Note: Descriptions are shown in the official language in which they were submitted.
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MESOPOROUS ZEOLITE-Y HYDROCRACKING CATALYST AND ASSOCIATED HYDROCRACKING
PROCESSES
FIELD OF THE INVENTION
[0001] This
invention relates to the composition, method of making and use of
a hydrocracking catalyst that is comprised of a new Y zeolite which exhibits
an
exceptionally low small mesoporous peak height around the 40 A (angstrom)
range as determined by nitrogen adsorption measurements and shown in the Bill
N2 Desorption Plot. The hydrocracking catalysts herein which comprise this
zeolite exhibit improved distillate yield and selectivity as well as improved
conversions at lower temperatures than conventional hydrocracking catalysts
containing Y zeolites.
BACKGROUND
[0002] Conversion
of high molecular weight petroleum feeds to more valuable
products by catalytic processes such as hydrocracking is important to
petroleum
processes. Hydrocracking of relatively high boiling point hydrocarbons, such
as
atmospheric and vacuum gasoil cuts from crude oil, is generally done to form a
converted product having a more useful boiling point, so that it can be
predominantly used in any one or more of a variety of fuels, such as naphtha
(motor gasoline), jet fuel, kerosene, diesel, and the like. Usually, however,
particularly when targeting distillate product fractions, the hydrocracking
reaction
is run at relatively low severity or relatively low hydrocracking conversion,
so
that the higher boiling point hydrocarbons are not cracked too much, as higher
conversions typically generate increasing quantities of material boiling in
the
ranges below naphtha, which low boiling material tends not to be as
commercially
useful as the fuel compositions. However, running at these lower temperatures
(severities), tend to reduce the overall product conversions. While
maintaining a
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better selectivity for distillates, overall conversion, as well as overall
distillate
production can be significantly decreased.
[0003]
Additionally, with hydrocracking catalysts of the art, low overall
process conversions leave behind higher quantities of higher boiling range
hydrocarbons that cannot be used as fuels and that tend to have poor
properties for
use in such applications as lubricants, without further significant processing
steps.
Such steps can add complexity and cost to dealing with such otherwise unusable
higher boiling range hydrocarbons, and options such as coking for such
hydrocarbons can offer relatively marginal return on investment.
100041 There are
many patent publications that disclose hydrocracking
processes for attaining good fuels properties, and also for attaining good
lubes
properties. A non-exclusive list of such publications includes, for example,
U.S.
Patent Nos. 5,282,958, 5,953,414, 6,413,412, 6,652,735, 6,723,889, 7,077,948,
7,261,805, and 7,300,900, U.S. Patent Application Publication Nos.
2003/0085154, 2004/0050753, 2004/0118744, and 2009/0166256, and European
Patent Nos. 0 649 896 and 0 743 351.
[0005] Nevertheless, it would be desirable to discover improved
hydrocracking catalysts compositions and associated hydrocracking processes in
which a higher boiling point hydrocarbon, such as a vacuum gasoil., can be
hydroprocessed (hydrocracked) to allow beneficial use of the converted portion
in
fuels compositions while increasing both the conversion of the 700 F boiling
point materials in the hydrocracker feedstream, while increasing the amount
that
is selectively cracked into distillate range materials (i.e., the "400-700 F
Yield").
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SUMMARY
[0006] This invention includes in part the composition, method of making
and use of a
hydrocracking catalyst that is comprised of a Y zeolite which exhibits an
exceptionally low
small mesoporous peak height around the 40 A (angstrom) range as measured by
nitrogen
adsorption and shown in the BJH N2 Desorption Plot. The hydrocracking
catalysts made from
this zeolite, and as described herein, exhibit improved rates of heavy oil
cracking with
improved low temperature conversion rates (i.e., "750 F+ Conversion") as well
as improved
selectivities of distillate yields ("i.e., 400-700 F Yield"). The present
invention includes the
composition, method of making and use of hydrocracking catalysts incorporating
an extra
mesoporous Y zeolite (termed herein as "EMY" zeolite) which has improved
mesoporous
properties over Y zeolites of the prior art, as well as a method of making the
zeolite and its
use in associated hydrocracking process. This zeolite is described herein as
well as described
further in parent application United States Serial Number 12/584,376 entitled
''Extra
Mesoporous Y Zeolite".
