Note: Descriptions are shown in the official language in which they were submitted.
W 0 95/21021
PCT/US95/00991
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This invention relates to an improved catalyst
composition comprising the zeolite MCM-22.
MCM-22 is a known zeolite, whose characterising X-ray
diffraction pattern and method of synthesis are described
in U.S. Patent No. 4,954,325. In particular, MCM-22 has an
X-ray diffraction pattern including the lines listed in
Table l, below:
T
Inten,~~anar d-Sy~acina 1A) Rglat~ve Tntena~+~ I/I x X00
12.36 ~ 0.4 M-VS
11.03 ~ 0.2 M-S
8.83 ~-0.14 M-VS
6.18 ~ 0.12 M-VS
6.00 ~ 0.10 W-M
4.06 ~ 0.07 W-S
3.91 ~ 0.07 M-VS
3.42 ~ 0.06 VS
It is also known, see U.S. Patent Nos. 4,983,276 and
5,039,640, that MCM-22 is useful in catalytic cracking,
such as fluid catalytic cracking (FCC), to increase the
total gasoline yield and the octane number of the gasoline
fraction.
It is desirable to improve the hydrothermal stability
of MCM-22 containing catalysts particularly where the
catalysts are subjected to repeated cycles of high
temperature steaming such as is experienced in the FCC
process.
In accordance with the present invention, there is
provided an improved catalyst composition comprising
phosphorus in combination with a zeolite having an X-ray
diffraction pattern including the following lines:
WO 95121021 ~ PCTlUS95100991
-a-
Internlanar d-Spacina lA1 Reiat we Tntensity T/T x X00
12.36 + 0.4 M-VS
11.03 + 0.2 M-S
8.83 + 0.14 M-VS
6.18 ~ 0.12 M-VS
6.00 + 0.10 W-M
4.06 + 0.07 W-S
3.91 + 0.07 M-VS
3.42 t 0.06 VS
A matrix material may be included in the catalyst
composition of this invention and the phosphorus may be
added to either the porous crystalline material, the matrix
material or both materials. Also the catalyst composition
of this invention may be admixed with a large pore
crystalline molecular sieve or mesoporous material. The
improved catalyst of this invention may be used in organic
conversion processes, such as catalytic cracking processes.
The catalyst composition of the present invention
comprises the aeolite MCM-22 which, in its calcined form,
has an X-ray diffraction pattern including the lines listed
in Table 1 above. Generally, the calcined form of MCM-22
has an X-ray diffraction pattern including the following
lines shown in Table 2 below:
TA8~.13 2
Integ~lanar d-Snacina (A1 Relative Intensity. I/2_ x 100
30.0 + 2.2 W-M
22.1 + 1.3 W
12.36 + 0.4 M-VS
11.03 ~ 0.2 M-S
8.83 t 0.14 M-VS
6.18 + 0.12 M-VS
6.00 + 0.10 W-M
4.06 + 0.07 W-S
3.91 + 0.07 M-VS
3.42 + 0.06 VS
t W0 95121021 ~ ~ ~ ~ ~ ~ - ° '~' r r , PCTIUS95100991
-3-
More specifically, the calcined form of MCM-22 has an
X-ray diffraction pattern including the following lines
shown in Table 3 below:
TABLE 3
I nterplana r -Spacing 1A) Relative Intensify. I/I_ x 100
d
12.36 0.4 M-VS
11.03 0.2 M-S
8.83 0.14 M-VS
6.86 0.14 W-M
6.18 0.12 M-VS
6.00 0.10 W-M
5.54 0.10 W-M
4.92 0.09 W
4.64 0.08 W
4.41 +_0.08 W-M
4.25 0.08 W
4.10 0.07 W-S
4.06 0.07 W-S
3.91 0.07 M-VS
3.75 0.06 W-M
3.56 0.06 W-M
3.42 0.06 VS
3.30 0.05 W-M
3.20 0.05 W-M
3.14 0.05 W-M
3.07 0.05 W
2.99 0.05 W
2.82 0.05 W
2.78 0.05 W
2.68 0.05 W
2.59 D.05 W
Most specifically, the calcined form of MCM-22 has an
X-ray diffraction pattern including the following lines
shown in Table 4 below:
WO 95121021 PGTIUS95100991
-4-
TAB LE 4
I nternlana r d-Snacina lA1 elative Intensity. j
R L
x 100
,
"
30.0 2.2 W-M
22.1 1.3 W
12.36 0.4 M-VS
11.03 0.2 M-S
8.83 0.14 M-VS
6.86 0.14 W-M
6.18 0.12 M-VS
6.00 0.10 W-M
5.54 0.10 W-M
4.92 0.09 W
4.64 0.08 W
4.41 0.08 W-M
4.25 0.08 W
4.10 0.07 W-S
4.06 0.07 W-S
3.91 0.07 M-VS
3.75 0.06 W-M
3.56 0.06 W-M
3.42 0.06 VS
3.30 0.05 W-M
3.20 0.05 W-M
3.14 0.,05 W-M
3.07 0.05 W
2.99 0.05 W
2.82 0.05 W
2.78 0.05 W
2.68 0.05 W
2.59 0.05 W
These values were determined by standard techniques.
