Title of Invention

FCC CATALYSTS PREPARED BY IN-SITU CRYSTALLIZATION OF ZEOLITE

Abstract A fluid catalytic cracking catalyst is provided with a high porosity by in-situ crystallizing an aluminosilicate zeolite from a reactive microsphere comprising metakaolin and hydrous kaolin. Any calcinations of the reactive microsphere before reaction with a zeolite-forming solution is done at low temperatures so as to ensure the hydrous kaolin is not converted to metakaolin.
Full Text FCC CATALYSTS PREPARED BY IN-SITU CRYSTALLIZATION OF ZEOLITE
BACKGROUND OF THE INVENTION
The present invention relates to novel fluid
catalytic cracking catalysts comprising microspheres
containing Y-faujasite zeolite and having exceptionally
high activity and other desirable characteristics, methods
for making such catalysts and the use of such catalysts
for cracking petroleum feedstocks, particularly under
short residence time processes.
Since the 1960's, most commercial fluid catalytic
cracking catalysts have contained zeolites as an active
component. Such catalysts have taken the form of small
particles, called microspheres, containing both an active
zeolite component and a non-zeolite component.
Frequently, the non-zeolitic component is referred to as
the matrix for the zeolitic component of the catalyst.
The non-zeolitic component is known to perform a number of
important functions, relating to both the catalytic and
physical properties of the catalyst. Oblad described
those functions as follows:
"The matrix is said to act as a sink for sodium in
the sieve thus adding stability to the zeolite
particles in the matrix catalyst. The matrix serves

the additional function of: diluting the zeolite;
stabilizing it towards heat and steam and mechanical
attrition; providing high porosity so that the
zeolite can be used to its maximum capacity and
regeneration can be made easy; and finally it
provides the bulk properties that are important for
heat transfer during regeneration and cracking and
heat storage in large-scale catalytic cracking."
A.G. Oblad Molecular Sieve Cracking Catalysts, The
Oil And Gas Journal, 70, 84 (March 27, 1972).
In prior art fluid catalytic cracking catalysts, the
active zeolitic component is incorporated into the
microspheres of the catalyst by one of two general
techniques. In one technique, the zeolitic component is
crystallized and then incorporated into microspheres in a
separate step. In the second technique, the in-situ
technique, microspheres are first formed and the zeolitic
component is then crystallized in the microspheres
themselves to provide microspheres containing both
zeolitic and non-zeolitic components.
It has long been recognized that for a fluid
catalytic cracking catalyst to be commercially successful,
it must have commercially acceptable activity,
selectivity, and stability characteristics. It must be
sufficiently active to give economically attractive

yields, it must have good selectivity towards producing
products that are desired and not producing products that
are not desired, and it must be sufficiently
hydrothermally stable and attrition resistant to have a
commercially useful life.
Two products that are particularly undesirable in
commercial catalytic cracking processes are coke and
hydrogen. Even small increases in the yields of these
products relative to the yield of gasoline can cause
significant practical problems. For example, increases in
the amount of coke produced can cause undesirable
increases in the heat that is generated by burning off the
coke during the highly exothermic regeneration of the
catalyst. Conversely, insufficient coke production can
also distort the heat balance of the cracking process. In
addition, in commercial refineries, expensive compressors
are used to handle high volume gases, such as hydrogen.
Increases in the volume of hydrogen produced, therefore,
can add substantially to the capital expense of the
refinery.
U.S. Patent No. 4,493,902, the teachings of which are
incorporated herein by cross-reference, discloses novel
fluid cracking catalysts comprising attrition-resistant,
high zeolitic content, catalytically active microspheres
containing more than about 40%, preferably 50-70% by

weight Y faujasite and methods for making such catalysts
by crystallizing more than about 40% sodium Y zeolite in
porous microspheres composed of a mixture of two different
forms of chemically reactive calcined kaolin, namely,
metakaolin (kaolin calcined to undergo a strong
endothermic reaction associated with dehydroxylation) and
kaolin calcined under conditions more severe than those
used to convert kaolin to metakaolin, i.e., kaolin
calcined to undergo the characteristic kaolin exothermic
reaction, sometimes referred to as the spinel form of
calcined kaolin. In a preferred embodiment, the
microspheres containing the two forms of calcined kaolin
are immersed in an alkaline sodium silicate solution,
which is heated, preferably until the maximum obtainable
amount of Y faujasite is crystallized in the microspheres.
In practice of the '902 technology, the porous
microspheres in which the zeolite is crystallized are
preferably prepared by forming an aqueous slurry of
powdered raw (hydrated) kaolin (Al2O3:2SiO2:2H2O) and
powdered calcined kaolin that has undergone the exotherm
together with a minor amount of sodium silicate which acts
as fluidizing agent for the slurry that is charged to a
spray dryer to form microspheres and then functions to
provide physical integrity to the components of the spray
dried microspheres. The spray dried microspheres'

containing a mixture of hydrated kaolin and kaolin
calcined to undergo the exotherm are then calcined under
controlled conditions, less severe than those required to
cause kaolin to undergo the exotherm, in order to
dehydrate the hydrated kaolin portion of the microspheres
and to effect its conversion into metakaolin, this
resulting in microspheres containing the desired mixture
of metakaolin, kaolin calcined to undergo the exotherm and
sodium silicate binder. In illustrative examples of the
'902 patent, about equal weights of hydrated kaolin and
spinel are present in the spray dryer feed and the
resulting calcined microspheres contain somewhat more
kaolin that has undergone the exotherm than metakaolin.
The '902 patent teaches that the calcined microspheres
comprise about 30-60% by weight metakaolin and about 40-
70% by weight kaolin characterized through its
characteristic exotherm. A less preferred method
described in the patent, involves spray drying a slurry
containing a mixture of kaolin previously calcined to
metakaolin condition and kaolin calcined to undergo the
exotherm but without including any hydrated kaolin in the
slurry, thus providing microspheres containing both
metakaolin and kaolin calcined to undergo the exotherm
directly, without calcining to convert hydrated kaolin to
metakaolin.

In carrying out the invention described in the '902
patent, the microspheres composed of kaolin calcined to
undergo the exotherm and metakaolin are reacted with a
caustic enriched sodium silicate solution in the presence
of a crystallization initiator (seeds) to convert silica
and alumina in the microspheres into synthetic sodium
faujasite (zeolite Y). The microspheres are separated
from the sodium silicate mother liquor, ion-exchanged with
rare earth, ammonium ions or both to form rare earth or
various known stabilized forms of catalysts. The
technology of the '902 patent provides means for achieving
a desirable and unique combination of high zeolite content
associated with high activity, good selectivity and
thermal stability, as well as attrition-resistance.
The aforementioned technology has met widespread
commercial success. Because of the availability of high
zeolite content microspheres which are also attrition-
resistant, custom designed catalysts are now available to
oil refineries with specific performance goals, such as
improved activity and/or selectivity without incurring
costly mechanical redesigns. A significant portion of the
FCC catalysts presently supplied to domestic and foreign
oil refiners is based on this technology. Refineries
whose FCC units are limited by the maximum tolerable
regenerator temperature or by air blower capacity seek

selectivity improvements resulting in reductions in coke
make while the gas compressor limitations make catalysts
that reduce gas make highly desirable. Seemingly a small
reduction in coke can represent a significant economic
benefit to the operation of an FCC unit with air blower or
regenerator temperature limitations.
Improvements in cracking activity and gasoline
selectivity of cracking catalysts do not necessarily go
hand in hand. Thus, a cracking catalyst can have
outstandingly high cracking activity, but if the activity
results in a high level of conversion to coke and/or gas
at the expense of gasoline the catalyst will have limited
utility. Catalytic cracking activity in present day FCC
catalysts is attributable to both the zeolite and non-
zeolite (e.g., matrix) components. Zeolite cracking tends
to be gasoline selective. Matrix cracking tends to be
less gasoline selective. After appropriate ion-exchange
treatments with rare earth cations, high zeolite content
microspheres produced by the in situ procedure described
in the '902 patent are both highly active and highly
gasoline selective. As zeolite content of these unblended
microspheres is increased, both activity and selectivity
tend to increase. This may be explained by the decrease
in matrix content with increase in zeolite content and the
decreasingly prominent role of nonselective matrix

