E - FCC Catalysts

Refining-Petrochemicals-Chemicals-Engineering
S.C. PETROTEL-LUKOIL S.A.
FLUID CATALYTIC CRACKING OPERATION AND TROUBLESHOOTING
E - FCC CATALYSTS
I - FUNCTION AND MODE OF ACTION OF CATALYSTS...............................................................1

1 - Transfer of reagents .................................................................................................................................1
2 - Catalytic reaction ......................................................................................................................................2
3 - Removal of products.................................................................................................................................2
II - DESCRIPTION OF FCC CATALYSTS ..........................................................................................3

1 - Generalities on alumino-silicates .............................................................................................................3
2 - Zeolite-based catalysts.............................................................................................................................6
3 - Matrix .......................................................................................................................................................17
III - REQUIRED PROPERTIES AND CHARACTERISTICS FOR AN INDUSTRIAL

CATCRACKING CATALYST........................................................................................................20
1 - Selectivity and activity of FCC catalysts................................................................................................20
2 - FCC catalyst stability ..............................................................................................................................27
3 - Regenerability .........................................................................................................................................27
4 - Mechanical and thermal properties........................................................................................................28
5 - Physical properties of catalyst powder ..................................................................................................29
IV - INDUSTRIAL PRODUCTION OF FCC CATALYSTS .................................................................30
RA FCC - 00097_A_A - Rev. 1 08/10/2007

2007 ENSPM Formation Industrie - IFP Training
1
I- FUNCTION AND MODE OF ACTION OF CATALYSTS

A catalyst is a substance which alters the speed of chemical reactions. In addition to this accelerating
effect, the catalyst exerts an orientating effect, by selective acceleration of the rates of the most useful
reactions. It therefore helps increase yields of useful products, and minimize the quantity of troublesome or
even harmful by-products.
The mechanism of catalytic action involves a transient association with reagent molecules, enabling it to
exert a specific exalting effect on reactivity, and then by orientating the chemical change.
This is therefore a far more selective effect than that of temperature. Thermal activation of chemical reactions
increases all reaction rates to varying degrees, producing non-selective acceleration.
Useful chemical reactions concern mixtures of fluids (gas or liquid), and the catalyst takes the form of a
porous solid in different forms, such as pearls, cylinders or powder.
Catalytic activation occurs during contact between reagent molecules and the catalyst surface. This
contact is obtained in several consecutive stages, each of which can have a determining influence on catalyst
performances. The three major phases in this mechanism are:
1- TRANSFER OF REAGENTS
It deals with the transfer of reagents from the gas or liquid phase to the surface of the catalyst (by
surface should be understood the INTERNAL surface of the grain of catalyst, resulting from the
porous nature of the solid).
The following figure provides a diagrammatic representation of the cross-section of a grain of catalyst.
It contains large channels, known as "macropores" and small channels, or "micropores". The arrows
show the direction taken by reagents R to reach the inside surface of the catalyst.
External surface
of the catalyst grain
R R
Micropores
Gas or liquid phase
containing the reactives
Macropores
D CH 065 B
The surface area for contact between catalysts and reagents can reach several hundreds of square
meters per gram.
00097_A_A 2007 ENSPM Formation Industrie - IFP Training

2
2- CATALYTIC REACTION
The catalytic reaction can be broken down into three successive steps:
- adsorption of reagent molecules on certain available sites on the surface, known as "active
sites".
- chemical reaction in the surface-adsorbed phase. This step is usually very quick, since the
chemical species formed by association with properly selected sites are far more reactive
than non-adsorbed molecules.
Furthermore, the catalyst brings together these reactive species locally in the adsorbed
phase, thereby considerably increasing their probability of meeting, which also helps
accelerate the chemical change.
- desorption of products formed by the reaction, thereby releasing the active sites for re-use.
3- REMOVAL OF PRODUCTS
The products migrate through the pores to the outside of the grain towards the liquid or the gas
homogeneous phase
These various elementary steps in catalysis are summarized on the following diagram
Pore inside the catalyst grain
R P
Rransportation Chemical P
Elimination of th
tants t reaction e produc
Reac ts
A d s orb e d Adsorbed
r e a ct a nts
R P products
t h e c a t aly st
Inside surface of
D CH 064 B
Active site
Use of the catalytic solid in such a mechanism involves the following requirements:
- its surface must be easily accessible to the reagents, and products must be able to move
away quickly to allow maximum use of active sites;
- the chemical nature of these same active sites must be appropriate for the reactions to be
catalyzed, which explains the wide variety of chemical formulae for catalysts.
Proper choice of accessible surface area and active sites governs catalytic activity and selectivity in
relation to the sought-for chemical change.
The catalytic solid must also be able to retain its activity and selectivity in time: it must therefore
possess good stability.

3
II - DESCRIPTION OF F.C.C. CATALYSTS

Nowdays, the main active acidic agent of the FCC catalyst is a zeolite on which we will come back later ( 3).
Before detailing the zeolite structure and properties, we will examine the former FCC catalysts in order to
better understand the catalytic mechanism involved.
The mechanism of catalytic cracking is known to involve the acid properties of the catalyst. These acid
properties result from the presence of numerous active sites containing H+ acid ions on the catalytic surface.
These H+ ions are identical to those released in solution in water by conventional liquid acids, such as
hydrochloric and sulfuric acids. Solids possessing such qualities usually belong to the silica-alumina group,
consisting, as their name indicates, of silica (SiO2) and alumina (Al2O3).
The first catalysts to be used were clays (natural silica-aluminas), treated and activated by acid attack.
From 1940 onwards, synthetic catalysts were developed, in the form of pellets (T.C.C.) or ground powder
(F.C.C.). These catalysts were more active, more selective and more stable. And although more expensive,
they replaced catalysts based on acidified natural clays.
1- GENERALITIES ON ALUMINO-SILICATES
The basic structural units of silica-alumina consist of tetrahedra in which the four vertices are occupied
by oxygen atoms (valency of 2), while the center is occupied either by a silicium atom (valency of 4) or
by an aluminium atom (valency of 3). These two elementary units are illustrated below.
Oxygen Negative charge

Si AI
D CH 1000 C
Basics units of alumina-silica
It may be noted that because of the trivalency of aluminium, the corresponding tetrahedron has a
residual negative charge.