[0007] In one embodiment herein is described a hydrocracking catalyst
comprised of:
- a Y zeolite with a Large Mesopore Volume of at least about 0.03 em3/g and a
Small Mesopore Peak of less than about 0.15 em3/g;
- an inorganic matrix; and
- at least one active metal selected from Group 6 and Group 8/9/10 metals.
[0008] In yet another embodiment herein is described a method of making a
hydrocracking catalyst, comprising the steps of:
a) making a zeolite from a zeolite precursor;
b) combining a binder precursor selected from a silica, an alumina, or a
combination
thereof, with a zeolite to form a catalyst mixture;
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c) drying the catalyst mixture to form a catalyst precursor; and
d) adding at least one active metal to the catalyst precursor to form the
hydrocracking catalyst;
wherein the zeolite is a Y zeolite with a Large Mesopore Volume of
at least about 0.03 cm3/g and a Small Mesopore Peak of less than about
0.15 cm3/g.
100091 In still yet
another embodiment herein is described a hydrocracking
process for selectively catalytically cracking a hydrocarbon feedstock to form
a
distillate product, comprising:
a) contacting the hydrocarbon feedstock, in the presence of hydrogen, with
a hydrocracking catalyst comprised of a Y zeolite with a Large Mesopore Volume
of at least about 0.03 cm3/g and a Small :Mesopore Peak of less than about
0.15
cm3/g; an inorganic matrix; and at least one active metal selected from Group
6
and Group 8/9/10 metals under hydrocracking conditions; and
b) producing at least one distillate product stream boiling in the range of
about 400 to 700 F, which has a lower average molecular weight than the
hydrocarbon feedstock;
wherein the zeolite has a Large Mesopore Volume of at least about 0.03
cm3/g, and a Small Mesopore Peak of less than about 0.15 cm3/g.
BRIEF DESCRIPTION OF THE DRAWINGS
100101 FIGURE 1 is
a BM N2 Desorption Plot of a USY zeolite from a
commercially available ammonium-Y zeolite (prior art).
100111 FIGURE 2 is
a BJH N2 Desorption Plot of the IJSY zeolite of Figure 1
(prior art) after it has been subjected to ion exchange/calcination steps and
long-
term deactivation steaming at 1400 F for 16 hours.
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100121 FIGURE 3 is
a RIP N2 Desorption Plot of an embodiment of an Extra
Mesoporous Y ("EMY") zeolite as utilized in the catalysts of the present
invention.
100131 FIGURE 4 is
a 13.1H N2 Desorption Plot of an embodiment of an Extra
Mesoporous Y ("EMY") zeolite after it has been subjected to ion-
exchange/calcination steps and long-term deactivation steaming at 1400 1' for
16
hours.
100141 FIGURE 5
shows the distillate product yields from the comparative
hydrocracking testing data from the "batch unit" high-throughput testing of
Example 3.
100151 FIGURE 6
shows the distillate product selectivities from the
comparative hydrocracking testing data from the "batch unit" high.-throughput
testing of Example 3.
100161 FIGURE 7
shows the distillate product yields from the comparative
hydrocracking testing data from the "flow unit" high-throughput testing of
Example 3.
[0017] _FIGURE 8
shows the distillate product selectivities from the
comparative hydrocracking testing data from the "flow unit" high-throughput
testing of Example 3.
[0018] FIGURE 9
shows the distillate product yields for four (4) comparative
hydroproccssing catalysts with respective platinum (Pt) metal loadings of 0.3
wt%, 0.6 wt%, 1.0 wt% and 2.0 wt%.
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[0019] FIGURE 10 shows the distillate product selectivities for four (4)
comparative
hydroprocessing catalysts with respective platinum (Pt) metal loadings of 0.3
wt%, 0.6 wt%,
1.0 wt% and 2.0 wt%.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0020] The hydrocracking catalyst of the present invention incorporates the
use of an
Extra Mesoporous Y ("EMY") zeolite and its use in hydrocarbon cracking
catalysts. This
zeolite is described herein as well as described further in United States
Serial Number
12/584,376 entitled "Extra Mesoporous Y Zeolite". The hydrocracking catalysts
herein
comprising this new zeolite have been unexpectedly found to exhibit improved
rates of heavy
oil cracking with improved low temperature conversion rates (i.e., "750 F+
Conversion") as
well as improved selectivities of distillate yields ("i.e., 400-700 F Yield")
when utilized in the
hydrocracking processes of the present invention.