cracking. Thus, increases in the zeolite content of the
high zeolite content microspheres have been reported to be
highly desirable.
The activity and selectivity characteristics of the
catalysts formed by the process of the '902 patent are
achieved even though, in general, the catalysts have
relatively low total porosity as compared to fluid
catalytic cracking catalysts prepared by incorporating the
zeolite content into a separate matrix. In particular,
the microspheres of such catalysts, in some cases, have a
total porosity of less than about 0.15 cc/g. or even less
than about 0.10 cc/g. In general, the microspheres of the
'902 patent have a total porosity of less than 0.30 cc/g.
As used herein, "total porosity" means the volume of pores
having diameters in the range of 35-20,000A , as
determined by the mercury porosimetry technique. The '902
patent noted that it was surprising that microspheres
having a total porosity of less than about 0.15 cc/g.
exhibit the activity and selectivity characteristics
found. For example, such a result is contrary to the
prior art disclosures that low pore volumes "can lead to
selectivity losses due to diffusional restrictions."
It is believed that the relatively low porosity of
the catalyst microspheres formed as in the '902 patent
does not adversely effect activity and selectivity

characteristics, since the microspheres of the '902 patent
are not diffusion limited relative to the typical FCC
processing conditions which were used at the time of the
patent. In particular, catalyst contact time with the
feed to be cracked was typically 5 seconds or more. Thus,
while typical FCC catalysts formed by mechanically
incorporating the zeolite within a matrix may have been
more porous, the reaction time in prior art FCC risers did
not yield any advantage in activity or selectivity. This
result inspired the conclusion that transport processes
were not at all limiting in FCC catalysts, at least
outside the zeolite structure. Assertions made to the
contrary were inconsistent with the facts and easily
dismissed as self-serving. Importantly, the attrition
resistance of the microspheres prepared in accordance with
the '902 patent was superior to the conventional FCC
catalysts in which the crystallized zeolite catalytic
component was physically incorporated into the non-
zeolitic matrix.
Recently, however, FCC apparatus have been developed
which drastically reduce the contact time between the
catalyst and the feed which is to be cracked.
Conventionally, the reactor is a riser in which the
catalyst and hydrocarbon feed enter at the bottom of the
riser and are transported through the riser. The hot

catalyst effects cracking of the hydrocarbon during the
passage through the riser and upon discharge from the
riser, the cracked products are separated from the
catalyst. The catalyst is then delivered to a regenerator
where the coke is removed, thereby cleaning the catalyst
and at the same time providing the necessary heat for the
catalyst in the riser reactor. The newer riser reactors
operate at lower residence time and higher operating
temperatures to minimize coke selectivity and delta coke.
Several of the designs do not even employ a riser, further
reducing contact time to below one second. Gasoline and
dry gas selectivity can improve as a result of the
hardware changes. These FCC unit modifications are
marketed as valuable independent of the type of catalyst
purchased, implying an absence of systematic problems in
state of the art catalyst technology.
The processing of increasingly heavier feeds in FCC
type processes and the tendency of such feeds to elevate
coke production and yield undesirable products have also
led to new methods of contacting the feeds with catalyst.
The methods of contacting FCC catalyst for very short
contact periods have been of particular interest. Thus,
short contact times of less than 3 seconds in the riser,
and ultra short contact times of 1 second or less have

shown improvements in selectivity to gasoline while
decreasing coke and dry gas production.
To compensate for the continuing decline in catalyst
to oil contact time in FCC processing, the "equilibrium"
catalysts in use have tended to become more active. Thus,
increases in the total surface area of the catalyst need
to be achieved and as well, the level of rare earth oxide
promoters added to the catalysts are increasing.
Moreover, cracking temperatures are rising to compensate
for the reduction in conversion. Unfortunately, it has
been found that the API gravity of the bottoms formed
during short contact time (SCT) often increases after a
unit revamp, leading some to suggest that the heaviest
portion of the hydrocarbon feed takes longer to crack.
Further, while a high total surface area of the catalyst
is valued, the FCC process still values attrition
resistance. Accordingly, while not obvious to those
participating in the art, it has become increasingly
likely that an optimization of FCC catalysts for the new
short contact time and ultra short contact time processing
which is presently being used is needed.
It is now theorized that, under the short contact
time processing of hydrocarbons, further improvements can
be gained by eliminating diffusion limitations that may
still exist in current catalysts. This is being concluded

even as these materials excel at the application. It is
theorized that improvements in these catalysts may be
produced by optimization of catalyst porosity and the
elimination of active site occlusion and diffusional
restrictions of the binder phases present in catalysts
prepared by the so-called incorporation method.
While the present assignee has produced zeolite
microspheres with increased zeolite content and increased
activity by increasing the macroporosity of the spray
dried microsphere zeolite precursors, the porosity of the
formed zeolite microsphere catalysts has not before been
considered a problem since there has been found no
diffusion limitation under the previous FCC processing
techniques. For example, commonly assigned, U.S. Patent
No. 4,965,233, to Speronello discloses increasing the
zeolite content of an in-situ catalyst by forming highly
porous precursor microspheres, which allow increased
amounts of zeolite to grow within the porous matrix. The
highly porous precursor microspheres are formed by spray
drying a slurry of hydrous kaolin, which is characterized
by the presence of a major amount of large (greater than 2
microns) kaolin stacks along with spinel calcined kaolin.
When spray dried, the coarse hydrous kaolin results in
microspheres having a desired high content of macropores
in which the zeolite Y can grow. Likewise, commonly

assigned, U.S. Patent No. 5,023,220, to Dight, et. al.
also increases the macroporosity of the precursor
microspheres by spray drying a mixture of hydrous kaolin,
metakaolin and spinel. These catalyst microspheres have a
substantial level of zeolite and are very active and
selective. Further, the high alumina, silica-alumina
matrix portion of the catalysts is often totally
surrounded by the zeolite formed in-situ such that the
matrix is only now understood to provide a reduced level
of bottoms cracking under the short contact time FCC
conditions.
In commonly assigned, copending application U.S.
Serial No. 09/956,250, filed September 20, 2001, novel
zeolite microspheres are disclosed. These zeolite
microspheres are macroporous, have sufficient levels of
zeolite to be very active and are of a unique morphology
to achieve effective conversion of hydrocarbons to cracked
gasoline products with improved bottoms cracking under SCT
FCC processing. The novel zeolite microspheres are
produced by novel processing, which is a modification of
technology described in U.S. Patent No. 4,493,902. It has
been found that if the non-zeolite, alumina-rich matrix of
the catalyst is derived from an ultrafine hydrous kaolin
source having a particulate size such that 90 wt. % of the
hydrous kaolin particles are less than 2 microns, and

which is pulverized and calcined through the exotherm, a
macro-porous zeolite microsphere can be produced. More
generally, the FCC catalyst matrix useful to achieve FCC
catalyst macroporosity is derived from alumina sources,
such as kaolin calcined through the exotherm, that have a
specified water pore volume, which distinguishes over
prior art calcined kaolin used to form the catalyst
matrix. The water pore volume is derived from an
Incipient Slurry Point (ISP) test, which is described in
the application.
The morphology of the microsphere catalysts which are
formed is unique relative to the in-situ microsphere
catalysts formed previously. Use of a pulverized,
ultrafine hydrous kaolin calcined through the exotherm
yields in-situ zeolite microspheres having a macroporous
structure in which the macropores of the structure are
essentially coated or lined with zeolite subsequent to
crystallization. Macroporosity as defined herein means
the catalyst has a macropore volume in the pore range of
600 - 20,000 A of at least 0.07 cc/gm mercury intrusion.
The novel catalyst is optimal for FCC processing,
including the short contact time processing in which the
hydrocarbon feed is contacted with a catalyst for times of
about 3 seconds or less.