4
Elementary tetrahedra associate with one another by the valency of the oxygen atoms remaining free.
They associate indiscriminately by their vertices, sides or edges, producing an anarchic assembly in
space. This produces the more or less porous structure, characterising AMORPHOUS alumino-
silicates catalysts. The following diagram illustrates a fraction of such a construction.
Na+
Na+

Al
Si Si Al
Na+
Si Al Si Si
Na + Na +
Al
Si Si Al
D CH 1000 B
Positive sodium ions Na + appear in the structure to compensate for negative charges resulting from
the presence of aluminium atoms in the silica-alumina.
This type of solid does not have any type of acid character and a major step in the manufacture of
cracking catalysts is an IONIC EXCHANGE, consisting of replacing all or part of the Na+ ions with
H + acid ions. Removal of the sodium also results in a spectacular increase in the stability of the
catalyst at high temperature in the presence of steam.
The first synthetic catalysts contained a low content of alumina, approximately 15% (so that they are
referred to as "Low-Alumina" or "L.A." catalysts). By 1954, manufacturers had succeeded in
overcoming the difficulty of producing synthetic catalysts with a higher alumina content, of
approximately 25% (these are "High-Alumina" or "H.A." catalysts). Such catalysts are obviously
more acid, because a large number of Na+ ions can be replaced by H+ ions through ionic
exchange.

5
The following table provides a comparison of the performance of these two types of catalysts for the
same feed, with constant coke production (6% weight in relation to feed).
Conversion, yield and properties of cracked Low Al2O3 (13%) High Al2O3 (25%)
products catalyst catalyst
Feed conversion, vol% 61 68

Cracked products yields
H 2, wt.% 0.074 0.072
C 1 + C2, wt.% 1.6 1.6
Total C3 s, vol.% 8.4 8.2
of which propylene 7.6 7.0
Total C4 s, vol.% 6.2 7.4
of which isobutane 2.0 3.5
butenes 4.0 3.6
Gasoline, vol.% 50,5 58.0
Light gas oil (LCO) vol.% 12.0 14.0
Properties of the gasoline
Density 0.72 0.751
Research octane rating (RON), clear 93.3 91.0
Research octane rating + 0.8% Pb 97.2 96.6
Motor octane rating (MON), clear 76.9 76.6
Saturated hydrocarbons, vol.% 23 34
Olefins, vol.% 43 35
Aromatic hydrocarbons, vol.% 34 31
Properties of light gas oil (LCO)

Density 0.915 0.925
Diesel index 29 24
Pour point, C + 8.9 + 7.2
The HA catalyst is seen to be more efficient, offering higher activity and better selectivity, although
the gasoline octane numbers (RON and MON) are rather lower than with LA Catalyst.

6
2- ZEOLITE-BASED CATALYSTS
Zeolite-based F.C.C. catalysts appeared on the market around 1964, and have made a considerable
contribution to catcracking. These catalysts are not only much more active than amorphous H.A.
catalysts, but also more selective and stable at high temperature.
At present the FCC catalyst is a solid complex composite acid with two main components: zeolite,
which is the main active acidic agent, and the matrix.
a - Crystalline structure of zeolites
ZEOLITES or MOLECULAR SIEVES are silica-alumina substances with a particular crystalline

structure. There is a very wide range of them, but the basic element still consists of the same SiO 4 or
AlO4- tetrahedra found in amorphous silica-alumina catalysts.
For convenience, these tetrahedra are represented as follows:
Si or Al
D CH 236 B
Al
Contrary to the case for amorphous silica-alumina catalysts, these elementary tetrahedra combine
only by their vertices in the zeolite structure.
The crystalline basic unit of F.C.C. zeolites is that of the sodalite, shown below:
D CH 306 A
This diagram shows all oxygen, silicium and aluminium atoms. To make the representation of this
sodalite unit clearer, all oxygen atoms not occurring on edges can first be eliminated (a), then only
silicone and aluminium atoms retained (b).

7
(a) (b)
D CH 303 A
Sodalite Unit
This polyhedron comprises 6 square sides and 8 hexagonal faces, and these units are assembled with
one another by either square or hexagonal faces.
Square side assembly: SIEVE A
These assemblies, which are repeated in space, produce very regular cavities, all interconnected,
endowing the solid with a very particular crystalline structure.
Location
of "cages"
Lattices assembled
by their square faces
D CH 146 B
The access orifices to cavities in type A sieves range from 3 to 5 in diameter, depending on the
nature of the positive ions included in the structure. It can be understood that this type of sieve is of no
use in F.C.C., given that the size of the feed molecules is greater than that of the openings giving
access to the inside surface. Type A sieves are however used in the industry to purify gases (by
drying), or separate the components of a mixture according to the sizes of their molecules, hence the
name of "molecular sieves".

8
Hexagonal side assembly: SIEVES X and Y
Hexagonal face lattice assembly
D CH 147 B
This offers quite a different crystalline structure: more specifically, access openings exceed 10 in
diameter, so that sieves X and Y can adsorb heavy hydrocarbons.
All cavities are also interconnected, which makes it easy for molecules to circulate inside the zeolite.
The difference between sieves X and Y lies in their composition. X sieves have a fairly low silica
content (average 60% silica, 40% alumina), while Y sieves contain more silica (average 75% silica,
25% alumina).