[0021] In the hydrocracking catalysts of the present invention is utilized
what is termed
herein as an EMY zeolite which is a Y structure zeolite with a suppressed
"small mesopore
peak" that is commonly found associated within the "small mesopores" (30 to 50
A pore
diameters) of commercial Y-type zeolites, while maintaining a substantial
volume of pores in
the "large mesopores" (greater than 50 to 500 A pore diameters) of the
zeolite. International
Union of Pure and Applied Chemistry ("IUPAC") standards defines "mesopores" as
having
pore diameters greater than 20 to less than 500 Angstroms (A). However, the
standard
nitrogen desorption measurements as used herein do not provide pore volume
data below
about 22 A. Additionally, since the "small mesopore peak" found in Y zeolites
are
substantially confined between the 30 and 50 A ranges, it is sufficient to
define the
measurable mesoporous pore diameter range for the purposes of this invention
as pore
diameters from 30 to 500 Angstroms (A).
[0022] Therefore, as utilized herein, the terms "Small Mesopore(s)" or
"Small
Mesoporous" are defined as those pore structures in the zeolite crystal with a
pore diameter of
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30 to 50 Angstroms (A). Similarly, the terms "Large Mesopore(s)" or "Large
Mesoporous" as
utilized herein are defined as those pore structures in the zeolite crystal
with a pore diameter
of greater than 50 to 500 Angstroms (A). The terms "Mesopore(s)" or
"Mesoporous" when
utilized herein alone (i.e., not in conjunction with a "small" or "large"
adjective) are defined
herein as those pore structures in the zeolite crystal with a pore diameter of
30 to 500
Angstroms (A). Unless otherwise noted, the unit of measurement used for
mesoporous pore
diameters herein is in Angstroms (A).
[0023] The term "Small Mesopore Volume" or "Small Mesoporous Volume" of a
material
as used herein is defined as the total pore volume of the pores per unit mass
in the Small
Mesopore range as measured and calculated by ASTM Standard D 4222
"Determination of
Nitrogen Adsorption and Desorption Isotherms of Catalysts and Catalyst
Carriers by Static
Volumetric Measurements"; ASTM Standard D 4641 "Calculation of Pore Size
Distributions
of Catalysts from Nitrogen Desorption Isotherms"; and "The Determination of
Pore Volume
and Area Distributions in Porous Substances, I. Computations from Nitrogen
Isotherms", by
Barrett, E.P.; Joyner, L.S.;, and Halenda, P.P.; Journal of American Chemical
Society; vol. 73,
pp. 373-380 (1951). Unless otherwise noted, the unit of measurement for
mesopore volume is
in cm3/g.
[0024] The term "Large Mesopore Volume" or "Large Mesoporous Volume" of a
material
as used herein is defined as the total pore volume of the pores per unit mass
in the Large
Mesopore range as measured and calculated by ASTM Standard D 4222
"Determination of
Nitrogen Adsorption and Desorption Isotherms of Catalysts and Catalyst
Carriers by Static
Volumetric Measurements";
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AS'TM Standard D 4641 "Calculation of Pore Size Distributions of Catalysts
from
Nitrogen Desorption Isotherms"; and "The Determination of Pore Volume and
Area Distributions in Porous Substances, I. Computations from Nitrogen
Isotherms", by Barrett, E.P.; Joyner, L.S.;, and Halenda, P.P.; J. Amer. Chem.
Soc.; vol. 73, pp. 373-380 (1951). Unless
otherwise noted, the unit of
measurement for mesopore volume is in cm3/g.
100251 The term
"Large-to-Small Pore Volume Ratio" or "LSPVR" of a
material as used herein is defined as the ratio of the Large Mesopore Volume
to
the Small Mesopore Volume (dimensionless).