In the broadest sense, the invention as disclosed in
U.S. Serial No. 09/956,250 is not restricted to
macroporous catalysts having a non-zeolite matrix derived
solely from kaolin. Thus, any alumina source which has
the proper combinations of porosity and reactivity during
zeolite synthesis and can generate the desired catalyst
macroporosity and morphology can be used. The desired
morphology comprises a matrix which is well dispersed
throughout the catalyst, and the macropore walls of matrix
are lined with zeolite and are substantially free of
binder coatings. Accordingly, not only is the large pore
surface area of the catalyst vastly improved over previous
catalysts, and the active matrix dispersed throughout the
microsphere, the zeolite crystals are readily accessible
to the hydrocarbon feed. While not wishing to be bound by
any theory of operation, it appears that previous
catalysts in which the zeolite is incorporated into a
matrix by physical mixing and glued with binder have
sufficient macroporosity, however the binder coats the
active zeolite catalyst thereby blocking accessibility
thereto. The novel microsphere catalysts have a
morphology which allows fast diffusion into the catalyst
due to the macroporosity and enhanced dispersion of the
matrix, and further provides the highest accessibility to
the zeolite inasmuch as the zeolite is freely coated onto

the walls of the pores. The term "freely" means that the
zeolite phase is present on the surface of the matrix and
is unobstructed by any binder phases. Merely having
macroporosity does not provide the results that have been
obtained, since conventional incorporated catalysts have
similar macroporosity. It is therefore the combination of
porosity and zeolite-coated macropore walls that give the
surprising selectivity results.
One would not have anticipated that contacting a
heavy hydrocarbon feed, whose molecules are frequently if
not generally too large to enter zeolite pores, with
zeolite prior to feed contact with the matrix would be
optimal, as has been found. Indeed, the prevailing
"staged cracking" theory suggests the opposite, that the
larger hydrocarbon molecules are first cracked on the
active matrix and the formed smaller molecules
subsequently cracked within the zeolite. Much research
and promotional activity has been done in pursuit or
support of this perceived ideal.
In view of the success of the macroporous in-situ-
formed zeolite microsphere as disclosed above, there is a
continuing need to find novel macroporous zeolite
catalysts in which the matrix is dispersed throughout the
catalyst and the zeolite crystals are free of binder
coatings and readily accessible to the hydrocarbon feed.

There is a need as well to find other methods of forming
such catalysts. Therefore, it is an object of the
invention to provide a novel method for reproducibly
preparing a catalyst that is an attrition resistant,
highly porous catalyst with a zeolite-coated matrix
morphology and provide novel catalysts having such
properties.
SUMMARY OF THE INVENTION
In accordance with the present invention, a novel
macroporous in-situ-formed zeolite catalyst is provided by
forming a precursor reactive microsphere which contains
reactive metakaolin and inert hydrous kaolin. The
microsphere is reacted with an alkaline silicate solution
to form the zeolite crystals. The presence of the hydrous
kaolin as a matrix precursor has been found to yield a
macroporous structure on the order of that disclosed in
the aforementioned copending application, U.S. Serial No.
09/956,250. In the copending application the macroporous
structure is achieved using a calcined, ultra-fine hydrous
kaolin as the matrix precursor. The catalyst of this
invention can also include a matrix derived in part from
kaolin calcined through the characteristic exotherm, as

well as a calcined boehmite alumina which has been found
useful for metal passivation.
In the process of forming the novel catalyst of the
present invention, metakaolin, hydrous kaolin, and a
silicate binder are spray dried to form a precursor
reactive microsphere. The hydrous kaolin is maintained as
an inert component even if the as-spray dried microsphere
is calcined by calcining at a lower temperature and
avoiding the endothermic transformation of hydrous kaolin
to metakaolin. The inert hydrous kaolin is not consumed
under the caustic crystallization conditions. The
metakaolin provides the reactive silica and alumina for
crystallization and also enables the presence of high pore
volume in the spray dried microsphere. The amount of
metakaolin, or more generally, the amount of soluble
alumina available to crystallize zeolite, is limited so
that yield of zeolite is limited during the
crystallization resulting in a sufficient macroporosity.
DETAILED DESCRIPTION OF THE INVENTION
Catalysts of the invention are made by spray drying a
feed mixture of hydrated kaolin, metakaolin, and a binder
such as silica sol or sodium silicate. The spray dried
microspheres are optionally acid-neutralized and washed to
reduce sodium content. The spray dried microsphere are

preferably subsequently calcined to form precursor porous
microspheres. Importantly in this invention, the hydrous
kaolin is maintained as an inert component by calcining at
lower temperatures so as to avoid the endothermic
transformation of the hydrous kaolin component to
metakaolin. Calcination temperatures of less than 1000°F,
preferably less than 800°F, can be used to calcine the
spray dried microspheres.
The amount of metakaolin in the spray dried and
optionally calcined microspheres provides the soluble
alumina available to grow zeolite. The amount of
metakaolin present in the spray dried microspheres is
limited with respect to the inerts such as hydrous kaolin
so that the yield of zeolite is limited during
crystallization. An excessive level of metakaolin in the
reactive microsphere would yield a high level of zeolite
that would reduce the porosity of the microsphere to an
undesired low level. Accordingly, the spray dried
microspheres after optional calcination will contain a
metakaolin content of up to 50 wt.%, preferably up to 45
wt%, and more preferably will be present in amounts of 30-
40 wt%.
Any binder used should contain only sodium, expressed
as Na2O, which is easily removed. Although the silica or
silicate binders traditionally used do bring these

nutrients into the zeolite crystallization process, their
main purpose is to provide mechanical strength to the
green microspheres sufficient to withstand processing up
until crystallization. Therefore, any binder capable of
fulfilling this role while not interfering with the other
constraints laid out herein would be adequate. Aluminum
chlorohydrol for example might be useful.
The precursor microspheres are reacted with zeolite
seeds and an alkaline sodium silicate solution,
substantially as described in U.S. Patent No. 5,395,809,
the teachings of which are incorporated herein by cross-
reference. The microspheres are crystallized to a desired
zeolite content (typically ca. 40-75%), filtered, washed,
ammonium exchanged, exchanged with rare-earth cations if
required, calcined, exchanged a second time with ammonium
ions, and calcined a second time if required.
Especially preferred compositions of the solids in
the slurries that are spray dried to form porous
microspheres, and later optionally calcined at low
temperature to prepare precursor reactive microspheres,
are expressed hereinafter below in Table 1 as the weight
percent of metakaolin and inerts including hydrated
kaolin, calcined boehmite for metal passivation, and
kaolin calcined through the exotherm (spinel or mullite)
on a binder-free basis; weight % SiO2 binder is based on

the grams of Si02 in the binder per gram of total weight
of moisture-free spray dried microspheres and provided by
sodium silicate. In general, the spray dried microspheres
will have a size of from about 20 to 150 microns.
Preferably, the size of the spray dried microspheres will
range from about 50 to 100 microns and, more preferably,
from about 69-90 microns.