9
F.C.C. catalysts are composed mainly of Y zeolites, because the high silica content ensures
greater stability at high temperature. The Y zeolite which as, perfectly organized faujasite structure,
contains a three-dimensional network of identical pores with an opening of about 8 as it is
shown:
z
y
Axis
111
D CH 147 C
Cubo-octahedron Supercage (26 faces) Patway of molecule
The silico-aluminate framework contains a large number of negatively-charged [AlO4] tetrahedra

which are the potential acidic sites. Each [AlO4] tetrahedron associated with a proton is a real acidic
site. All the acid sites are accessible via the very dense pore network.
b - Acidity through ionic exchange
The manufacturing process for these zeolites is quite complex, in particular involving an ionic
+
exchange operation, not with H+ ions, but usually either with NH4 or with rare earth (R.E.) ions such
as cerium or lanthanum, giving this type of zeolite very high acidity combined with very good
thermal stability. Acid sites in a zeolite that has undergone R.E. exchange are 50 to 100 times more
numerous than in an amorphous silica-alumina. These sites also have greater strength, giving 1,000
to 10,000 times more activity than in conventional catalysts. However, this final point raises some
problems when zeolites are used in industrial units.
10
+
Ionic exchange with NH4
+
Na + is replaced by NH4
+ + +
Na Na Na
0 0 0 0 0 0 0 0
SI AL SI AL SI AL SI
0 0 0 0 0 0 0 0 0 0 0 0 0 0
Ion exchange
+ + +
NH4 NH4 NH4
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0
Calcination
+ + +
H H H
0 0 0 0 0 0 0 0
D CH 182 A
0 0 0 0 0 0 0 0 0 0 0 0 0 0
Theoretically (Ideal case): 1 proton per Al
Ionic exchange with rare earths
Na + can also be replaced by rare earth cations
3+ +
3 (Na+) Y + REsol (RE3+) Y + 3 Nasol
The rare earths improve the thermal stability of the zeolite structure and protect its acidity.

11
Consequently, the commonest commercial catalysts consist of 10 to 40% zeolites diluted in a non-
crystalline matrix, which may be either L.A. or H.A. amorphous silica-alumina, or natural silica-alumina,
or in most cases more or less modified natural clays (kaolin).
Industrially-produced zeolites are non-spherical crystalline pearls ranging in size from 1 to 5 microns.
These particles are usually added before final preparation by spraying in the gel of the amorphous
matrix of the catalyst.
The following diagram illustrates the structure of a grain of FCC zeolitic catalyst.
Zeolites
Filler
1 6 microns
Pores
Binder
D CH 1466 B
Microstructure Mesostructure
Mesopores
of the matrix Particle of zeolite
of 1 to 5 microns
Macropores
of the matrix
0.1 to 1 micron
D CH 065 F
65 microns (average)
Macrostructure
The Y zeolites used in the catalysts occur in different forms:
moderately or totally exchanged with rare earths: REHY and REY

modified by heat and/or chemical treatment, they are either free of rare earhs or slightly
back-exchanged with rare earths: H-USY or RE-H-DY.

12
c - Hydrothermal stabilisation and ultrastabilisation
Stabilisation
Above about 500C, the aluminium atoms associated with protons are progressively extracted from
their tetrahedral sites. They deposit in the pores in the form of oxyhydroxides, they migrate and more
or less recombine depending on the temperature to form extra-lattice fragments. In the zones of the
silico-aluminate structure in which an excessively large number of aluminium atoms are extracted
locally, a portion of the structure collapses, leaving a large cavity filled with amorphous silico-
aluminate fragments. At this stage, the silico-aluminate framework thus exhibits atomic vacancies left
by the departure of the aluminium resulting in large cavities (80 to 200 in diameter approximately). If
matters continued to proceed in this way, the structure, which is weakened by the loss of an
excessive amount of aluminium, would ultimately be totally destroyed. The following figure illustrates
this point:
D CH 146 D
Si/Al 3 a 24.65 Si/Al 30 a 24.28
a is measured by X-ray diffraction (XRD)
"steaming" of y zeolite between 500 and 800C

PH2O: from 0.1 to a few bar
A few minutes to a few hours
Increase of the Si/Al ratio of the framework

13
The presence of steam helps to remove silicium from the amorphous silica-alumina fragments, to
cause it to migrate and be reinserted in the local vacancies of the framework. On the whole, the silica-
alumina framework is thus enriched in silicon and simultaneously improves its solidity and hence its
stability, as it is shown on the following scheme:
Alumina extraction
+
Silica migration
Framework aluminium
Silica-alumina debris
Extraramework alumina
Stabilized zeolite
D CH 181 A
Stabilized HY
The aluminium depletion of the zeolite framework corresponds to a decrease in the number of
acidic sites (note that only the aluminium associated with a proton can be extracted).
Ultrastabilisation
As mentioned above, calcination under steam at a temperature above 500C allows to stabilise the
structure by modifying the alumino-silicates squeleton up to a limit fixed by Na+ content.