The radiation was the K-alpha doublet of copper and a
diffractometer equipped with a scintillation counter and an
associated computer was used. The peak heights, I, and the
positions as a function of 2 theta, where theta is the
~~80.~~~ _
W095121021 '~ ' ' f'P - , PCTIUS95I00991
-5-
Bragg angle, were determined using algorithms on the
computer associated with the diffractometer. From these,
the relative intensities, 100 I/Io, where Io is the
intensity of the strongest line or peak, and d (obs.) the
interplanar spacing in Angstrom Units (A), corresponding to
the recorded lines, were determined. In Tables 1-4, the
relative intensities are given in terms of the symbols W =
weak, M = medium, S = strong, VS = very strong. In terms
of relative intensities, these may be generally designated
as follows:
W - 0-20
M - 20-40
S = 40-60
VS - 60-100
Zeolite MCM-22 has a chemical composition expressed by
the molar relationship:
X203:(n)Y02,
where X is a trivalent element, such as aluminum, boron,
iron and/or gallium, preferably aluminum, Y is a
tetravalent element such as silicon and/or germanium,
preferably silicon, and n is at least 10, usually from 10
to 150, more usually from 10 to 60, and even more usually
from 20 to 40. In the as-synthesized form, zeolite MCM-22
has a formula, on an anhydrous basis and in terms of moles
of oxides per n moles of Y02, as follows:
(0.005-0.1)Na20:(1-4)R:X203:nY02
where R is an organic component. The Na and R components
are associated with the zeolite as a result of their
presence during crystallization, and are easily removed by
conventional post-crystallization methods.
As is evident from the above formula, MCM-22 is
synthesized nearly free of Na cations and thus possesses
acid catalysis activity as synthesized. It can, therefore,
be used as a component of the catalyst composition herein
without having to first undergo an ion exchange step. To
the extent desired, however, the original sodium cations of
CA 02180115 2004-12-06
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the as-synthesized material can be replaced at least in
part by established techniques including ion exchange with
other cations. Preferred replacement cations include metal
ions, hydrogen ions, hydrogen precursor ions, e.g.,
ammonium and mixtures of such ions. Particularly preferred
cations are those which tailor the activity of the catalyst
for cracking. These include hydrogen, rare earth metals
and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB,
and VIII of the Periodic Table of the Elements.
Zeolite MCM-22 can be prepared from a reaction mixture
containing sources of alkali or alkaline earth metal (M),
e.g., sodium or potassium, cation, an oxide of trivalent
element X, e.g, aluminum, an oxide of tetravalent element
Y, e.g., silicon, an organic (R) directing agent, described
below, and water. The reaction mixture has a composition,
in terms of mole ratios of oxides, within the following
ranges:
Rgactants sefu Preferred
Y02/X203 10 - 60 10 - 40
H20/Y02 5 - 100 10 - 50
OH /Y02 0.01 - 1.0 0.1 - 0.5
M/Y02 0.01 - 2.0 0.1 - 1.0
R/Y02 0.05 - 1.0 0.1 - 0.5
The organic directing agent for use in synthesizing
zeolite MCM-22 from the above reaction mixture is
hexamethyleneimine.
In a preferred method of synthesizing zeolite MCM-22,
the Y02 reactant contains a substantial amount of solid
Y02, e.g., at least about 30 wt.% solid Y02. Where Y02 is
silica, the use of a silica source containing at least
about 30 wt.% solid silica, e.g., Ultrasil (a precipitated,
spray dried silica containing about 90 wt.% silica) or
HiSil (a precipitated hydrated Si02 containing about 87
wt.% silica, about 6 wt.% free Ha0 and about 4.5 wt.% bound
H20 of hydration and having a particle size of about 0.02
WO 95!21021 ' ' a ' ,.. PCTlU595100991
2180.~1~
-.,- " 9,
micron) favors crystal formation from the above mixture.
If another source of oxide of silicon, e.g., Q-Brand (a
sodium silicate comprised of about 28.8 wt.% of Si02, 8.9
wt.% Na20 and 62.3 wt.% H20) is used, crystallization may
yield impurity phases of other crystal structures, e.g.,
ZSM-12. Preferably, therefore, the Y02, e.g., silica,
source contains at least about 30 wt.% solid Y02, e.g.,
silica, and more preferably at least about 40 wt.% solid
Y02, e.g., silica.
Crystallization of the MCM-22 crystalline material can
be carried out at either static or stirred conditions in a
suitable reactor vessel such as, e.g., polypropylene jars
or teflon-lined or stainless steel autoclaves, at a
temperature of 80'C to 225'C for 25 hours to 230 days,
after which the crystals are separated from the liquid and
recovered.
The present invention concerns a composition
comprising a porous crystalline material characterized by
an X-ray diffraction pattern including values substantially
as set forth in Table 1 of the specification, said porous
crystalline material having been contacted With a source of
phosphorus. The composition may further comprise at least
one matrix material, non-limiting examples of which include
at least one of clay, alumina, silica and mixtures thereof.
Either the porous crystalline material, the matrix
material, or both may be contacted with the source of
phosphorus .
One embodiment of the present invention is a method
for manufacture of a composition comprising the steps of
modifying a porous crystalline material characterized by an
X-ray diffraction pattern including values substantially as
set forth in Table 1 of the specification by contacting
said porous crystalline material with a source of
phosphorus and forming a catalyst particle from the
phosphorus modified porous crystalline material.
W095/21021 ~~a~~~~ PCT/US95/00991
G~ 1 _g_
Another embodiment of the present invention is a
method for manufacture of a composition comprising the
steps of combining a porous crystalline material
characterized by an X-ray diffraction pattern including
values substantially as set forth in Table 1 of the
specification and a source of phosphorus and at least one
of a source of clay, a source of silica, a source of
alumina, and mixtures thereof, and forming catalyst
particles from said combination.