Hydrous kaolin is used as an inert in the slurry and
acts as an alumina-containing matrix precursor of the
catalyst. Thus, once crystallized, the zeolite catalyst
will contain a silica-alumina matrix derived from the
hydrous kaolin. The hydrous kaolin used as the alumina-
containing matrix precursor of the catalytic microspheres
is not singularly critical and can be obtained from a wide
variety of commercial sources. The hydrous kaolin can
suitably be either one or a mixture of ASP® 600 or ASP® 400

kaolin, derived from coarse white kaolin crudes. Finer
particle size hydrous kaolins can also be used, including
those derived from gray clay deposits, such as LHT
pigment. Purified water-processed kaolins from Middle
Georgia have been used with success. The particle size of
the hydrous kaolin is generally known to have an impact on
microsphere porosity, so the resultant crystallized
catalyst macroporosity can be manipulated in part by
manipulation of the hydrous kaolin particle size. The
present assignee for example has shown that coarser
hydrous kaolin yields higher macropore volume in
microspheres. Since the present invention comprises
several parameters that effect changes in catalyst
macroporosity, there remains some flexibility in the
choice of the hydrous kaolin particle size.
Calcination of these hydrous kaolins at temperatures
of 1200°F results in endothermic dehydroxylation of the
hydrous kaolin to metakaolin which can be used as the
metakaolin component of the feed slurry.
Silicate for the binder is preferably provided by
sodium silicates with SiO2 to Na2O ratios of from 1.5 to
3.5 and especially preferred ratios of from 2.00 to 3.22.
The non-zeolitic, alumina-containing matrix of the
catalysts of the present invention can further be derived
in part from a hydrous kaolin source that is in the form

of an ultrafine powder that is pulverized and calcined
through the exotherm. Typical zeolite microspheres have
been formed with an alumina-containing matrix derived from
kaolin having a larger size than used in this invention
and which is calcined at least substantially through its
characteristic exotherm. Satintone® No. 1, (a
commercially available kaolin that has been calcined
through its characteristic exotherm without any
substantial formation of mullite) is a material used on a
commercial basis to form the alumina-containing matrix.
Satintone® No. 1 is derived from a hydrous kaolin in which
70% of the particles are less than 2 microns. Other
sources having been used to form the alumina-containing
matrix include finely divided hydrous kaolin (e.g., ASP®
600, a commercially available hydrous kaolin described in
Engelhard Technical Bulletin No. TI-1004, entitled
"Aluminum Silicate Pigments" (EC-1167)) calcined at least
substantially through its characteristic exotherm.
Booklet kaolin has found the most widespread commercial
use and has met tremendous success worldwide. Before the
invention disclosed in previously mentioned U.S. Serial
No. 09/956,250, these larger kaolin particles represented
the state of the art in forming the alumina-containing
matrix of the catalyst microsphere and had no perceived
deficits.

What is meant by "ultrafine" powder is that at least
90 wt. % of the hydrous kaolin particles must be less than
2 microns in diameter, preferably less than 1 micron
determined by Sedigraph™ (or sedimentation) . It has been
found that, in particular, use of hydrous kaolin pigments
with this particle size distribution upon pulverization
and calcination through the characteristic exotherm
results in a greater quantity of macroporosity in the
catalyst microsphere subsequent to zeolite
crystallization. The loose packing of the calcined
ultrafine kaolin, which has been found, can be likened to
a "house of cards" in which the individual particulates
are aligned randomly with respect to adjacent particles in
a non-parallel manner. Moreover, the calcined ultrafine
kaolin exists as porous aggregates of the "house of cards"
morphology, providing not only a porous aggregate but
additional porous areas between aggregates. Pulverization
of the ultrafine hydrous kaolin is required to provide the
random stacking of the individual kaolin platelets.
The pulverized ultrafine hydrous kaolin, optionally
used to derive a portion of the alumina-containing matrix,
is calcined through its characteristic exotherm with or
without the formation of mullite. An especially preferred
matrix source which can be used in this invention to form
in part the macroporous zeolite microspheres is Ansilex®

93. Ansilex® 93 is made from the fine size fraction of a
hard kaolin crude, by spray drying, pulverizing and
calcining to prepare low abrasion pigments as described in
U.S. Patent No. 3,586,523, to Fanselow, et. al., the
entire contents of which are herein incorporated by
reference. The ultrafine hydrous matrix source is spray
dried, pulverized and then calcined through the exotherm,
optionally to mullite. The aforementioned U.S. Patent No.
4,493,902 discloses calcining the kaolin to mullite until
the X-ray diffraction intensities are comparable to a
fully crystalline reference standard. While it is within
the scope of the present invention to calcine the
ultrafine hydrous kaolin beyond the exotherm such that the
X-ray diffraction intensities are comparable to a fully
crystalline referenced standard as disclosed in the '902
patent, it is preferred to calcine the ultrafine hydrous
kaolin beyond the characteristic exotherm so as to convert
the kaolin to small crystallite size mullite. The small
crystallite size mullite has the appropriate diffraction
lines and leached chemical composition of a fully
crystalline mullite standard, but the diffractional lines
are weaker inasmuch as the crystallites are smaller. The
relationship between diffraction intensity/line width and
crystallite size is well-known. It is preferred to
calcine the kaolin beyond the exotherm to a small

crystallite mullite matrix inasmuch as fully calcining the
kaolin to mullite takes excessive time and temperature in
practice. Furthermore, calcining kaolin beyond the
exotherm to fully crystalline mullite can result in the
macroporosity being lost due to sintering. Moreover, bulk
density after calcining kaolin to fully crystalline
mullite can be substantially increased. Thus, it is
preferred that the ultrafine hydrous kaolin calcined
through the exotherm has 20-80% of the integrated X-ray
diffraction peak areas of a kaolin reference sample
containing well crystallized mullite. More preferably,
the ultrafine kaolin is calcined through the exotherm such
that it has 50-70% of the integrated X-ray diffraction
peak areas of fully crystallized mullite.
What is unusual about the use of the Ansilex®
material is that it is derived from hard kaolin. Hard
kaolins typically have a gray tinge or coloration and are,
thus, also referred to as "gray clays". These hard
kaolins are further characterized by breaking into
irregularly shaped fragments having rough surfaces. Hard
kaolins also contain a significant iron content, typically
about 0.6 to 1 wt. % of Fe203. Hard kaolin clays are
described in Grim's "Applied Clay Mineralogy", 1962,
MaGraw Hill Book Company, pp. 394-398 thereof, the
disclosure of which is incorporated by reference herein.

The use of these materials to form part of the alumina-
containing matrix for in situ FCC microsphere catalysts
has not been known previous to U.S. Serial No. 09/956,250
although their use in the incorporated routes is well
established. Hard kaolins have also occasionally been
used as sources of metakaolin for in situ microspheres,
but not with advantage. Without wishing to be bound by any
theory, it would appear that previous use of the calcined
gray clays in the in situ matrix art would be precluded by
(a) the high iron content thereof and the possibility that
this could lead to coke and gas production, and (b) the
dilatant nature of slurries formed therefrom, leading to
apparently senseless waste of process time and increased
cost in making down high viscosity slurries which spray
dry at low solids. We now believe these dilatancy problems
and porosity benefits are intrinsically and fundamentally
linked. As for the former point, reduced coke and gas was
an especially sought-after object for in situ catalysts,
since the original formulations of Haden made coke and gas
commensurate with their extraordinarily high level of
amorphous matrix activity. This led to lower and lower
levels of iron and spinel in subsequent inventions. It is
a surprising finding that there appears to be no
relationship between the iron and coke and gas
selectivities after all. Instead, substantial

improvements in FCC dry gas and coke were obtained through
process modifications like improved feed injection and
riser termination devices reducing contact time.
The matrix can be derived at least in part from
alumina-containing materials more generally characterized
by the porosity thereof provided during the packing of the
calcined material. A test has been developed to determine
the pore volume of the calcined alumina-containing
material which can be used to ultimately form a part of
the matrix of the inventive catalyst. The test
characterizes the water pore volume of the calcined
alumina-containing material by determining the minimum
amount of water needed to make a slurry from a sample of
the solids. In the test, a powder sample is mixed with
water containing a dispersant such as, for example,
Colloid 211, Viking Industries, Atlanta, GA, in a cup
using a stirring rod or spatula. Just enough water is
added to the dry sample to convert the dry powder to a
single mass of dilatant mud which only just begins to flow
under its own weight. The incipient slurry point (ISP) is
calculated from the weights of the sample and water used.
The incipient slurry point can be calculated as follows:
ISP = [(grams of dry sample)/(grams of dry sample plus
grams of water added)] x 100. The units are dimension-less
and are reported as percent solids.