14
This structure can be further modified by reducing Na+ content through ionic exchange, followed by a
second calcination in presence of steam. This step, called ultrastabilisation, allows to deeply modify
the squeleton and takes place either by the catalyst manufacturer or in situ in the regenerator.
d - Role of rare earths
Until the late 1970s, the Y zeolite in FCC catalysts was strongly exchanged with rare earth ions. It is
now known that these ions replace the protons and hence decrease the number of acidic sites. Yet
they also block the extraction process of the aluminium atoms, maintaining them strongly in the
tetrahedral sites of the framework. For example, when a lanthanum ion neutralizes one or two acidic
sites (the rare earth ions are complex and poorly known), two possibilities occur:
O 2+ O 4+
La La La La
or
D CH 1481 B
O O
It protects several sites due to specific crystallographic positions in the structure. This means that the
richer the zeolite in rare earths, the more effectively it preserves its acidic sites in the severe
hydrothermal conditions of the regenerator.
Hence the manufacturer enjoys the possibility of somehow "programming" the acidity that the zeolite
will develop in the equilibrium catalysts, by introducing more or less rare earth ions into it as shown
below.
a0 ()
Al rich zeolite
24.40
Equilibrated zeolite unit
High acidity
24.35
24.30
Al poor zeolite
24.25
D CH 1512 A
Low acidity Wt% RE2O3

0 2 4 6 8 10 12 14 16
Degree of Rare Earth Exchange

15
If the Y zeolite is very rich in rare earth, it preserves many acidic sites in the equilibrium catalyst.
Hence this catalyst has high activity, but produces a great deal of coke and mediocre quality
gasoline. These two drawbacks are due to the high density of acidic sites, which favors the
bimolecular hydrogen transfer reaction.
Since the early 1980s, demand has grown steadily for catalyst exhibiting better coke selectivity and a
greater ability to favor the gasoline octane rating. To reduce hydrogen transfer, the manufacturers
thus considerably decrease the rare earths content. In doing so, zeolite preserves far fewer acidic
sites in the catalyst, which is one desirable effect, but it poorly withstands the conditions of the
regenerator in the first few hours after its introduction.
In fact, if the partial pressure of steam is insufficient, the aluminium extraction process is faster than the
silica reinsertion process, culminating in a widespread collapse of the zeolite structure, if the Na
content of the zeolite is too high ( 2.5 to 3 wt% Na 2O). This risk is high in the regenerator where the
proportion of steam in the atmosphere is generally less than 25 to 30%. This is why the manufacturers
themselves prefer today to induce the modifications of zeolites which have very few or no rare earths.
They operate in conditions that favor the maintenance of an excellent zeolite cristallinity, but they only
intentionally achieve a part of the modification: it is sufficient to remove only 50% of the aluminium and
replace it by silicium to permanently stabilize the structure. This modified zeolite is called Ultrastable
or USY (Ultrastable Y).
The presence of steam under severe thermal conditions negatively contributes to the ageing of the
zeolitic catalyst. The first thing that happens is the aluminium extraction from the framework, the
second one is the silicium migration. This induces a decrease of the zeolite acidity.
The rare earths have the property to limit the dealumination of the framework, but consequently they
enhance the hydrogen transfer reaction which is, as previously mentioned, detrimental to the gasoline
quality.
At the present time, the tendency, is to reduce or annul the rare earth content in the zeolite and to
pretreat the catalyst in order to get the ultrastable zeolite.

16
Typical Y zeolite derivatives in FCC catalysts
TYPE UCS () Wt% NA2O
NaY 24.68 13.0
NH4Y 24.73 2.5
REY 24.50/24.56 2.5
CREY 24.65 0.3

RENH4Y 24.70 2.5
CREHY 24.50/24.56 0.3
HY
24.55 2.5
NH4Y 24.53 0.3
24.35 0.3
USY
RENH4Y 24.50/24.56 0.3
Sodalite
cage
Supercage
UNIT CELL SIZE

D CH 146 F
Has a total of 4 complete, 6 half and 8 one-eighth

cages. It contains 192 Si and Al atoms

17
3- MATRIX
a - Description
For the manufacturer, the matrix consists of a diluent (filler) and a binder. The filler is an inert
compound such as kaolinite. The binder is either a sol of silica or alumina, or a silica/alumina gel.
The user who argues more in terms of catalyst performance distinguishes between the active matrix
and the inactive matrix. The active matrix includes all the active constituents other than the zeolite:
silica/alumina or transition alumina. By contrast, the inactive matrix includes all the inert or only slightly
active constituents: silica and kaolinite.
Active matrix
Silica/alumina, with a composition close to that of zeolite, differs considerably from it in its properties. It
has no crystalline organization and hence does not posses the structural microporosity of zeolite. A
large number of [AlO 4] tetrahedra present are either encapsulated in the mass, hence inaccessible,
or electrically neutral and hence not potentially acidic (due to a disorganized spatial arrangement
different from that of zeolites). On the whole, it is much less acidic, and hence far less active. It is also
less selective.
Transition alumina is added in two essentially distinct forms: in the form of a alumina sol which plays
the role of binder (i.e. confers good mechanical strength to the catalyst), or in the form of discrete
particles of pseudoboehmite, which improve the cracking activity. Quantities of alumina up to 20 to
30% weight are often added to catalysts designed for very heavy feedstocks, for which it offers better
performance.
Inactive matrix
The silica introduced in the form a sol as a binder only contributes very low activity in comparison with
that of alumina.
Kaolinite is introduced in variable proportions in FCC catalysts in order to:
- dilute the activity of zeolite (as a filler)

- confer good macroporosity to the catalyst
- play the role of a thermal well (removal of heat to protect the zeolite during regeneration)
In the temperature conditions of the regenerator, the kaolinite is irreversibly converted to

metakaolinite.
In the Engelhard in situ technique, the kaolinite is directly formed by atomization, transformed to
metakaolinite, and then partly crystallized to reveal the zeolite at its surface. The metakaolinite and the
crystal fragments play the role of a binder.