100261 The term
93JH N2 Desorption Plot" as used herein is defined as a plot
of the change in unit volume of a mesoporous material as a function of the
pore
diameter of the mesoporous material. Herein, the "Bin N2 Desorption Plot" is
shown as the pore volume calculated as dV/dlogD (in cm3/g) vs. the pore
diameter
(in nanometers) as determined by the ASTM Standard D 4222, ASTM Standard
1) 4641, and "The Determination of Pore Volume and Area Distributions in
Porous Substances, I. Computations from Nitrogen Isotherms", by Barrett, E.P.;
Joyner, L.S.;, and Halenda, P.P.; Journal of American Chemical Society; vol.
73,
pp. 373-380 (1951), (i.e., the "BJH method" for calculating the pore
distribution
of a porous substance) as referenced in the definitions above. The BJH N2
Desorption Plot should be generated from approximately 15 to 30 data points at
approximately equidistant positions on a logarithmic x-axis of the pore
diameter
(nanometers) between the values of 3 to 50 nanometers (30 to 500 A). The pore
volume value on the y-axis of the plot is commonly calculated in industry
equipment as an interpolated value of the incremental change in volume, dV
(where V is in cm, and dV is in cm3) divided by the incremental change in the
log
of the pore diameter, dlogD (where D is in nanometers, and dlogD is unitless)
and
is adjusted to the unit weight of the sample in grams. Therefore, the "pore
volume" (which is the common term utilized in the industry) as shown on the y-
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axis of the BJH N2 Desorption Plot may be more appropriately described as an
incremental pore volume per unit mass and is expressed herein in the units
em3/g.
It should be noted that the "pore volume" value on the y-axis of the BJH N2
Desorption Plot is not synonymous with the "Small Mesopore Volume" and
"Large Mesopore Volume" as described above which are calculated unit pore
volumes over a range of pore diameters. However, these calculations and terms
as used herein are familiar to those of skill in the art. All measurements and
data
plots as utilized herein were made with a Micromeritics Tristar 3000
analyzer.
100271 The term
"Small Mesopore Peak" as used herein refers to the property
of a zeolite and is defined as the maximum pore volume value calculated as
dV/dlogD (y-axis) on a Bill N2 Desorption Plot as described above (pore volume
vs. pore diameter) between the 30 A and 50 A pore diameter range (x-axis).
Unless otherwise noted, the unit of measurement for the small mesopore peak is
in
cm /g.
ig.
100281 The term "40
A Peak" or "40 A Peak Height" as used herein refers to
the property of a catalyst and is defined as the maximum pore volume value
calculated as dV/dlogD (y-axis) on a BJH N2 Desorption Plot as described above
(pore volume vs. pore diameter) at 40 A pore diameter (x-axis). Unless
otherwise
noted, the unit of measurement for the 40 A Peak is in cm3/g.
100291 The term
"Large Mesopore Peak" used herein refers to the property of
a zeolite and is defined as the maximum pore volume value calculated as
dV/dlogD (y-axis) on a BJH N2 Desorption Plot as described above (pore volume
vs. pore diameter) between the 50 A and 500 A pore diameter range (x-axis).
Unless otherwise noted, the unit of measurement for the large mesopore peak is
in
cm3/g.
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[0030] The term
"BET Surface Area" for a material as used herein is defined
as the surface area as determined by ASTM Specification D 3663. Unless
otherwise noted, the unit of measurement for surface area is in m2/g.
[0031] The term
"Unit Cell Size" for a material as used herein is defined as
the unit cell size as determined by AST:M Specification D 3942. Unless
otherwise
noted, the unit of measurement used for unit cell size herein is in Angstroms
(A).
[0032] While not
wishing to be held to any specific theory, it is believed
herein that a problem that exists with the existing Y zeolites in the industry
in that
some of these Y-type zeolites (e.g., Na-Y zeolites), while widely used in the
industry, exhibit a "peak" in the small mesopore range (30 to 50 A pore
diameters)
while exhibiting no significant pore volume associated with the large mesopore
range (50 to 500 A pore diameters). Conversely, other Y-type zeolites (e.g.,
USY
zeolites), exhibit a significant "peak" in the small mesopore range (30 to 50
A
pore diameters) when some large mesopores are present. It is believed and is
discovered herein that the pore volume in the small mesopore range (30 to 50 A
pore diameters) of these zeolite contributes to unwanted adverse conversion
effects when utilized in hydrocarbon cracking processes.