This amount of water is larger than the (internal)
water pore volume of the sample, but is clearly related to
the water pore volume. Lower incipient slurry point
percent solids values indicate higher water absorption
capacities or higher pore volume in the sample. The
calcined alumina-containing materials from which the high-
alumina matrix can be at least in part derived in
accordance with this invention will have incipient slurry
points less than 57% solids, preferably 48 to 52% solids.
This compares with Satintone® No. 1 which yields over 58%
solids in the incipient slurry point test.
Accordingly, not only is the ultrafine hydrous kaolin
useful as an alumina-containing material which can be used
to derive a portion of the matrix of the catalyst
microspheres, but the matrix may also be derived in part
from delaminated kaolin, platelet alumina and precipitated
alumina. Means for delaminating booklets or stacks of
kaolin are well-known in the art. Preferred are those
methods, which use a particulate grinding medium such as
sand, or glass microballoons as is well-known. Subsequent
to delamination, the platelets are pulverized to derive
the random packing or "house of cards" morphology.
An advantage of the matrix precursors meeting the ISP
test specification is that they bring higher pore volume
per unit matrix surface area. This maximizes the

effectiveness of the catalyst by minimizing both catalytic
coke (pore volume) and contaminant coke (matrix surface
area) .
It is also within the scope of this invention to
derive the matrix in part from chemically synthesized
spinel and/or mullite. Thus, Okata, et al.,
"Characterization of spinel phase from SiO2-Al2O3 xerogels
and the formation process of mullite", Journal of the
American Ceramic Society, 69 [9] 652-656 (1986), the
entire contents of which are incorporated herein by
reference disclose that two kinds of xerogels can be
prepared by slow and rapid hydrolysis of tetraethyoxy
silane and aluminum nitrate nonahydrdate dissolved in
ethanol. The slow hydrolysis method involves gelling the
above mixture in an oven at 60° C. for one to two weeks
whereas the rapid hydrolysis method involves adding
ammonium hydroxide solution to the mixture and drying in
air. Xerogels prepared by the slow hydrolysis method
crystallized mullite directly from the amorphous state on
firing whereas the xerogels formed by rapid hydrolysis
crystallized a spinel phase before mullite formation. As
long as such calcined synthetic materials have a water
pore volume within the scope of this invention, such
materials can be used to derive at least in part the high-
alumina matrix of the catalyst of this invention.

In order to passivate contaminant metals, such as
nickel and vanadium, the catalyst matrix may further
include an alumina source derived from highly dispersible
boehmite. Other aluminas such as pseudo-boehmite with low
dispersibility, and gibbsite can be used, but are not as
effective. Dispersibility of the hydrated alumina is the
property of the alumina to disperse effectively in an
acidic media such as formic acid of pH less than about
3.5. Such acid treatment is known as peptizing the
alumina. High dispersion is when 90% or more of the
alumina disperses into particles less than about 1 micron.
The surface area (BET, nitrogen) of the crystalline
boehmite, as well as the gamma - delta alumina conversion
product, upon calcination is below 150 m2/g, preferably
below 125 m2/g, and most preferably below 100 m2/g, e.g. 30
- 80 m2/g.
Following are typical properties of fully peptizable
and dispersible crystalline boehmites which can be used in
practice of the invention


Monoprotic acids, preferably formic, can be used to
peptize the crystalline boehmite. Other acids that can be
employed to peptize the alumina are nitric and acetic.
During production, the crystalline boehmite is
calcined prior to incorporation into the microsphere. As
a result of calcination, the crystalline boehmite is
converted to a porous gamma phase and to a lesser extent a
delta alumina. The BET surface area of this material only
increases marginally, e.g., increases from 80 m2/g to 100
m2/g. The calcined boehmite converted to the gamma phase
is added to the slurry of hydrous kaolin, metakaolin, and
other alumina matrix components and spray dried into the
microspheres. Upon zeolite crystallization, the gamma
alumina will not be leached from the microspheres by the
alkaline silicate solution. When the dispersed alumina
solution is calcined and spray dried with the kaolin and
binder, the resulting microsphere contains uniformly
distributed gamma alumina throughout the microsphere.
Preferably, the pore volume of the crystallized
zeolite microsphere of this invention, which is formed
using hydrous kaolin to form the catalyst matrix, is
greater than 0.15 cc/gm, more preferably greater than 0.25
cc/gm, and most preferably greater than 0.30 cc/gm of Hg
in the range of 40-20,000A diameter. More particularly,
the catalyst of this invention has a macropore volume

within pores having a size range of 600 to 20,000A of at
least 0.07 cc/gm of Hg, and preferably at least 0.10 cc/gm
of Hg. While conventional zeolite-incorporated catalysts
have macroporosities comparable to the catalysts of this
invention, the incorporated catalysts do not have the
novel zeolite-on-matrix morphology nor performance of the
catalysts of this invention. The catalysts of this
invention will have a BET surface area less than 500 m2/g,
preferably less than 475 m2/g and most preferably within a
range of about 300-450 m2/g. The moderate surface area of
the catalysts of this invention in combination with the
macroporosity achieves the desired activity and
selectivities to gasoline while reducing gas and coke
yields.
One skilled in the art will readily appreciate that
it is the steam-aged surface area and activity that is
truly significant and which must be balanced against the
available pore volume. The cited preferred surface areas
for finished product (fresh) catalyst are chosen such that
the surface area after a 1500° F, four hour steaming at 1
atm steam pressure are generally below 300 m2/gm.
It has further been found that the macroporosity of
the catalyst of this invention is maintained even if a
portion of the matrix is derived from calcined or
additional coarse alumina-containing materials which

otherwise have a low water pore volume as determined by
the ISP test described above.
A quantity (e.g., 3 to 30% by weight of the kaolin)
of zeolite initiator may also be added to the aqueous
slurry before it is spray dried. As used herein, the term
"zeolite initiator" shall include any material containing
silica and alumina that either allows a zeolite
crystallization process that would not occur in the
absence of the initiator or shortens significantly the
zeolite crystallization process that would occur in the
absence of the initiator. Such materials are also known
as "zeolite seeds". The zeolite initiator may or may not
exhibit detectable crystallinity by x-ray diffraction.
Adding zeolite initiator to the aqueous slurry of
kaolin before it is spray dried into microspheres is
referred to herein as "internal seeding". Alternatively,
zeolite initiator may be mixed with the kaolin
microspheres after they are formed and before the
commencement of the crystallization process, a technique
which is referred to herein as "external seeding".
The zeolite initiator used in the present invention
may be provided from a number of sources. For example,
the zeolite initiator may comprise recycled fines produced
during the crystallization process itself. Other zeolite
initiators that may be used include fines produced during