18
b - Matrix role
An important function of the matrix is to pre-crack big molecules to correctly feed the zeolite.
A Zeolite pore Pore A

SA/ PD
B
C
20 40 50
Pore dia Pore C Large molecule
Pore B
D CH 1513 A
Effect of pore size distribution on bottoms conversion
A - pores: Not accessible to large molecules

B - pores: Accessible, high surface area contribution - Pore size 2 to 6 times of molecular size
C - pores: Accessible, low surface area contribution
It implies to optimise their matrix/zeolite ratio:
78
Conversion Gasoline selctivity
76 Gasoline selectivity
74
(W/W)
72
70
68
66
102 Bottom conversion
Wt%
98
94
90
0.018
H2 yield Wt%
0.014 H2 yield
0.010
0.006
0.002
Coke yield
4.5
Coke yield Wt%
4.0
D CH 1514 A
3.5
3.0
0
8
Amorphous/Zeolite ratio
Effect of matrix on selectivity (no metals)

19
A synthesis of FCC catalysts is given below:
A- Old catalysts (before 1962)
Amorphous silica-aluminas:
- low alumina (Lo Al): 15 wt % Al2O3

- high alumina (Hi Al): 25 wt % Al2O3
B- Modern catalysts (zeolite based catalysts)
B-1 Main component = Y zeolite (10 to 45 wt %)

Y zeolite = RE-Y, US-Y or RE-US-Y
B-2 The matrix
- the filler = kaolin or metakaloin (20 to 60 wt %)

role: diluting, porosity, thermal well, mechanical strength
- the binder:
silica sol
alumina sol
silica-alumina gel
- some active extra particles such as alumina (pseudoboehmite)
Inactive matrix = kaolin and silica

Active matrix = alumina and silica-alumina
B-3 Additives (incorporated or in separated particles)
- CO combustion promoters (Pt): CO CO2
- SOx additives: Mg based additives, rare earths, (limitation of SOx emissions in the
flue gas)
- metal traps (V): MgO, CaO, Re2 O3 , Ba-Sr titanates, sacrificial zeolite, etc.
- octane additive: ZSM 5 zeolite (MFI)

20
III - REQUIRED PROPERTIES AND CHARACTERISTICS FOR AN INDUSTRIAL

CATCRACKING CATALYST
In addition to the essential catalytic properties of selectivity and activity, F.C.C. used in industrial units must
also possess a number of other properties, including stability, regenerability, mechanical and thermal
properties and grain size, which are also fundamental to proper operation of the process.
1- SELECTIVITY AND ACTIVITY OF FCC CATALYSTS

a -Selectivity
The selectivity of a catalyst characterizes its ability to encourage reactions leading to useful
products, to the detriment of those generating by-products which are less valuable or interfere with the
process.
In the case of F.C.C., the search is to develop catalysts producing maximum gasoline with high
octane number and yielding minimum light gases and coke. The selectivity of a catalyst, however is
an interesting criteria only if it is also sufficiently active.

21
INFLUENCE OF THE DEGREE OF Y ULTRASTABILIZATION

ON CATALYTIC PERFORMANCES
RON
65 % Conv.
92
91.5
91
90.5
90
24.30 24.40 24.50

Zeolite unit cell size ()
Coke on catalyst (Wt%)
65 % Conv.
0.9
0.8
0.7
0.6
0.5
D CH 1292 B
24.30 24.40 24.50


22
INFLUENCE OF THE DEGREE OF Y ULTRASTABILIZATION

ON CATALYTIC PERFORMANCES
Conv. 2
100 - Conv. /SA, g/m
Specific
0.03 activity
0.02
Steam deactivated catalyst
0.01 Equilibrium catalyst
24.30 24.40 24.50

Olefins in gasoline (Wt %)
24 65 % Conv.
22
20
18
16
14
D CH 1291 B
24.30 24.40 24.50


23
b - Activity
The activity of a catalyst measures its effectiveness in accelerating desired chemical reactions. A
catalyst with higher activity helps:
- reducing severity of treatment for the same conversion rate,
- reducing contact time between feed and catalyst: for example, the introduction of zeolite
catalysts, which are far more active than amorphous silica-alumina catalysts, led to a
significant increase in the capacity of many existing units, without major alterations to the
reaction section.
Activity can be linked in particular to specific surface area, porosity and density and of active sites
on the catalyst:
Specific surface area
This is expressed in m2/g, and represents the area of surface actually available to reagents per
gram of catalyst. It is measured by nitrogen adsorption (BET method: Brunauer, Enett and Teller)
at low temperature. The principle consists of reducing a single layer of nitrogen molecules on the
accessible surface area of the catalysts. The quantity of nitrogen thereby adsorbed can be used to
estimate the specific surface area.
New F.C.C. catalysts have large specific areas, around 300 to 400 m2/g. This drops considerably
under operating conditions, and "equilibrium catalysts" have surface areas of around 100 m2/g.
Porosity
High specific surface area cannot be obtained unless the catalyst grains possess high porosity.
Such porosity must also be properly distributed in pore size, so that the surface area is effectively
accessible. As stated above, the porous network must consist of large channels (macropores) which
distribute reactants to smaller channels (micropores), so as to reduce any "bottlenecks" and supply
the active surface area properly.
It is easy to realize that the size of catalyst grains is an important factor. They must not be too large,
so that the pores are shorter and transport of reagents and products faster. In this respect, the small
size of F.C.C. catalyst grains is a very favorable point.
The porous volume, average pore diameter and size distribution are used to assess the overall
qualities of catalyst porosity. The porous volume is expressed in cc/g, and is measured very simply by
pouring water over a given quantity of catalyst. This water is adsorbed on the inside surface of each
grain, and gradually fills the inside volume. Once the catalyst pores are completely full, a little surplus
water glues the powder together by capillary effect, forming a compact "cake". The exact quantity of
water needed to obtain this phenomenon is measured to determine the porous volume, which is
around 0.3 cc/g for F.C.C. equilibrium catalysts.
The average pore diameter can be measured easily from the specific surface area and porous volume.
The following equation is approximate, since it assumes that pores are perfectly cylindrical:
average pore 40.000 x porous volume (in cc/g)

diameter in = specific surface area (m2/g)

