & co-precipitation can be carried out in batch

or continuous operations.
 23-Mar-16

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.

ction of Catagsns by ation

Mixed metal Sodium
nitrates tank carbonate tank

Drier and Mixed oxides

and carbonates
calciner

Miil

Powder mixing bin

Weighing
machines Catalyst pellets
 23-Mar-16

/
_ _=_ /
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
 23*Mar-16

lysts Prepared by Go-precipitation

Reaction Cataly'tic elements

Catalysts
Hydrogenation Ni1Ai

Steam reforming Ni,'At. Ni'\{9. Al

Methanol synthesis CuiZn'AI, ZtlCr,CwZil
HiglrerAlcoholsynthesis Cu,tColZt,'Al,CtlColZn/
Fischer-Tropsch CoiCr. Feir\l

Supports fbr catalysts

Basic srqrport N{glAl

hsupported Gatalysts
The sol - gel process
6i The sol - gel process involves the formation of a sol,
followed by the creation of a gel.

6v A sol (liquid suspension of solid particles smaller than 1 mm)

is obtained by the hydrolysis & partial condensation of an
inorganic salt or a metal alkoxide.

6, Further condensation of sol particles into a three-

dimensional network results in the formatlon of a gel. The
porosity & the strength of the gel are strongly affected by
conditions of its formation. For example, slow coagulation,
elevated temperature, or hydrothermal posttreatment
increase the crystalline fraction of the gel.
 23-Mar-16

-nsupported Gatalysts
The sol - gel process

rtll
I

tI
/\
./\
)/l
,/\

ksl M
x.rdt.r Aerogel

\'1r ql,.i lli rr

1.;. i;j,.';, I : i; 1--r'ri'"

":ii;' o.,:,'!';'.,',',''
I
I
ll i{ t|l

.\1'1,tqL:l

-W\
\ril
\',,. -\"tl

\;,1-{,r,1 ltllilt,ri,r*.ir.'s
\
 23-Mar-16

hsupported Gatalysts
The sol - gel process
Example: Preparation of Au/CeOrcatalysts for selective
catalytic oxidation of CO in the presence of H,

L The single step sol-gel catalysts are prepar-e_d_by--

hydrolyiing a lolution of Ge acetate and HAuGlo:xHrO
with NHTOH.
& The reaction mixture is kept at 353 K while the pH 9.0-9.5.
g; Then, HNO3 is added until gelation,

(, The catalysts are dried overnight at 383 K & calcined at

773Kfor5h.
 zJ-tvtar- to

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.

& Additionally, some supports can alter the catalytic properties

of the active phase. This so-called strong metal - support
interaction (SMSI) can decrease, for example, the
chemisorption capacity of supported metals (Pt *TiO2).
 23-[/ar- 1 3

{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)

S Alhh nletals Bl Nonttrerals

6l AlL:aLne eatdr r:retals & i'lobie gases
6 Trausihon n'retals & Laurhanide series
@l Other rnetals &lAchnrde series
I

23-Mar-'16

Prgimoters ----_- ' ' -'4

ffimoters are of two kinds: i;l textural & A chemical.
# Textural promoters are generally used to
(i) facilitate the preparation of well-dispersed catalytic phases and
(ii) maintain their well-dispersed state during reaction conditions.

Textural promoters include supports as well as additives such

as alumina, silrca or other relatively inert, high-surface oxides
that serve the above two purposes.

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.

@ Cnemical promoters are additives that enhance the activity or

selectivity of the catalytic phase.

leparation of Supported Gatalysts

lmpregnation
Objective:
To fill pores of the support with a solution of the catalyst
precursor, e.9., a metal salt of sufficient concentration to
achieve the desired loading.

& lncipient wetness (Dry), usually applied to pelletized

qgpports. The amount of solution added is just enough to
fill the pore volume.