A more specific embodiment of this invention is a
method for manufacture of a composition comprising the
steps of preparing a slurry of a porous crystalline
material characterized by an X-ray diffraction pattern
including values substantially as set forth in Table 1 of
the specification, then blending a source of clay into the
slurry, then adding a source of phosphorus to the slurry,
then adding a source of silica and a source of alumina to
the slurry, and finally forming catalyst particles from the
slurry. The phosphorus may be added to any one or all of
the slurries used to make the product. The phosphorus may
also be added to the formed particle or to any particle
used in the composition.
Non-limiting examples of the source of phosphorus
useful in the present invention include ammonium
monohydrogen phosphate, ammonium dihydrogen phosphate,
triammonium phosphate, ammonium hypophosphate, ammonium
orthophosphate, ammonium dihydrogen orthophosphate,
ammonium monohydrogen orthophosphate, ammonium
hypophosphite, ammonium dihydrogen orthophosphite,
phosphoric acid and mixtures thereof, more specifically
phosphoric acid and ammonium dihydrogen phosphate, and most
specifically, phosphoric acid.
After treatment with the phosphorus source, but prior
to use, the catalyst composition of the invention is
preferably heated in the presence of oxygen, such as in
air, typically at a temperature of 150 to 750'C. The
WO 95/21021 ' .' ~' ~' ? r~
PCT/US95/00991
w4 y~i -
-9-
phosphorus is typically added in an amount sufficient to
yield a concentration of at least 0.1 wt.%, preferably 0.5
to l5wt%, on the finished catalyst. It will be appreciated
that the phosphorus on the final catalyst will probably not
be present in elemental form but rather as an oxide.
Non-limiting examples of the matrix material include
clays and inorganic oxides. Naturally occurring clays which
can be used as matrix material include the montmorillonite
and kaolin family, which families include the
subbentonites, and the kaolins commonly known as Dixie,
McNamee, Georgia, and Florida clays or others in which the
main mineral constituent is halloysite, kaolinite, dickite,
nacrite, or anauxite. Inorganic oxides which can be used as
the matrix material include silica, alumina, silica-
alumina, silica-magnesia, silica-zirconia, silica-thoria,
silica-berylia, silica-titanic, as well as ternary oxide
compositions such as silica-alumina-thoria, silica-alumina-
zirconia, silica-alumina-magnesia, and silica-magnesia-
zirconia. The relative proportions of catalyst components)
and matrix can vary widely with the content of the former
ranging from 1 to 95, and more usually from 10 to 70,
weight percent, of the composite.
Preferred examples of materials useful in this
invention include kaolin clay as the source of clay,
phosphoric acid or ammonium dihydrogen phosphate as the
source of phosphorus, colloidal silica as the source of
silica, and pseudoboehmite alumina as the source of
alumina. Preferably, the catalyst should be formed and
dried as rapidly as possible after mixing.
The composition of this invention may be useful in
catalytic cracking, either alone, combined with a matrix,
combined with a large pore crystalline molecular sieve,
which is itself catalytically active, combined with a
mesoporous material, or with combinations of the above.
The large pore (e. g., greater than about 7 Angstrome,~
crystalline molecular sieve which may be used is a material
~ CA 02180115 2004-12-06
-1G-
normally having a Constraint Index (as defined in U.S.
Patent No. 4,016,218)
less than 1. Large pore crystalline molecular sieves are
well known i.n the art and include faujasite, mordenite,
zeolite X, rare-earth exchanged zeolite X (REX), zeolite Y,
zeolite Y (HY), rare earth-exchanged ultra stable zeolite Y
(RE-USY), dealuminized Y (DAY), ultrahydrophobic zeolite Y
(UHP-Y), dealuminized silicon enriched zeolites such as LZ-
210, zeolite ZK-5, zeolite ZK-4, zeolite Beta, zeolite
l0 Omega, zeolite L, ZSM-20 and other natural or synthetic
zeolites.
Other large pore crystalline molecular sieves which
are useful herein include pillared silicates and/or clays:
aluminophosphates, e.g., ALP04-5, VPI-5; silicoalumino-
phospates, e.g., MCM-9, SAPO-5, SAPO-37, SAPO-31, SAPO-40,
SAPO-41: and other metal aluminophosphates. These
materials are variously described in U.S. Patent Nos.
4,440,871; 4,554,143: 4,567,029: 4,666,875; 4,742,033
The mesoporous materials useful in the present
invention include crystals having uniform pores within the
range of from about 13 A to about 200 A in diameter, more
usually from about 15 A to about 100 A. Since these pores
are significantly larger than those of other crystalline
materials, it is also appropriate to refer to them as
ultra-large pore size materials. For the purposes of this
application, a working definition of "porous" is a material
that absorbs at least 1 gram of a small molecule, such as
Ar, N2, n-hexane, or cyclohexane, per 100 grams of solid.
Non-limiting examples of mesoporous material are MCM-41 and
MCM-48, which are substantially described in U.S. Patent
Nos. 5,098,684; 5,102,643: 5,198,203. These mesoporous
materials are useful in catalytic cracking processes as
disclosed in U.S. Patent No. 5,232,580.
The amount of the porous crystalline material of Table
1 which is added to the large pore or mesoporous
crystalline cracking catalyst component may vary from
W 0 95/21021 PCT/OS95100991
.'-~ .;
-11-
cracking unit to cracking unit depending upon the desired
octane number, total gasoline yield required, the nature of
the available feedstock and other similar factors. For
many cracking operations, the weight percent of the porous
crystalline material (e. g., MCM-22) relative to the total
quantity of catalyst composition can range from 0.1 to 90
wt.%, specifically from 1 to 75 wt.%, more specifically
from 2 to 50 wt.%., and most specifically from 4 to 25
wt.%.