the crystallization process of another zeolite product or
an amorphous zeolite initiator in a sodium silicate
solution. As used herein, "amorphous zeolite initiator"
shall mean a zeolite initiator that exhibits no detectable
crystallinity by x-ray diffraction.
The seeds may be prepared as disclosed by in
4,493,902. Especially preferred seeds are disclosed in
4,631,262.
After spray drying, the microspheres may be calcined
at low temperature, e.g., for two to four hours in a
muffle furnace at a chamber temperature of less than 1000°
F. It is important that during calcination the hydrated
kaolin component of the microspheres is not converted to
metakaolin, leaving the hydrous kaolin, and optional
spinel or gamma alumina components of the microspheres
essentially unchanged. Alternatively, if the microspheres
are formed with a sodium silicate binder, the microspheres
may be acid-neutralized to enhance ion exchange of the
catalysts after crystallization. The acid-neutralization
process comprises co-feeding uncalcined, spray dried
microspheres and mineral acid to a stirred slurry at
controlled pH. The rates of addition of solids and acid
are adjusted to maintain a pH of about 2 to 7, most
preferably from about 2.5 to 4.5 with a target of about 3
pH. The sodium silicate binder is gelled to silica and a

soluble sodium salt, which is subsequently filtered and
washed free from the microspheres. The silica gel-bound
microspheres are then calcined at low tempature.
Y-faujasite is allowed to crystallize by mixing the
kaolin microspheres with the appropriate amounts of other
constituents (including at least sodium silicate and
water), as discussed in detail below, and then heating the
resulting slurry to a temperature and for a time (e.g., to
200°-215° F. for 10-24 hours) sufficient to crystallize Y-
faujasite in the microspheres. The prescriptions of
4,493,902 may be followed as written. Equivalent,
reformatted recipes are provided as follows, however.
The crystallization recipes we employ are based on a
set of assumptions and certain raw materials. The seeds
are described by 4,631,262 and are preferably used
externally. The SiO2, A1203, and Na20 components of
metakaolin, seeds, sodium silicate solution, calcined
sodium silicate binder, and silica gel are assumed to be
100% reactive. The silica-alumina and alumina derived
from the hydrous kaolin and calcined boehmite,
respectively, are assumed to be completely unreactive for
zeolite synthesis. The alumina and silica in kaolin
calcined through the exotherm to the spinel form are
assumed to be 1% and 90% reactive respectively. Although
these two values are in use, they are not believed to be

accurate. The alumina and silica in kaolin calcined
through the exotherm to the mullite form are assumed to be
0% and 67% reactive, respectively. These two values are
believed to be accurate, representing the inertness of 3:2
mullite in crystallization and the full solubility of the
free silica phase. Since metakaolin alumina is the
limiting reagent in the synthesis and the volume of
zeolite is much larger than the corresponding volume of
metakaolin, it is important to limit the zeolite yield
appropriately for a given microsphere pore volume.
Otherwise, there will result little or no residual pore
volume after crystallization. Such is the case for the
prior art. On the other hand, if insufficient limiting
reagent is available in the microsphere to grow sufficient
zeolite to appropriately strengthen the catalyst,
additional nutrient alumina may be added in the form of
metakaolin microspheres, as is well known in this art.
Thus, tight process control is enabled for pore volume and
attrition resistance.
Using these assumptions, the following weight ratios
for reactive components are used in the overall
crystallization recipes. Inert components do not enter
into the ratios, except in the case of the seeds dose,
which is defined as the ratio of the grams of seeds A1203
to total grams of microspheres.


The sodium silicate and sodium hydroxide reactants
may be added to the crystallization reactor from a variety
of sources. For example, the reactants may be provided as
an aqueous mixture of N® Brand sodium silicate and sodium
hydroxide. As another example, at least part of the
sodium silicate may be provided by the mother liquor
produced during the crystallization of another zeolite-
containing product.
After the crystallization process is terminated, the
microspheres containing Y-faujasite are separated from at
least a substantial portion of their mother liquor, e.g.,
by filtration. It may be desirable to wash to
microspheres by contacting them with water either during
or after the filtration step. The purpose of the washing
step is to remove mother liquor that would otherwise be
left entrained within the microspheres.
"Silica Retention" may be practiced. The teachings
of U.S. Patent No. 4,493,902 at column 12, lines 3-31,
regarding silica retention are incorporated herein by
cross-reference.

After crystallization by reaction in a seeded sodium
silicate solution, the microspheres contain crystalline Y-
faujasite in the sodium form. In order to obtain a
product having acceptable catalytic properties, it is
necessary to replace sodium cations in the microspheres
with more desirable cations. This may be accomplished by
contacting the microspheres with solutions containing
ammonium or rare earth cations or both. The ion exchange
step or steps are preferably carried out so that the
resulting catalyst contains less than about 0.7%, most
preferably less than about 0.5% and most preferably less
than about 0.4%, by weight Na2O. After ion exchange, the
microspheres are dried to obtain the microspheres of the
present invention. In order to make 0 (zero) wt. % rare
earth (REO) catalysts, the Na+ cations are exchanged by
using only an ammonium salt such as NH4NO3 and without
using any rare earth salt during exchange. Such 0 (zero)
wt. % REO catalysts are especially beneficial as FCC
catalysts that give higher octane gasoline and more
olefinic product. Rare earth versions of catalysts of
this invention, post treated after crystallization by ion-
exchange with high levels of rare earth, e.g., by
procedures such as described in the '902 patent, are
useful when exceptionally high activity is sought and the
octane rating of the FCC gasoline produce is not of prime

importance. Rare earth levels in the range of 0.1% to 12%
usually between 0.5% and 7% (weight basis) are
contemplated. Following ammonium and rare earth exchange,
the catalyst is calcined at 1100°-1200° F. for 1-2 hours
and unit cell size of the Y zeolite is reduced.
Preferably, this calcination is done in a covered tray
with 25% free moisture present.
The preferred catalyst of the invention comprises
microspheres containing at least 15% and preferably from
40 to 65% by weight Y faujasite, expressed on the basis of
the as-crystallized sodium faujasite form zeolite. As
used herein, the term Y faujasite shall include synthetic
faujasite zeolites exhibiting, in the sodium form, an X-
ray diffraction pattern of the type described in Breck,
Zeolite Molecular Sieves, p. 369, Table 4.90 (1974), and
having a crystalline unit cell size, in the sodium form
(after washing any crystallization mother liquor from the
zeolite), of less than about 24.75 A as determined by the
technique described in the ASTM standard method of testing
titled "Determination of the Unit Cell Size Dimension of a
Faujasite Type Zeolite" (Designation D3942-80) or by an
equivalent technique. The term Y faujasite shall
encompass the zeolite in its sodium form as well as in the
known modified forms, including, e.g., rare earth and
ammonium exchanged forms and stabilized forms. The


Conditions useful in operating FCC units utilizing
catalyst of the invention are well-known in the art and
are contemplated in using the catalysts of the invention.
These conditions are described in numerous publications
including Catal. Rev. - Sci. Eng., 18 (1), 1-150 (1978),
which is incorporated herein by cross-reference. The
catalysts of this invention that contain the calcined
dispersable boehmite are particularly useful in cracking
residuum and resid-containing feeds having a Ni+V metals
content of at least 2,000 ppm and a Conradson carbon
content greater than 1.0.
The catalyst of the present invention, like all
commercial fluid catalytic cracking catalysts, will be
hydrothermally deactivated during the operation of the
cracking unit. Accordingly, as used herein, the phrase
"cracking the petroleum feedstock in the presence of a
catalyst" shall include cracking the petroleum feedstock
in the presence of the catalyst in its fresh, partially
deactivated, or fully deactivated form.
From the prior art discussed previously, it was
thought that the less porous catalyst microspheres were
superior products in view of the excellent attrition
resistance, high activity and selectivity provided,

especially in light of the well established fact that
these catalysts have selectivity at least equivalent to
lower surface area, higher pore volume catalysts, and
frequently better selectivity at short contact time.
Assertions to the contrary would easily be dismissed as
self-serving and would also be tantamount to saying the
so-called incorporated catalysts were diffusion-limited at
short residence time. It has only recently been
discovered that under the short contact time FCC
processing, FCC catalysts technologies may be diffusion
limited with respect to transport in pores external to the
zeolite. This is proposed to be the reason that the API
gravity of the bottoms fraction has often risen after SCT
revamp. Less obvious than that, it now appears that
conventional, prior art catalysts fail to provide all of
the potential gains of the SCT hardware. But heretofore
there was no way to know what benefits were absent.
Accordingly, the catalyst microspheres of this invention
have a substantially different morphology than the
previous catalyst microspheres, especially with respect to
the increased pore volume, zeolite-on-matrix morphology,
and moderate surface area. Attrition resistance of these
catalysts is good and effective for the SCT FCC processing
conditions.