24
The following table shows the main properties of two cracking catalysts, one amorphous and the other
zeolite. These properties are given for new and equilibrium catalysts in the industrial unit.
Amorphous Catalyst H.A. Zeolite catalyst XZ-2
Fresh Equilibrium Fresh Equilibrium

catalyst catalyst catalyst catalyst
Composition
Alumina (wt.%) 28 28 31 31
Iron (ppm) 300 3900 700 3700
Physical properties
Surface area (m 2/g) 415 140 335 97
Pore volume (cm3/g) 0.88 0.43 0.60 0.45
Average pore diameter () 85 123 72 186
Bed density 0.39 0.70 0.52 0.62
Granulometry (weight%)
0-20 m 2 0 2 0
0-40 m 17 8 19 6
0-80 m 68 69 75 75
more than 80 m 32 31 25 25
average bead diameter (in m) 65 63 62 62
Catalytic activity
Conversion MAT in vol % 60* 59 85* 73
"Coke factor" 1.0* 1.1 0.6* 0.6
"Hydrogen factor" 1.0* 1.1 0.2* 0.7
*Results obtained after steam treatment
Changes in active surface area, porous volume and average pore diameter of the equilibrium catalyst
in the course of operation are very valuable factors in operating the unit and diagnosing incidents.
Active site density
The catalytic activity of the surface is known to be due to the presence of more or less numerous
active sites of different natures depending on the reactions required.
In the case of catalytic cracking, catalytic activity results from acid sites on the surface, which associate
transiently with reagent molecules, to guide cracking in the direction of useful products.
While with conventional catalysts, cracking activity could be taken to be proportional to the surface
area of the catalyst, and therefore the number of sites, this is absolutely no longer the case with zeolite
catalysts, where the number and strength of acid sites are quite different from those of amorphous
catalysts.

25
c - Activity and selectivity measurement - MICRO-ACTIVITY tests
All these remarks show that the activity and selectivity of F.C.C. catalysts while in use cannot be
deduced solely from measuring the physical properties mentioned above. Various standardized
evaluation methods have been developed by manufacturers of F.C.C. catalysts for routine activity and
selectivity testing of equilibrium catalysts. These are Micro-Activity Tests (MAT). Although equipment
and operating conditions differ from one company to another, the principle of the test remains the
same. A brief description will show its main factors.
In order to measure catalytic properties, an example of equilibrium catalyst (a few grams), from which
any residual coke has been removed, is placed in a small fixed-bed reactor, as shown in the following
diagram.
Pump syringe
Standard feed Syringe

of FCC
Sweeping gas
Preheating area
Reactor
temperature Catalyst to be tested
control
Reactor
CONDENSER
D ANA 1062 B
Gas and Results

liquids measure
ANALYZER
Principle of MAT apparatus
A given quantity of standard F.C.C. feedstock is injected through the catalytic bed, under standard
cracking conditions. After cooling, cracking products are measured and analyzed.

26
The following table shows MAT conditions for three different manufacturers:
DAVISON TEST KATALISTIKS TEST AKZO TEST

Method 600
Catalyst quantity 5g 4g 6g
Feed 2 cm3 1.3 g 1g
Reaction time 75 s 75 s 50 s
Reaction 482C (900F) 482C 482C
temperature
Feed West Texas Devonian Standard Kuwait Distillate

IBP 260C 198C 5% at 330C
EBP 427C 572C 95% at 530C
%S 0.64 wt % 2.53 wt %
d - MAT results
MAT activity is usually defined as the value of CONVERSION obtained during testing. Any variation
in MAT activity results from a change in the level of activity in the unit. On the other hand, it is very
difficult to correlate MAT activity with real conversion rates obtained in the unit, since conditions of
severity and properties of feedstocks are very different.
Selectivity - The selectivity of equilibrium catalysts is identified by various factors:
COKE FACTOR (CF)

HYDROGEN FACTOR (HF)
GAS FACTOR (GF)
(C 1 to C4 gases)
and sometimes ratio
H2
in the gases produced
CH4
The first three factors are defined in the same way. For example, the quantity of coke produced in the
MAT is measured for the catalyst sample, and for a standard catalyst from the maker (for the same
conversion rate in both cases). The coke factor is the ratio of these two quantities of coke. A coke
factor of more than 1 shows that the equilibrium catalyst produces more coke for the same conversion
as the reference catalyst.
New F.C.C. catalysts are very active, and MAT results would not be representative of their
performances in the unit after a few hours' use. Standardized artificial ageing is therefore applied to
them before testing. For example, AKZO proposes a "standard MAT" carried out on a new catalyst
after steaming at 750C for 17 hours, and a "severe MAT" after the same steaming but at 795C.
MAT INTERPRETATION: The chapter on F.C.C. unit operating variables examines how to interpret
MAT results, which are very helpful in directing and optimizing unit operation.