Although the phosphorus-containing catalyst
composition of the invention need not be steamed prior to
use in a catalytic cracking process, and, in fact, will
typically not be steamed prior to use therein, it may be
steamed at a temperature of 300°C to 800'C for a time of 1
to 200 hours in 5 to 100 % steam.
As mentioned earlier, the catalyst composition of this
invention is useful as a catalyst for organic compound,
e.g., hydrocarbon compound, conversion. Non-limiting
examples of processes for organic compound conversion
include Fluid Catalytic Cracking (FCC) and other forms of
catalytic cracking including moving bed catalytic cracking
and hydrocracking.
Suitable catalytic cracking conditions include a
temperature ranging from 370 to 700'C (700 to 1300'F) and a
pressure ranging from subatmospheric to several hundreds of
atmospheres. The catalytic cracking process can be either
fixed bed, moving bed, transfer line, or fluidized bed, and
the hydrocarbon flow may be either concurrent or
countercurrent to the catalyst flow. The process of the
invention is particularly applicable to the Fluid Catalytic
Cracking (FCC) or Thermofor Catalytic Cracking (TCC)
processes. In both of these processes, the hydrocarbon
feed and catalyst are passed through a reactor and the
catalyst is regenerated. The two processes differ
substantially in the size of the catalyst particles and in
WO 95121021 ~ ~ ~~~ PCTIUS95100991
~1 -
the engineering contact and transfer which is at least
partially a function of catalyst size.
The TCC process is a moving bed and the catalyst is in
the shape of pellets or beads having an average particle
size of about one-sixty-fourth to one-fourth inch. Active,
hot catalyst beads progress downwardly cocurrent with a
hydrocarbon charge stock through a cracking reaction zone.
The hydrocarbon products are separated from the coked
catalyst and recovered, and the catalyst is recovered at
the lower end of the zone and regenerated.
Typical TCC conversion conditions include an average
reactor temperature of 450°C to 540°C; catalyst/oil volume
ratio of 2 to 7; reactor volume hourly space velocity of 1
to 5 vol./hr./vol.; and recycle to fresh feed ratio of
from 0 to 0.5 (volume).
The process of the invention is also applicable to
Fluid Catalytic Cracking (FCC). In fluidized catalytic
cracking processes, the catalyst is a fine powder of 10 to
200 microns. This powder is generally suspended in the
2o feed and propelled upward in a reaction zone. A relatively
heavy hydrocarbon feedstock, e.g., a gas oil, is admixed
with a suitable cracking catalyst to provide a fluidized
suspension and cracked in an elongated reactor, or riser,
at elevated temperatures to provide a mixture of lighter
hydrocarbon products. The gaseous reaction products and
spent catalyst are discharged from the riser into a
separator, e.g., a cyclone unit, located within the upper
section of an enclosed stripping vessel, or stripper, with
the reaction products being conveyed to a product recovery
zone and the spent catalyst entering a dense catalyst bed
within the lower section of the stripper. In order to
remove entrained hydrocarbons from the spent catalyst prior
to conveying the latter to a catalyst regenerator unit, an
inert stripping gas, e.g., steam, is passed through the
catalyst bed where it desorbs such hydrocarbons conveying
them to the product recovery zone. The fluidizable
2~~~.~.1 J
W095121021 ~ , ~ ,_ PCT/US95100991
"~d . r
-13- ' v
catalyst is continuously circulated between the riser and
the regenerator and serves to transfer heat from the latter
to the former thereby supplying the thermal needs of the
cracking reaction which is endothermic.
The FCC conversion conditions include a riser top
temperature of 500'C to 595'C, specifically 520'C to 565'~C,
and most specifically 530'C to 550'C; catalyst/oil weight
ratio of 3 to 12, specifically 4 to 11, and most
specifically 5 to 10; and catalyst residence time of 0.5
to 15 seconds, specifically 1 to 10 seconds.
It is generally necessary that the catalysts be
resistant to mechanical attrition, that is, the formation
of fines which are small particles, e.g., less than 20 ~Cm.
The cycles of cracking and regeneration at high flow rates
and temperatures, such as in an FCC process, have a
tendency to break down the catalyst into fines, as compared
with an average diameter of catalyst particles of 60-100
microns. In an FCC process, catalyst particles range from
10 to 200 microns, preferably from 20 to 150 microns.
Excessive generation of catalyst fines increases the
refiner's catalyst costs.
The feedstock, that is, the hydrocarbons to be
cracked, may include in whole or in part, a gas oil (e. g.,
light, medium, or heavy gas oil) having an initial boiling
point above about 204'C, a 50 % point of at least about
260'C, and an end point of at least about 315'C. The
feedstock may also include deep cut gas oil, vacuum gas
oil, thermal oil, residual oil, cycle stock, whole top
crude, tar sand oil, shale oil, synthetic fuel, heavy
hydrocarbon fractions derived from the destructive
hydrogenation of coal, tar, pitches, asphalts, hydrotreated
feedstocks derived from any of the foregoing, and the like.
As will be recognized, the distillation of higher boiling
petroleum fractions above about 400'C must be carried out
under vacuum in order to avoid thermal cracking. The
boiling temperatures utilized herein are expressed in terms
W0 95121021 PCTIUS95I00991
-14-
of convenience of the boiling point corrected to
atmospheric pressure. Resids or deeper cut gas oils having
an end point of up to about 700'C, even with high metals
contents, can also be cracked using the invention.