The method of preparation and subsequent properties
such as mercury pore volume, the catalyst of this
invention includes a macroporous matrix in which the
macropores of the matrix are formed from a random
configuration of porous matrix planar structures which are
lined with the zeolite crystals. Thus, the macropores of
the catalyst are lined with the active zeolite crystals.
The macroporosity of the catalyst allows the hydrocarbons
to enter the catalyst freely and the increased macropore
surface area thereof allows such hydrocarbons to contact
the catalytic surfaces. Importantly, the hydrocarbons can
contact the zeolite unobstructed, rendering the catalyst
very active and selective to gasoline. While conventional
incorporated zeolite catalysts, in which the zeolite
crystals are incorporated within a binder and/or matrix,
have a highly porous matrix, at least a portion of the
binder coats or otherwise obstructs the zeolite crystals.
In the present microspheroidal catalysts, there is no need
for a separate physical binder which glues the zeolite to
the matrix surface other than any minute amounts of
silicate which may remain subsequent to zeolite
crystallization. It is believed that the microsphere
catalysts formed in accordance with the process of the
present invention yield the highest accessibility to the
zeolite of any zeolite/matrix catalyst.

Also optionally present in a highly dispersed state
are the particles of metal-passivating alumina. While
there is a preponderance of zeolite lining the macropore
walls of the invention, smaller particles presumed to be
formed from the dispersed boehmite and/or mullite are also
seen.
It has been found that the microspheroidal catalysts
of the present invention provide high conversions via low
coke_selectivity and higher selectivities to gasoline
relative to previous FCC catalysts presently on the
market. It is surprising that this catalyst can
consistently outperform conventional incorporated
catalysts of similar or even higher porosity and lower
surface area. This shows that having added porosity alone
is not sufficient. It is now believed that the novel
structured catalysts, being both macroporous and with the
macropore walls lined with zeolite and with the mesoporous
or microporous matrix substantially behind the zeolite
layer are the reasons the catalyst excels at gasoline, LCO
and coke selectivity. The present catalyst is sufficient
to crack the heavier hydrocarbons and anticipated to
improve the API gravity of the bottom fraction, especially
during the short contact time processing.
The examples, which follow, illustrate the present
invention:

EXAMPLE 1
The microspheres of this Example were made in a pilot
plant with nozzle-type atomizer. The following components
as set forth in Table 3 were mixed in a Cowles mixer and
spray dried. The sodium silicate was added directly to
the slurry, resulting in flocculation. Solids were
adjusted appropriately in order to enable spray drying.

The microspheres were calcined at 700°F for 4 hours
before further use.
EXAMPLES 2 and 3
Two reactions were run to grow zeolite in the
microsphere of Example 1 with and without the addition of
a microsphere containing 100% metakaolin to adjust zeolite
content. The reaction components for each example are
shown in Table 4.


The corresponding ratios of reactive components were
SiO2/Na2O=2.70 w/w, H2O/Na2O =7.0 w/w, SiO2/Al2O3=7.0 w/w and
seeds Al2O3/grams microsphere of 0.0044 w/w. The as-
crystallized sample of Example 2 had a Hg pore volume of
0.31 cc/g (40-20K pore diameter).
Properties of the finished product of Example 3 were as
follows:

EXAMPLES 4 and 5
The microspheres of Examples 4 and 5 contain
ultrafine kaolin(Ansilex 93®) calcined through the
characteristic exotherm and were spray dried at a Pilot
plant with a wheel-type atomizer. The weight percentages

of each component forming the spray dried slurry are shown
in Table 5. The weight percentage of each kaolin
component is on a binder-free basis.

The spray dried microspheres were calcined at 700°F
for 4 hours before further use.
EXAMPLES 6 and 7
Two reactions were run to grow zeolite using the
microspheres of Examples 4 and 5. The reaction components
for each example are shown in Table 6.


Properties of the finished products of Examples 6 and 7
are shown below.


The finished products of Examples 3, 6, and 7 show
similar macropore size distribution with peak maxima in
the range of 500-700A in radius. The introduction of
Ansilex-93® gives rise to an increased pore volume in the
range of 25-30 A pore radius. All of the above
catalyst examples did not contain metal tolerant alumina
and are intended for cracking of a feed with a minimum
metals content.
EXAMPLES 8 and 9
These examples disclose the preparation of
microsphere containing metal tolerant alumina. In
general, metal tolerant highly dispersable boehmite was
first calcined at 1450°F for 2h to gamma alumina. The
gamma alumina was then milled to reduce APS to about 2
microns in aqueous media. The milled gamma alumina
slurry, either peptized or not, was added to a slurry
containing metakaolin, hydrous kaolin, and Ansilex-93® when
applicable, in a Cowles mixer. Sodium silicate (3.22
SiO2/Na2O) was then added into the slurry, along with

sufficient water to form a mixture suitable for
atomization. The slurry was spray dried in a pilot plant
with a wheel-type atomizer. The weight percentages of
each component of the slurry are set forth in Table 7.
Again, the percentages of the alumina components are on a
binder-free basis.

The spray dried microspheres were calcined at 700°F
for 4h and were used for the following crystallization.


The properties of the finished product of Examples 10
and 11 are shown below.

EXAMPLES 12-16
These examples measure the performance of the
catalysts of the present invention (Examples 3, 6, and 7)
against that of two comparative examples. The two
comparative examples represent the catalysts of U.S.
Serial No. 09/956,250 (Comparative 1) and U.S. 5,395,908
(Comparative 2. The catalyst samples were laboratory
deactivated at 1450°F for 4h in 100% steam. The
deactivated catalysts were then tested in an ACE™
fluidized bed test unit at 970°F with 1.125" injector
height with an aromatic feed having a Conradson carbon of
about 6%. The activity was changed by changing the amount
of active FCC catalyst. The total amount of inert
microspheres and active catalyst in the ACE unit was kept
constant at 12.0 g. The yields are reported at 70%
convention.



Compared to the Comparative 2 sample, the current
invention clearly demonstrates the improved gasoline yield
and bottom cracking, especially in the presence of small
amounts of bottom upgrading matrix (spinel and/or
mullite)in the microsphere. In general, the presence of
macroposity and bottom upgrading matrix (spinel and/or
mullite) greatly improves the yields of the desired
products.
EXAMPLES 17-21
Examples below measure the performance of catalysts
of the present invention (Examples 10 and 11) against
catalysts of U.S. Serial No. 09/956,250 (Comparative 3),
U.S. Serial No. 09/978,180, filed October 17, 2001
(Comparative 4), and U.S. Serial No. 10/164,488, filed
June 6, 2002 (Comparative 5) . Comparative catalysts 4 and
5 represent a class of catalysts for residuum cracking.
The catalyst samples were presteamed at 1350°F for 2h in
100% steam, and 3000/3000 PPM Nickel and Vanadium were
added via incipient wetness using nickel octoate and
vanadium naphthenate, followed by poststeaming at 1450°F
for 4h in a mixture of 90% steam and 10% air. The
performance of each catalyst was then measured using ACE

following the protocols described in the above Examples.
Yields were compared at 70% conversion.