[0033] As
discussed, conventional Y zeolites contain a significant volume
associated with pores in the range of 30 to 50 A diameter, which are easily
observed by a standard nitrogen adsorption-desorption test as interpreted by
the
Bill method. Figure 1 shows a typical the Bill N2 Desorption Plot of a typical
USY zeolite. As can be seen in Figure I, the USY exhibits a high volume of
pores in the "small mesoporous" range (30 to 50 A pore diameter) as well as a
significant "small mesopore peak" in the BJH N2 Desorption Plot of about 0.20
cm3/g or more in this small mesopore range. This high peak in the 30 to 50 A
pore diameter range of the Bill N2 Desorption Plot is a common feature for Y-
zeolite materials that possess a significant pore volume in the mesoporous
range
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(30 to 500 A pore diameters). This peak exhibited in the BJH N2 Desorption
Plot of the Y
zeolites is termed herein as the "Small Mesopore Peak" of the zeolite and is
defined above.
Without wishing to be held to any theory, it is believed that this phenomenon
occurs due to a
"bottlenecking" of some of the mesoporous structures in the zeolite creating
an ink-bottle
effect wherein a significant amount of the nitrogen inside the internal pore
cavities cannot be
released during the desorption phase of the test until the partial pressure is
reduced below the
point associated with this small mesopore peak point. Typically in a standard
nitrogen
adsorption/desorption test this peak is associated at a point in the
desorption branch at a
relative nitrogen pressure (P/Po) of about 0.4 to about 0.45. See
"Characterization of Porous
Solids and Powders: Surface Area, Pore Size and Density", by Lowell, S.,
Shields, J.E.,
Thomas, M.A., and Thommes, M., pp. 117-123, (Springer, Netherlands 2006).
[0034] As can further be seen in Figure 1, there is no significant "large
mesopore peak"
associated with the large mesoporous structure (50 to 500 A pore diameter
range) of the USY
zeolite. The USY sample of this example is further described in Example 1.
While USY
zeolites do not possess a significant volume of large mesopores (in the 50 and
500 A diameter
range) upon fabrication, they may develop these large mesopores upon steaming
at high
temperatures. A common test in the industry is to contact the zeolite with a
high temperature
steam (for example, 100% partial pressure steam at 1400 F for 16 hours) to
determine the
hydrothermal stability of the zeolite. However, upon severe steaming, Y-type
zeolites also
tend to increase the pore volume associated with the large mesopores, and the
surface area of
the zeolite tends to diminish as the steaming conditions become more severe.
[0035] According to the details of Example 1, a conventional USY sample as
described
above and shown in Figure 1 was further ammonium ion-exchanged
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three times and then steamed at 1400 for 16 hours
to determine the resulting
pore distribution and surface area stability of the USY zeolite under these
hydrothermal conditions. Figure 2 shows the B.TH N2 Desorption Plot of the ion-
exchanged USY zeolite after long-term deactivation steaming. As can be seen
from Figure 2, the steamed USY develops a "large mesopore peak" in the large
mesoporous structures (50 to 500 A pore diameter range) of the zeolite.
However,
as also can be seen in Figure 2, the "small mesopore peak", associated with
pores
in the 30 to 50 A pore diameter range of the steamed USY, is not significantly
decreased as compared to the small mesopore peak of the un-steamed USY
sample as shown in Figure 1. Here, the small mesopore peak of the steamed USY
is about 0.19 cm3/g.
100361 While not
wishing to be held to any theory, it is believed that the small
and large mesoporous pore structures of the zeolite are created by defects
and/or
deterioration of the zeolite crystalline structure, thereby creating
structural defect
voids (or equivalent "pores") that are larger in size than those of the as-
synthesized (pure crystal) structure of the zeolite.
100371 The
hydrocracking catalysts of the present invention utilize a highly
stable Y-zeolite that has a significantly suppressed small mesopore peak in
both
the as-fabricated and as-steamed conditions while maintaining a high volume of
large mesopores (50 to 500 A pore diameter range). In another embodiment of
the present invention, is a hydrocracking catalyst comprised of a highly
stable Y-
zeolite that has a significantly suppressed small mesopore peak in both the as-
fabricated and as-steamed conditions while maintaining a high ratio of large-
to-
small mesoporous volume. The zeolite utilized in the hydrocracking catalysts
of
this invention is termed herein as an "Extra Mesoporous Y" (or "EMY") zeolite.