The invention will now be more particularly described
with reference to the Examples and the accompanying
drawing, which is a graph showing the effect of phosphorus
addition on the alpha activity of MCM-22 catalysts exposed
to steam at 540'C.
In the Examples, when alpha value is examined, it is
noted that the alpha value is an approximate indication of
the catalytic cracking activity of the catalyst compared to
~a standard catalyst and it gives the relative rate constant
(rate of normal hexane conversion per volume of catalyst
per unit time). It is based on the activity of silica-
alumina cracking catalyst taken as an alpha of 1 (rate
constant is 0.016 sec 1). The alpha test is described in
U.S. Patent No. 3,354,078: in the Journal of Catalysis,
Vol. 4, p 527 (1965): Vol. 6, p. 278 (1966): and Vol. 61,
p. 395 (1980). The experimental conditions of the test
used herein include a constant temperature of 538'C and a
variable flow rate as described in detail in the Journal of
Catalysis, Vol. 61, p. 395. The higher alpha values
correspond with a more active cracking catalyst.
When ion-exchange capacity and temperature of the
maximum rate of ammonia desorption are examined, they are
determined by titrating, with a solution of sulfamic acid,
the gaseous ammonia evolved during the temperature-
programmed decomposition of the ammonium-form of the
zeolite or its phosphorus incorporated form (TPAD). The
basic method is described in Thermochimica Acta, Vol. III,
pp. 113-124, 1971, by G. T. Kerr and A. W. Chester.
The 130.3 Mh2 27A1 nuclear magnetic resonance (NMR)
quantitative data were obtained using 1.5 ~s pulses with
the solution 90'=9.0 ~s and a 100 ms recycle. The method
is similar to that described in Klinowski, J., Thomas, J.
~~80.~.IJ
WO95/21021 ~ f ~ , rr PCT/US95100991
'f X~ ,:,
M., Fyfe, C. A., Gobbi, G. C., and Hartman, J. S., Inora.
Chem., 22 (1983) 63.
Whenever sorption data are set forth for comparison of
sorptive capacities for water, cyclohexane and/or n-hexane,
they are Equilibrium Adsorption values determined as
follows:
A weighed sample of the calcined adsorbent was
contacted with the desired pure adsorbate vapor in an
adsorbent chamber, evacuated to less than 1 mm Hg and
contacted with 1.6 kPa (12 Torr) of water vapor or 5.3 kPa
(40 Torr) of n-hexane or 5.3 kPa (40 Torr) of cyclohexane
vapor, pressures less than the vapor-liquid equilibrium
pressure of the respective adsorbate at 90'C. The pressure
was kept constant (within about ~ 0.5 mm Hg) by addition of
adsorbate vapor controlled by a manostat during the
adsorption period, which did not exceed about 8 hours. As
adsorbate was adsorbed by the MCM-22 crystalline material,
the decrease in pressure caused the manostat to open a
valve which admitted more adsorbate vapor to the chamber to
restore the above control pressures. Sorption was complete
when the pressure change was not sufficient to activate the
manostat. The increase in weight was calculated as the
adsorption capacity of the sample in g/100 g of calcined
adsorbent. Before phosphorus addition, zeolite MCM-22
exhibits equilibrium adsorption values than about 1o wt.%
for water vapor, greater than about 4.5 wt.%, usually
greater than about 7 wt.% for cyclohexane vapor and greater
than about 10 wt.% for n-hexane vapor.
Catalysts of this invention were prepared and tested
for attrition resistance as represented by an Attrition
Index (AI). The Attrition Index is defined as the weight
percentage of the fines generated during the test that are
20 microns or less in size relative to the amount of
material larger than 20 microns present before the test.
In the test, a 7 cc catalyst sample is contacted in a 1
inch (inside diameter) U-tube with an air jet formed by
WO 95121021 ~ ~ PCTlUS95100991
-16-
humidified (60%) air through an 0.07 inch nozzle at
21 liters per minute for one hour.
wt.% fines AA - wt.% fines BA
AI = 100
100 - wt.% fines BA
where BA is before attrition test and AA is after attrition
test. The lower the Attrition Index, the more attrition
resistant is the catalyst.
Example 1
MCM-22, synthesized according to U.S. Patent
4,954,325, was calcined at 480'C (900'F) in nitrogen for 3
hours and then in air at 540'C (1,000'F) for 9 hours. MCM-
22 was then ammonium exchanged, dried at 250'F and air
calcined at 1,000'F for 3 hours. The resulting catalyst is
designated Catalyst A and has the following properties:
Phosphorus content, Wt.% 0
Alpha activity 280
TPAD 0.63 meq NH3/g
Td A1203, wt.%, 27A1 NMR 3.2
A sample prepared similarly to that of Example 1 was
contacted with an aqueous solution of ammonium dihydrogen
phosphate to incorporate a nominal 1 wt.% phosphorus, dried
at 120'C (250'F) and calcined in air at 540'C (1,000'F) for
3 hours. It was then steamed at 540'C (1,000'F) for 2.5
hours. The resulting catalyst is designated Catalyst 8 and
has the following properties:
Phosphorus content, Wt.% 1
Alpha activity 154
TPAD 0.22 meq NH3/g
Td A1203, wt.%, 27A1 NMR 2.1
CA 02180115 2004-12-06
-1~-
The catalyst of Example 2 showed a reduction of 45% in
alpha activity, 65% in TPAD value, and 34% in 27A1 NMR
value after steaming.