27
2- F.C.C. CATALYST STABILITY

Generally speaking, a good stability of a catalyst means that the latter evolves slowly in the course of
time under the operating conditions. The causes of the performance degradation can be various: coke
formation, progressive adsorption of poisons, sintering of particles, loss of volatile active agent, change
in the cristalline structure of the support,
An industrial F.C.C. catalyst must retain its selectivity and activity as long as possible under industrial
unit operating conditions. This ability to keep its properties is referred to as STABILITY, which
involves in particular:
- ability to withstand high temperatures in the presence of variable quantities of steam

("thermal" and "hydrothermal" stability)
- lowest possible sensitivity to the various substances with which it may come into contact
Certain compounds, however, cause permanent damage to catalyst activity or selectivity: these are
POISONS. Any metals present in F.C.C. feedstocks, mainly nickel, vanadium and sodium, will
poison F.C.C. catalysts.
3- REGENERABILITY
It is only in theory that the catalyst is found intact at the end of the reaction. All catalysts are ageing;
and when their activities or their selectivities have become insufficient, they must be regenerated
through a treatment that will return part or all of their catalytic properties. The most common treatment
is burning off of carbon, but scrubbing with suitable gases is also frequently done to desorb certain
reversible poisons; hydrogenolysis of hydrocarbon compounds may be done when the catalyst permits
it, as well as an injection of chemical compounds. When the treatment does not include burning off
carbon deposits, it often called rejuvenation. The shorter the cycle of operating time between two
regenerations, the more important the regeneration. It becomes apparent that it is not enough for the
catalyst to recover its activity and selectivity, it must also preserve its mechanical strength during
successive regenerations or rejuvenations.
In the FCC process, it obviously deals with the burning off of carbon which acts continuously in the
regenerator.
Regenerability is an essential property for F.C.C. catalysts. The coke that is bound to be formed
during cracking reactions blocks reagent access to the catalyst surface, and poisons it. However, coke
is only a temporary poison, provided that the catalyst can withstand its removal by combustion under
very severe temperature conditions. If this is so, regeneration will restore nearly all its original
qualities.

28
4- MECHANICAL AND THERMAL PROPERTIES

a - Mechanical strength
The mechanical strength of a catalyst is demonstrated by its resistance to crushing, which enables the
catalyst to pass undamaged through all the strains, both foreseen and accidental, that occur within the
catalyst bed. Mechanical strength is also demonstrated by the resistance of the grains to attrition
through rubbing, which produces fines and can cause an increase in the pressure drop in a catalytic
bed. In the case of powdered catalysts destined for fluid or boiling beds, a resistance to abrasion on
the walls or to erosion by the fluids is also required.
F.C.C. catalysts are used in fluidized beds, with pneumatic movement. The grains must not wear
down too quickly to form fines, which cannot be separated out by the cyclones, resulting in serious
losses of catalysts. Grains are worn down by both abrasion (friction between grains and walls) and
attrition (friction among grains themselves).
Numerous tests have been proposed for determining resistance of catalysts to the attrition in fluid
system. In practice, all these tests use the same type of equipment and differ only in their operating
conditions and the duration of the test. The principle remains the same: under controlled pressure, a
flow of air passes upwards through a perforated plate at a rate sufficient to provoke fluidization in the
lower tube of the apparatus. The upper tube suffices to separate fines from particles of catalyst that fall
back into the fluidized bed. Entrained, the fines pass out of the tube and are collected in the filtration
flask.
In order to avoid electrostatic coagulation of the particles, the catalyst may be humidified beforehand.
For example, a fluid bed cracking catalyst will be humidified with 10% water.
In the test of attrition in fluid beds used at IFP and Procatalyse (see diagram below), this experiment
lasts 7 h, and a curve is drawn giving the percentage of fines as a function of time for each catalyst.
Flask for
fines
recovery
Elutriator
= 50 mm
h = 300 mm
Attrition tube
= 25 mm
h = 500 mm
Catalyst
60 g Pressure indicator
(4 bar)
D ANA 1061 B
Perforations
= 0.4 mm PI 425 Nl/h
air

29
b - Thermal properties
For some catalysts, thermal conductivity and specific heat require consideration. High thermal
conductivity of the catalytic mass leads to reduced temperature gradients within the grain, as well as in
the catalytic bed, for endothermic or exothermic reactions, by improving heat transfert.
A high specific heat permits a catalytic cracking catalyst to carry a large thermal load from the
combustion of coke back to the endothermic cracking reaction, i.e. between the regenerator and the
riser, where it is usefully consumed.
Thermal conductivity governs the capacity of the catalyst to transfer coke combustion heat quickly to
the gas phase of the regenerator; it must be high enough to prevent excessive temperature rises inside
the catalyst grain, which could destroy its porous structure. The catalytic solid must therefore possess
high thermal conductivity, to ensure good thermal stability for the catalyst.
5- PHYSICAL PROPERTIES OF CATALYST POWDER

Average Bulk Density (ABD)
This property reveals the link between a given tonnage of catalyst and the volume occupied in storage
silos. It must not be confused with fluidized catalyst density, which is of course less, given the volume
occupied by fluidization gases. However, a catalyst with a higher apparent bulk density than another
usually produces a relatively denser fluidized bed.
The ABD for FCC commercial catalysts may differ considerably, as shown in the following table:
Company G. Davison CCIC AKZO Engelhard
Commercial name Octa 4 Orion Harmorex Vision Octidyne
Density of the standstill bed 0.74 0.72 0.75-0.80 0.72-0.73 0.89
These catalysts are especially adapted to R2R processes (cracking of residues)
ABD for equilibrium catalysts is measured directly, whereas for new catalysts it is done after specific
heat treatment (e.g. 340C for three hours).
Grain size
Suitability for fluidization depends not only on the average size of catalyst particles but also on their
grading.
The size distribution of catalyst particles is measured by microscreening. A sample of 1.5 to 2 g of

catalyst, previously dampened to avoid any static electricity, is placed at the top of a stack of
standardized sieves in which the mesh size increases from top to bottom. The set of sieves is vibrated
for 20 minutes and the content of each sieve is weighed, and the result converted into a percentage of
the initial weight.
The results of grading analyses are very useful for an FCC unit, making it possible to track down and
diagnose any problems of fluidization, circulation, attrition or loss in cyclone separations.