100381 In an
embodiment of the hydrocracking catalysts of the present
invention, is utilized an EMY zeolite, which can be obtained from a starting
material of a conventional Na-Y type zeolite with a sodium oxide (Na2O)
content
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of about 10 to 15 wt%. In an embodiment of the present invention, the EMY
zeolite precursor is ammonium-exchanged to lower the Na2O content to a desired
level for the production of an EMY zeolite. Generally, about one to about
three
ammonium-exchanges are required to reduce the Na2O content of a typical Na-Y
precursor to a desired level for the production of an EMY zeolite. Based on
fabrication testing, it is believed by the inventor at this time that the
sodium level
of the EMY precursor must be maintained in certain ranges in order to obtain
an
EMY zeolite. In a preferred embodiment of the present invention, the Na20
content of the ammonium-exchanged Na-Y zeolite precursor is brought to about
2.0 to about 5.0 wt% Na2O. More preferably, the Na2O content of the
ammonium-exchanged Na-Y zeolite precursor is brought to about 2.3 to about 4.0
wt% Na20. In this preferred embodiment, it is believed that the number of ion-
exchange steps performed is not essential to the formation of EMY as long as
the
Na2O content of the EMY precursor is within a desired range. Unless otherwise
noted, the Na20 content is as measured on the zeolite precursor prior to high
temperature steam calcination and reported on a dry basis.
100391 The EMY
precursors or the final EMY zeolite may also be rare earth
exchanged to obtain a rare earth exchanged E.MY or "RE-EMY" zeolite. The
zeolites may be rare earth exchanged in accordance with any ion-exchange
procedure known in the art. It Should also be noted that the weight
percentages
used herein are based on the dry weight of the zeolite materials.
100401 The ammonium-
exchanged Na-Y precursor thus obtained is subjected
to a very rapid high temperature steam calcination. In this high temperature
steam
calcination process, the temperature of the steam is from about 1200 to about
1500 F. More preferably the temperature of the steam is from about 1200 to
about 1450 F., more preferably from about 1250 to about 1450 F, and even
more
preferably from about 1300 to about 1450 7. These high temperature steam
calcination temperatures for the production of an EMY zeolite are generally
higher than those used in the production of conventional USY zeolites which
are
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high temperature steam calcined at temperatures from about 1000 to about 1200
"F and do not undergo the rapid heating in the high temperature calcination
step as
the EMY zeolites of the present invention.
100411 It has been
discovered that it is important in achieving the EMY zeolite
structure that the zeolite precursor be brought up close to the desired
steaming
temperature in a very rapid manner. The temperature of the zeolite during the
steaming process may be measured by a thermocouple implanted into the bed of
the EMY zeolite precursor.
100421 in a
preferred embodiment of making the EMY zeolite, the temperature
of the zeolite is raised from a standard pre-calcination temperature to within
50 "IF
(27.8 "C) of the steam temperature during the high temperature steam
calcination
step in less than about 5 minutes. In a more preferred embodiment of making
the
EMY zeolite, the temperature of the zeolite is raised from a standard pre-
calcination temperature to within 50 "F (27.8 "C) of the steam temperature
during
the high temperature steam calcination step in less than about 2 minutes.
Although not critical to the fabrication process and not so limited as to the
claimed invention herein, typically the pre-calcination temperature in a Y-
type
zeolite manufacturing process is from about 50 F to about 300 'F.
100431 Example 2
herein describes the synthesis of one embodiment of an
Extra Mesoporous Y ("EMY") zeolite. Figure 3 shows the Bill N2 Desorption
Plot of the EMY zeolite sample from Example 2 prior to additional ammonium
exchange and long-term deactivation steaming. As can be seen in Figure 3, the
EMY zeolite exhibits a very low volume of pores in the "small mesoporous"
range
(30 to 50 A pore diameter) as well as a very low "small mesopore peak" of
about
0.09 cm3/g in this small mesopore range. In comparing Figure 1 (1.7SY zeolite)
and Figure 3 (EMY zeolite) it should be noted that this "small mesopore peak"
has
been substantially depressed in the EMY zeolite. It can be seen in Figure 1
that
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this small mesopore peak is about 0.20 cm3/g for the USY as compared to the
small mesopore peak of about 0.09 crn3/g for the EMY as shown in Figure 3.