EEamDl~
A sample of the catalyst prepared in Example 1 above
was steamed at 540°C (1,000°F) for 2.5 hours. The catalyst
was not contacted with phosphorus before steaming. The
resulting catalyst is designated Catalyst C and has the
following properties:
Phosphorus content, Wt.%- 0
Alpha activity 72
TPAD 0.15 meq NH3/g
Td A1203, wt.%, 27A1 NMR 1.6
The catalyst of Example 3 showed a decrease of 74% in
alpha activity, 76% in TPAD, and 50% in 27A1 NMR value
after steaming. Examples 2 and 3 show that incorporation
of phosphorus improves retention of framework aluminum and,
correspondingly cracking activity, in steamed catalysts.
Example 4
A phosphorus modified fluid catalyst containing 25
wt.% zeolite MCM-22 was prepared by first making a slurry
of zeolite MCM-22, synthesized according to U.S. Patent
4,954,325. The zeolite slurry was prepared by calcining
zeolite MCM-22 for 3 hours at 480°C (900°F) and then
ballmilling the calcined zeolite for 16 hours at 25% solids
with deionized water (DI) and using o.6 wt.% dispersant
(Marasperse N-22, Reed-Lignin, Inc., Greenwich, CT).
Kaolin clay (Kaopaque 10S, a Georgia kaolin clay, Dry
Branch Chemical Co., Dry Branch, GA) was then blended into
the zeolite slurry. To the zeolite and clay slurry,
sufficient phosphoric acid (J. T. Baker Co., Phillipsburg,
NJ) was added to result in a phosphorus level of 1.9 wt.%
on the finished catalyst. A silica-alumina binder was then
CA 02180115 2004-12-06
-18-
x~
added to the slurry by first adding colloidal silica (Nalco
1034A, Nalco Chemical Co., Chicago, IL) and then alumina
(Condea Pural, SBIII pseudoboehmite alumina, Condea Chemie
GMBii, Hamburg, Genaany) peptized with formic acid. The
matrix contains about 50 wt.% clay and about 50 wt.% binder
and the binder contains about 5 parts by weight silica and
about 1 part by weight alumina. The resulting slurry was
spray dried (Niro Inc., Columbia, MD, spray dryer) at an
outlet temperature of 180°C (360°F). The spray dried
material was calcined for two hours at 540°C (1,000°F) in
air. The resulting catalyst is designated Catalyst D and
has the following properties:
Phosphorus content, Wt.% 1.9
Alpha activity 51
EESmDle 5
A phosphorus modified fluid catalyst containing 25
wt.% zeolite MCM-22 was prepared by first making a slurry
of zeolite MCM-22. The zeolite slurry was prepared by
precalcining zeolite MCM-22 for 3 hours at 480°C (900°F) in
nitrogen and then ballmilling the calcined zeolite for 16
hours at 25% solids with deionized water (DI) and using 0.6
wt.% dispersant (Marasperse N-22). Kaolin clay (Kaopaque
10S, a Georgia kaolin clay) was then blended into the
zeolite slurry. To the zeolite and clay slurry, sufficient
ammonium dihydrogen phosphate (Sigma-Aldrich Corp.,
Milwaukee, WI) was added to result in a phosphorus level of
1.6 wt.% on the finished catalyst. A silica-alumina binder
was then added to the slurry by first adding colloidal
silica (Nalco 1034A) and then alumina (Condea Pural, SBIII
pseudoboehmite alumina) peptized with formic acid. The
matrix contains about 50 wt.% clay and about 50 wt.% binder
composed of about 5 parts by weight silica and about 1 part
by weight alumina. The resulting slurry was spray dried at
an outlet temperature of 180°C (360°F). The spray dried
material was calcined for two hours at 540°C (1,000°F) in
WO 95121021 ~ ~ ~' ' a ' ' pCT/US95100991
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air. The resulting catalyst is designated Catalyst E and
has the following properties:
Phosphorus content, Wt.% 1.6
Alpha activity 50
ExamDl~ 6
A catalyst compositionally similar to the catalysts
prepared in Examples 4 and 5 was prepared without the use
of phosphorus by mixing the silica-alumina binder (Nalco
1034A silica and Condea Pural SBIII pseudoboehmite alumina,
peptized with formic acid), and subsequently adding the
kaolin clay (Kaopaque 10S) and then the ballmilled zeolite
slurry. The ballmilled zeolite slurry was prepared by
precalcining zeolite MCM-22 for 3 hours at 480'C (900°F) in
nitrogen and ballmilling the calcined zeolite for 16 hours
at 25% solids with deionized water (DI) and 0.6 wt.%
dispersant (Marasperse N-22). The matrix contains about 50
wt.% clay and about 50 wt.% binder compsed of about 5 parts
by weight silica and about 1 part by weight alumina. The
resulting slurry was spray dried at an outlet temperature
of 180'C (360'F). The spray dried material was calcined
for 2 hours in air at 540'C (1,000'F). The resulting
catalyst is designated Catalyst F and has the following
properties:
Phosphorus content, Wt.% 0
Alpha activity ~2
A comparison of the properties of the catalysts of
Examples 4, 5, and 6 shows that the incorporation of
phosphorus into the catalyst composition initially
decreases the alpha activity of the catalyst.