A- Wet impregnation which normally used for powdered

supports. Since wet impregnation involves larger volumes
of metal solution, continuoub stirring should be undertaken
while the drying operation is in progress.
f

/ <,-
='

lmpregnation
lmpregnated catalysts are prepared by impregnating a metal
salt on a porous support. The metal loading in the finished
catalysts typicallyl -5%.

pellets
\ 7 Oore-titrinO
\ r' solulion
)r
I I oore sa uraled
oell-'ts
I I
,#-,i-r,-
,{\1, o.u"r,ror 1 drYrns 19
hj \\*- ysrartire '" I erla,geo oe el
/ \\ l'f- pore

@'?,aA@aAAAAa@AQ-
Schematic of steps in the preparation of supported catalysts
by impregnation to incipient wetness

Distribution of precursor at different conditions of

impregnation and drying
Precursor Conditions of lnlpreg[$tion atd drl ing
dlstrlhutiorr

I-lug shcll tlislrihtttiort l. Slr(,rlg rdsorlrlittn t,l'prccttrs.rrs .lurittr itttprcgnrtiott

f. iligh visr;osity rrf irttprtgttatitru soltrtiott
3. Skls'ttrfing rcginrc li)r loN conccllltttirln- lorv viscosity
arrd \,clk adsorpliou totttliliorts

Igg yolk tlistrihLrtion l. ln prcscncc rtl'conrpcliltr iotts lhirl hrve slntnger

/- -\
inlcraelion ir illt lhe sttppot ls

(r))
\-
). l:rsl clrl in3 rr'gitrr' rr ith l)rcd(,rlrr rl,rrll baek dil lirsiorr

--/

t.jrri [irrnr tli;lribttl irrn L ['rccrrrsors lrnr] corrrlclilL;rs itrtcrrcl cqtrall;'lit1r lllc
su rlit c c.
,/--\, 1.
() i.
lntprcgtlttittg strlutiott ir cr)t)ccrllrlle(l rtlrl r iscous
I(oorrr ler)pcrillLrrc drvinlt rritlt tvt'aklv ar.lsr.rtbinil
\--_,/
Prccuf\ofs
 23-Mar-'16

repar n

:.:'a'-: : r'

Suplort to b:
imp egna:ed

lnl)ltgritli! bi5 n

Wet lmpregnation Dry

lmpregnation
i!
 23-Mar-1e

:"
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.

catalyst loading can be determined using Atomic absorption

spectroscopy (AAS) to find the wt% of metal load (1.4 wt% Ni
and 9.6 wt% Mo).

Advantages & Disadvantage of the impregnation

method
Advantages include its
Relative simplicity
Rapidity
capability for depositing the precursor at high metal roading.

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.
 23-Mar-16

paration of Supported GatalYsts

Adsorption
& lt is a very good method to achieve uniform deposition of
small amounts of active component on a support.
Powders or particles exposed to metal salt solutions adsor-
equilibrium quantities of salt ions, in accordance with
adsorption isotherms.

& Adsorption may be either cationic or anionic, depending

on the properties of the carrier surface.

6,v For example, alumina (depending on the adsorption

conditions, mainly on the pH of the solution) adsorbs both
cations and anions. Silica weakly adsorbs cations, while
magnesia strongly adsorbs anions.

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

&3
iol,/
I --"-
!o II / /
c-o

W !L qt?rr,
-
Concentration l.^.*l
ldO"Obl
 23-Mar-16

--===-=--
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*.

tuThis method is used mainly in the preparation of metal-

containing zeolites, e.g., Ni- or Pd-containing Y zeolites.

l-exchange S-Na* + Ni 2* ll S'Ni e* + Na*

Effect of catalyst load & the presencW

rt on the f,lyst

Unsupported powdered catalYst

Example:

rr"ffiS" ---P"# Powdered Platinum

black catalyst (Pt) can

-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
 23-Mar-16

rcffi ffiffi
m*A \

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.

@ StrOitirution of mechanical properties: The catalysts sample is subjected to

a more severe heat treatment than that is likely to be encountered in a
reactor. This ensures the stability of its textural & structural properties
during reaction.

: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.

:-:, Change in phase distribution: Higher temperature cause matertal to

crystallize into different structural forms.
23-Mar-16