The catalysts of current invention show dramatic
improvement in gasoline yield and bottom upgrading
compared to comparative samples 3 and 4. The inventive
catalysts also provide the lowest H2 yield among the
catalysts tested, indicating better metal passivation.
EXAMPLES 22-24
These examples also show improved metal passivation
of the catalysts of the present invention against the
Comparative 5 catalyst and a commercial resid catalyst
(Comparative 6) . The ACE data were generated from the
catalysts deactivated in a different way compared to those
in Examples 17-21. The three samples were laboratory
deactivated in a prestream, fluid bed crack on nickel and
vanadium, post steam deactivation protocol. Typical Ni
and V loadings were 2800 PPM and 3600 PPM respectively.
The deactivated catalysts were then tested in an ACE unit
at 8 WHSV, 2.125" injector height, and 998°F crack

temperature with the same feed as that used in the
examples above. The amount of catalyst in the ACE unit
was constant at 9.0 g and the activity was changed by
changing the amount of oil delivered. Product yields were
given at 75% conversion.

Again, the catalyst of current invention results in a
dramatic improvement in metal passivation as indicated by
the low H2 yield. The catalyst of Example 10 contains no
bottom cracking matrix such as spinel or mullite.
Modification of this catalyst with the addition of small
amounts of spinel and/or mullite would improve the bottom
upgrading with little or no penalty in metal passivation.

WE CLAIM:
1. A zeolitic fluid catalytic cracking catalyst comprising:
(a) at least [about] 40% by weight of an aluminosilicate zeolite crystallized
in-situ from a metakaolin-containing calcined reactive microsphere; and
(b) an alumina-containing matrix formed from hydrous kaolin contained
in said reactive microsphere, said calcined reactive microsphere
containing at least 5 wt.% hydrous kaolin.

2. The catalyst of claim 1 wherein said reactive microsphere comprises
based on [the] alumina-containing components 5-80 wt.% hydrous
kaolin, 20-50 wt.% metakaolin, 0-30 wt.% calcined boehmite, and 0-30
wt.% of a kaolin which has been calcined through the characteristic
exotherm, [the ratio of metakaolin to kaolin which has been calcined
through the characteristic exotherm being at least 1.33.]
3. The catalyst of claim 2 wherein said reactive microsphere comprises 10-
75 wt.% hydrous kaolin, 25-45 wt.% metakaolin, 10-25 wt.% calcined
boehmite, and 5-30 wt.% of said [calcined] kaolin which has been
calcined through the characteristic exotherm, said percentage being
based upon the weight of alumina-containing components.
4. The catalyst of claim 1 having a mercury pore volume of greater than
0.25 cc/gm in a pore diameter range of 40-20,000 angstroms.

5. A fluid catalyst cracking catalyst comprising catalytic microspheres
containing at least 40% by weight Y-faujasite crystallized in-situ from a
metakaolin-containing reactive microsphere, said catalytic microspheres
having a mercury porosity of greater than about 0.15 cc/g for pores
having diameter in a range of 40-20, 000 angstroms, said catalytic
microspheres comprising:
a non-zeolitic, alumina-containing matrix derived from hydrous
kaolin contained in said calcined reactive microsphere containing at least
5 wt.% hydrous kaolin.
6. The fluid catalytic cracking catalyst of claim 5 wherein said alumina-
containing matrix is further derived from an alumina-containing
precursor having an incipient slurry point of less than 57% solids.
7. A process of forming a fluid catalytic cracking catalyst comprising:

a) spray drying an aqueous slurry comprising hydrous kaolin and
metakaolin to form reactive microspheres having a diameter in the range
of from 20-150 microns, and calcining said reactive microspheres, said
calcined reactive microspheres containing at least 5 wt.% hydrous
kaolin.
b) reacting said spray dried, calcined microspheres with an aqueous
alkaline silicate solution at a temperature and a time to form in-situ at
least 40 wt.% crystallized Y-faujasite from said reactive microspheres.
8. The process of claim 7 wherein said spray dried microspheres are
calcined at a temperature of less than 1000°F prior to reacting such
spray dried microspheres with said aqueous alkaline silicate solution.

9. The process of claim 8 wherein said aqueous slurry contains 50-80 wt. %
hydrous kaolin, 20-50 wt. % metakaolin, 0-30 wt. % calcined boehmite,
and 0-30 wt.% of a kaolin calcined through the characteristic exotherm.
10. A method of cracking a hydrocarbon feed under FCC conditions,
comprising contacting said hydrocarbon feed with the catalyst as claimed
in claim 1.


A fluid catalytic cracking catalyst is provided with a high porosity by in-situ crystallizing
an aluminosilicate zeolite from a reactive microsphere comprising metakaolin and
hydrous kaolin. Any calcinations of the reactive microsphere before reaction with a
zeolite-forming solution is done at low temperatures so as to ensure the hydrous kaolin
is not converted to metakaolin.

Documents:

02335-kolnp-2005-abstract.pdf

02335-kolnp-2005-claims.pdf

02335-kolnp-2005-description complete.pdf

02335-kolnp-2005-form 1.pdf

02335-kolnp-2005-form 2.pdf

02335-kolnp-2005-form 3.pdf

02335-kolnp-2005-form 5.pdf

02335-kolnp-2005-international publication.pdf

2335-KOLNP-2005-ABSTRACT 1.1.pdf

2335-KOLNP-2005-ASSIGNMENT 1.1.pdf

2335-kolnp-2005-assignment.pdf

2335-KOLNP-2005-CLAIMS.pdf

2335-KOLNP-2005-CORRESPONDENCE 1.1.pdf

2335-kolnp-2005-correspondence.pdf

2335-KOLNP-2005-DESCRIPTION (COMPLETE) 1.1.pdf

2335-KOLNP-2005-EXAMINATION REPORT REPLY RECIEVED.pdf

2335-KOLNP-2005-EXAMINATION REPORT.pdf

2335-KOLNP-2005-FORM 1 1.1.pdf

2335-KOLNP-2005-FORM 18 1.1.pdf

2335-kolnp-2005-form 18.pdf

2335-KOLNP-2005-FORM 2 1.1.pdf

2335-KOLNP-2005-FORM 3.pdf

2335-KOLNP-2005-FORM 5 1.1.pdf

2335-KOLNP-2005-FORM 5.pdf

2335-KOLNP-2005-GPA 1.1.pdf

2335-kolnp-2005-gpa.pdf

2335-KOLNP-2005-GRANTED-ABSTRACT.pdf

2335-KOLNP-2005-GRANTED-CLAIMS.pdf

2335-KOLNP-2005-GRANTED-DESCRIPTION (COMPLETE).pdf .pdf

2335-KOLNP-2005-GRANTED-FORM 1.pdf

2335-KOLNP-2005-GRANTED-FORM 2.pdf

2335-KOLNP-2005-GRANTED-SPECIFICATION.pdf .pdf

2335-kolnp-2005-international publication.pdf

2335-kolnp-2005-international search report.pdf

2335-KOLNP-2005-OTHERS.pdf

2335-kolnp-2005-pct request form.pdf

2335-KOLNP-2005-REPLY TO EXAMINATION REPORT 1.1.pdf


Patent Number 253478
Indian Patent Application Number 2335/KOLNP/2005
PG Journal Number 30/2012
Publication Date 27-Jul-2012
Grant Date 25-Jul-2012
Date of Filing 22-Nov-2005
Name of Patentee ENGELHARD CORPORATION
Applicant Address 101, WOOD AVENUE, P.O. BOX 770, ISELIN, NJ
Inventors:
# Inventor's Name Inventor's Address
1 STOCKWELL, DAVID, MATHESON 100 NELSON PLACE, WESTFIELD, NJ 07090
2 XU, MINGTING 215, MONROE AVENUE, EDISON, NJ 08820
PCT International Classification Number B01J 29/08
PCT International Application Number PCT/US2004/014651
PCT International Filing date 2004-05-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/440,608 2003-05-19 U.S.A.