~samDlB 7
Three identical samples of the calcined catalyst of
Example 4 were treated in 100% steam at 540'C (1,000'F) ~t
atmospheric pressure for either 2, 5, or 10 hours. These
WO 95/21021 PCTlUS95100991
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steam treated catalysts are designated Catalysts G, H, and
I and have the following properties:
Catalyst Steaming Phosphorus Alpha
Designation Time. hrs Content, wt.% Aotivitv
G 2 1.9 30
H 5 1.9 26
I 10 1.9 16
~z~yple 8
Three identical samples of the calcined catalyst of
Example 5 were treated in 100% steam at 540' (1,000'F) at
atmospheric pressure for either 2, 5, or 10 hours. These
steam treated catalysts are designated Catalysts J, R, and
L and have the following properties:
Catalyst Steaming Phosphorus Alpha
Designation Time. hrs Content, wt.% Activity
J 2 1.6 29
K 5 1.6 26
I. 10 1. 6 17
A comparison of the alpha activities of the catalysts
of Examples 7 and 8 shows that the incorporation of
phosphorus into the catalyst via either phosphoric acid or
ammonium dihydrogen phosphate results in a similar response
of alpha as a function of steaming time.
>;xample 9
Three identical samples of the calcined catalyst of
Example 6 were treated in 100% steam at 540'C (1,000'F) at
atmospheric pressure for either 2, 5, or 10 hours. These
steam treated catalysts are designated Catalysts M, N, and
O and have the following properties:
CA 02180115 2004-12-06
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Catalyst Steaming Phosphorus Alpha
Designation Time, hrs Content, wt.% Activitv
M 2 0 10
N 5 0 8
O 10 0 3
A comparison of the alpha activities of the catalysts
presented in Example 9 with those presented in Examples 7
and 8 shows that the incorporation of phosphorus into the
catalyst composition improves the hydrothermal stability of
the catalyst. The catalysts prepared according to Examples
4 and 5 have a higher alpha activity after exposure to
steam than the catalyst prepared according to Example 6.
The alpha activity data presented in Examples 4
through 9 are shown graphically in Figure 1.
Eaam~le 10
A phosphorus modified fluid catalyst was prepared by
first ammonium exchanging as-synthesized (containing the
organic directing agent) MCM-22 with 1 N NH4N03, 25 cc/g
wet cake. Then a zeolite slurry was prepared by
ballmilling the zeolite for 16 hours at 8.8 % solids with
deionized water (DI) and using 0.6 wt.% dispersant
(Marasperse N-22) and kaolin clay (Thiele RC-32, Thiele
Kaolin Co., Sandersonville, GA) was added to the zeolite
slurry. Next, phosphoric acid was added to the slurry to
result in a phosphorus level of 2.8 wt.% on the finished
catalyst. A silica-alumina binder was then added to the
slurry by first adding colloidal silica and then alumina
(Condea Pural, SBIII pseudoboehmite alumina) peptized with
formic acid. The resulting slurry (18 wt.% solids) was
spray dried at an outlet temperature of 177°C (350°F). The
spray dried material was calcined for two hours at 540°C
(1,000°F) in air. The resulting catalyst is designated
Catalyst P and includes about 40 wt.% zeolite. The matrix
R'O 95121021 ~ PCT/1JS95100991
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contains about 50 wt.% clay and about 50 wt.% binder and
has a binder silica-alumina ratio of about 5:1.
X19 1l
A phosphorus modified fluid catalyst was prepared by
first ammonium exchanging as-synthesized (containing the
organic directing agent) MCM-22 with 1 N NH4N03, 25 cc/g
wet cake. Then the zeolite was nitrogen precalcined for 3
hours at 480'C (900'F). Next, a zeolite slurry was
prepared by ballmilling the zeolite for 16 hours at 23 %
solids with defonized water (DI) and using 0.6 wt.%
dispersant (Marasperse N-22) and kaolin clay (Kaopaque 10S)
was added to the zeolite slurry. Phosphoric acid was added
to the slurry to result in a phosphorus level of 3.1 wt.%
on the finished catalyst. A silica-alumina binder was then
added to the slurry by first adding colloidal silica and
then alumina (Condea Pural, SBIII pseudoboehmite alumina)
peptized with formic acid. The resulting slurry (28 wt.%
solids) was spray dried at an outlet temperature of 177'C
(350'F). The spray dried material was calcined for two
hours at 540'C (1,000'F) in air. The resulting catalyst is
designated Catalyst Q and includes about 40 wt.% zeolite.
The matrix contains about 50 wt.% clay and about 50 wt.% of
binder and has a binder silica-alumina ratio of about 5:1.
A phosphorus modified fluid catalyst was prepared by
first ammonium exchanging as-synthesized (containing the
organic directing agent) MCM-22 with 1 N NH4N03, 25 cc/g
wet cake. Then the zeolite was hybrid calcined [e. g.,
nitrogen precalcined for 3 hours at 480'C (900'F) and then
air calcined for 6 hours at 540'C (1,000'F)]. Next, a
zeolite slurry was prepared by ballmilling the zeolite for
16 hours at 30 % solids with deionized water (DI) and using
0.6 wt.% dispersant (Marasperse N-22) and kaolin clay
r W095I21021 , PCTIUS95I00991
-23-
(Raopaque 10S) was added to the zeolite slurry. Phosphoric
acid was added to the slurry to result in a phosphorus
level of 2.9 wt.% on the finished catalyst. A silica-
alumina binder was then added to the slurry by first adding
colloidal silica and then alumina (Condea Pural, SBIII
pseudoboehmite alumina) peptized with formic acid. The
resulting slurry (28 wt.% solids) was spray dried at an
outlet temperature of 177'C (350'F). The spray dried
material was calcined for two hours at 540'C (1,000°F) in
air. The resulting catalyst is designated Catalyst R and
includes about 40 wt.% zeolite. The matrix contains about
50 wt.% clay and about 50 wt.% binder and has a binder
silica-alumina ratio of about 5:1.