30
IV - INDUSTRIAL PRODUCTION OF F.C.C. CATALYSTS

The following diagram illustrates the main stages in the manufacture of conventional F.C.C. catalysts:
Filtration Ionic
Silicon salt Aluminium salt water solution
SiO2 Al2O3
FILTRATION DRYING DRYING
Water WASHING-FILTRATION
NaOH OF THE GEL Water
T, P, pH: controlled
D CH 1366 A
MANUFACTURE
OF ALUMINA-SILICA GEL
Traditionally catalysts were produced by precipitating silica and alumina in an aqueous solution. The silica-
alumina micelles organize in space to form a gel imprisoning water. The porousness, surface area and other
properties of the future catalyst depend on the conditions under which this gel "ripens": temperature, pH,
stirring, reaction time, to mention only the main ones.
Micelles of Ripening
alumina-silica of the gel
D CH 1467 B
gel

31
Water is then filtered out, and the mixture is washed several times, using water with variable pH. After being
dried, the silica-alumina is acidified by ion exchange, then pre-dried. F.C.C. catalysts are no longer
prepared by grinding the calcined material, since a spray-drying technique was introduced at the end of the
50s. This consists in pulverizing the gel into fine droplets which are immediately dried by a powerful stream of
hot air. The resulting fine particles are then separated from the hot air in cyclone separators.
A flowsheet and a view of an industrial spray-drying unit are shown below:
Product Gas washing

feed tower
Air feed Cyclone
D MEQ 1369 B
Burner
Atomized product

32
The manufacturing schemes for the new octane FCC catalysts are presented below:
ACID SODIUM SILICATE
SiO2 hydrosol
pH 3.0
CLAY
Mixing
SiO2 /clay
NaY or Na-HSY slurry
Mixing
Zeolite/clay/SiO2
slurry (< 40% solids)
Spray drying
Catalyst
precusor
Ion exchage, H2O wash
Wet catalyst
Flash drying
D CH 1515 A
FCC catalyst

33
The manufacturing schemes for the new octane FCC catalysts are presented below:
Sodium Sodium
aluminate hydroxide
(NH4)2SO4 Spray drier
Sodium Seeds H 2O
silicate
wash
FILTER CALCINER
NaY NH4, NaY Exchange agent, H2O
H 2O H 2O
Na Zeolite NaY ion

Na-USY
crystallization exchange BEDT FILTER FLASH FILTER
80-90C Clay
Al2O3 source Exchange agent Additve
8-24 hr FCC catalyst (optional)
SiO2 source precursor wash
Storage
FCC catalyst
D CH 1366 C
H 2O
Mixing of zeolite with

matrix components
Manufacturing scheme for octane FCC catalysts, with USY zeolite exchanged after incorporation into the
matrix.

E - FCC Catalysts

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E - FCC Catalysts

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Refining-Petrochemicals-Chemicals-Engineering

S.C. PETROTEL-LUKOIL S.A.

FLUID CATALYTIC CRACKING OPERATION AND TROUBLESHOOTING

I - FUNCTION AND MODE OF ACTION OF CATALYSTS...............................................................1

II - DESCRIPTION OF FCC CATALYSTS ..........................................................................................3

III - REQUIRED PROPERTIES AND CHARACTERISTICS FOR AN INDUSTRIAL

IV - INDUSTRIAL PRODUCTION OF FCC CATALYSTS .................................................................30

RA FCC - 00097_A_A - Rev. 1 08/10/2007

I- FUNCTION AND MODE OF ACTION OF CATALYSTS

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

II - DESCRIPTION OF F.C.C. CATALYSTS

Oxygen Negative charge

Basics units of alumina-silica

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Feed conversion, vol% 61 68

Properties of light gas oil (LCO)

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

a - Crystalline structure of zeolites

ZEOLITES or MOLECULAR SIEVES are silica-alumina substances with a particular crystalline

For convenience, these tetrahedra are represented as follows:

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Square side assembly: SIEVE A

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Hexagonal side assembly: SIEVES X and Y

Hexagonal face lattice assembly

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Cubo-octahedron Supercage (26 faces) Patway of molecule

The silico-aluminate framework contains a large number of negatively-charged [AlO4] tetrahedra

b - Acidity through ionic exchange

Theoretically (Ideal case): 1 proton per Al

Ionic exchange with rare earths

Na + can also be replaced by rare earth cations

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

The Y zeolites used in the catalysts occur in different forms:

moderately or totally exchanged with rare earths: REHY and REY

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

c - Hydrothermal stabilisation and ultrastabilisation

a is measured by X-ray diffraction (XRD)

"steaming" of y zeolite between 500 and 800C

Increase of the Si/Al ratio of the framework

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

d - Role of rare earths

Low acidity Wt% RE2O3

Degree of Rare Earth Exchange

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Typical Y zeolite derivatives in FCC catalysts

TYPE UCS () Wt% NA2O

NaY 24.68 13.0

NH4Y 24.73 2.5

REY 24.50/24.56 2.5

CREY 24.65 0.3

CREHY 24.50/24.56 0.3

NH4Y 24.53 0.3

UNIT CELL SIZE

Has a total of 4 complete, 6 half and 8 one-eighth

00097_A_A 2007 ENSPM Formation Industrie - IFP Training

Kaolinite is introduced in variable proportions in FCC catalysts in order to:

- dilute the activity of zeolite (as a filler)

In the temperature conditions of the regenerator, the kaolinite is irreversibly converted to