TABLE 5
MCM-22 Preparation
Catalyst p Q R
Nitrogen Hybrid
P~'ooertv As SvnthA=i~p~ precalci i
d
ne Calc
Attrition Index, AI 3 12 ned
3
Packed Density, g/cc 0.54 0.64 0.64
Sodium, ppm 1,083 1,215 1,255
Phosphorus, wt.~ 2.8 3.1 2.9
Surface Area, m /g 193 153 153
Real Density, g/cc 2.3 2.3 2.3
Particle Density, g/cc 0.9 1.0 1.0
Pore Volume, cc/g 0.7 0.6 0.6
Sornt_iOri CdDdCitieA q/'100 Q
Water 9.2 7.9 7.0
n-Hexane 6.0 4.1 3.0
Cyclohexane 6.0 4.9 4.2
Hvdrot_hermal Stabiiit~n ~Dha
Calcined 54 46 81
Steamed @ 540C, 2 hours 32 27 14
Steamed @ 540C, 5 hours 25 20 g
Steamed @ 540'C, 10 hours 21 11 6
Steamed @ 790'C, 10 hours 8 4 3
(45% H20, 0 psig)
lNOteO
Upon retesting, this calcined catalyst sample had an
alpha activity of 16 .
R'O 95121021 PCTlUS95100991
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As shown in Table 5, above, the use of hybrid calcined
(Catalyst R) or as-synthesized (Catalyst P) MCM-22 resulted
in better attrition resistance (lower AI) than the use of
nitrogen precalcined MCM-22. Packed density suffered,
however, for the as-synthesized catalyst. This catalyst
(Catalyst P) also had greater surface area, higher sorption
capacities, and a lower particle density than the other two
catalysts (Catalysts Q and R). After prolonged steaming
time, the nitrogen precalcined (Catalyst Q) or as-
synthesized (Catalyst P) catalysts had higher alpha
activity than the non-phosphorus containing (Catalysts M,
N, and O) and hybrid-calcined (Catalyst R) catalysts.
$xample 13
A phosphorus modified fluid catalyst was prepared by
first nitrogen precalcining (3 hours at 480'C) as-
synthesized (still containing organic directing agent) MCM-
22. Next, a zeolite slurry was prepared by ballmilling the
zeolite for 16 hours at 25 % solids with deionized water
(DI) and using 0.6 wt.% dispersant (Marasperse N-22) and
kaolin clay (Kaopaque 10S) was added to the zeolite slurry.
Phosphoric acid was added to the slurry to result in a
phosphorus level of 1.9 wt.% on the finished catalyst. A
silica-alumina binder was then added to the slurry by first
adding colloidal silica and then alumina (Condea Pural,
SBIII pseudoboehmite alumina) peptized with formic acid.
The resulting slurry was immediately spray dried at an
outlet temperature of 177'C (350'F). The spray dried
material was calcined for two hours at 540' (1,000'F) in
air. The calcined material was steam deactivated at 790'C
(1,450'F) for 10 hours in 45% steam at atmospheric
pressure. The resulting catalyst composition is designated
Catalyst S and includes about 25 wt.% zeolite. The matrix
contains about 50 wt.% clay and about 50 wt.% binder and
has a binder silica-alumina ratio of about 5:1. A control
catalyst used in the present study Was a rare earth Y type
2I8011;
W 0 95121021 PCTlUS95100991
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zeolite (REY) catalyst removed from a commercial FCC unit
following oxidative regeneration and is designated Catalyst
T. Two additional catalysts were prepared for fixed
fluidized bed (FFB) testing from Catalyst S and Catalyst T.
Catalyst U was prepared from 2 wt.% Catalyst S and 98 wt.%
Catalyst T. Catalyst V was prepared from 25 wt.% Catalyst
S and 75 wt.% Catalyst T. These cataysts were FFB tested
at 515°C (960°F) for 1 minute using a sour heavy gas oil
having the properties shown in Table 6. The results of the
l0 FFB testing (after interpolation at 70% conversion) are
shown in Table 7.
~harae Stock Property Sour Heavv Gas O
Pour point, F (C) i
95 (35)
CCR, wt.% 0.56
Kinematic viscosity, cs @ 40C 104.8
Kinematic viscosity, cs @ 100C
7.95
Aniline point, F (C) 168.5 (75.8)
Bromine number 6.g
Gravity, API 20.1
Carbon, wt.% 85.1
Hydrogen, wt.%
12.3
Sulfur, wt.% 2.6
Nitrogen, wt.% 0.2
Basic nitrogen, ppm 465
Nickel, ppm 0.5
Vanadium, ppm 0.3
Iron, ppm
1.2
Copper, ppm <0.1
Sodium, ppm O.g
WO95121021 ~ PCTIU595100991
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TABLB 7
Effect of MCM-22 with Phosphorus Catalytic Performance
on
Yield shifts at 7o vol.% conversion
Co ntrol delta Yields
Catalyst T U V
Zeolite REY MCM-22 MCM-22
-
Percent Additive in Blend ~ ~ 25%
C5+ Gasoline, vol.% 52.4 (1.7) (7.4)
C4's, vol.% 14.6 0.5 3.8
C3's, vol.% 10.5 1.6 3.7
C2 , wt.% 3.3 (0.2) -
Coke, wt.% 7.0 (0.1) 1.0
C3 , vol.% 7.2 0.7 3.1
C4~, vol.% 5.5 0.2 1.4
C5 , vol.% 3.7 (0.8) (0.2)
Potential Alkylate, vol.% 21.0 1.5 7.5
RON, C5~ Gasoline 91.5 (1.0) 1.3
( ) denotes a negative value