[0044] As can
further be seen in Figure 3, there is beneficially a significant
"large mesopore peak" associated mainly with the large mesoporous structures
(50
to 500 A pore diameter range) of the EMY zeolite. Comparing this to the B.11-1
N2
Desorption Plot of the USY zeolite in Figure 1, it can be seen that the EMY
zeolite in Figure 3 exhibits a significant large mesopore peak of about 0.19
cm3/g
whereas the USY zeolite in Figure 1 shows no significantly comparable large
mesopore peak in this range.
100451 The pore
volumes in each of the ranges, 30 to 50 Angstroms as well as
50 to 500 Angstroms were determined by utilizing the pore volume data from the
13311 N2 Desorption tests and interpolating the data to the necessary
endpoints.
This method for calculating the pore volumes is explained in detail in Example
1
and the same method for calculating the pore volumes was utilized throughout
all
examples herein. The method as described therein defines how to interpret and
calculate the pore volume values of the zeolites within each of the defined
pore
diameter ranges.
100461 The "small
mesopore" and "large mesopore" pore volumes and the
BET surface areas for the USY and EM Y zeolites of Figures 1 and 3,
respectively,
were measured and are shown in Table 1 as follows:
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Table 1
Zeolite Properties prior to Long-Term Steaming
Zeolite Small (30- Large (50- Large- Situ 11 BE!' Unit
50A) 500A) to-Small Mesopore Surface Cell
Mesopore Mesopore Pore Peak, Area Size
Volume Volume Volume dV/dlogD (m2/g) (A)
(cm3/g) (cm3/g) Ratio (cm' /g)
USY 0.0193 0.0195 1.01 0.20 811 24.55
(Figure 1)
EMY 0.0109 0.0740 6.79 0.09 619 24.42
(Figure 3)
100471 It should be
noted that Figures 1 and 3, as well as the data in Table 1,
reflect the USY and EM Y zeolite samples after the high temperature steam
calcination step and prior to any subsequent treating. As can be seen in Table
1,
the volume of small mesopores is larger in the USY zeolite than in the EMY
zeolite. However, it can also be seen that the volume of large mesopores in
the
EMY zeolite is significantly larger than the volume of large mesopores in the
USY zeolite. As discussed, it is desired to lower the amount of pore volume in
the small mesopore range and increase the amount of pore volume in the large
mesopore range of the zeolite. Therefore, an important characteristic of the
zeolite is the ratio of the large mesopore volume ("LMV") to the small
mesopore
volume ("SMV") of the subject zeolite. We term this ratio of the LMV:SMV as
the "Large-to-Small Pore Volume Ratio" or "LSPVR" of the zeolite.
100481 As can be
seen from Table 1, the Large-to-Small Pore Volume Ratio or
"LSPVR" of the sample USY zeolite is about 1.01 wherein the LSPVR of the
sample EMY zeolite is about 6.79. This is a significant shift in the Large-to-
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Small Pore Volume Ratio obtained by the present invention. In a preferred
embodiment, the LSPVR of the EMY is at least about 4.0, more preferably at
least
about 5.0, and even more preferably, the LSPVR of the EMY is at least about
6.0
immediately dier the first high temperature steam calcination step as
described
herein.
100491
Additionally, the EMY zeolites of the present invention may be used in
processes that are not subject to exposure to high temperature hydrothermal
conditions. It can be seen from Table 1, that one of the remarkable aspects of
the
EMY zeolites of the present invention is that they exhibit very high Large
Mesopore Volumes as compared to the comparable USY of the prior art. This
characteristic of the EMY zeolites of the present invention can be valuable to
many commercial processes. In preferred embodiments, the as-fabricated EMY
zeolites of the present invention have a Large :Mesopore Volume of at least
0.03
en-fig, more preferably at least 0.05 cm3/g, and even more preferably at least
0.07
cm 1g.
1g.
100501 As utilized
herein, the term "as-fabricated" or "as-fabricated zeolite" of
the present invention is defined as the zeolite and its properties as obtained
directly after the high temperature steam calcination step (i.e., when the EMY
zeolite is formed). As one of skill in the art will be aware, subsequent
additional
steps (e.g., further ion-exchange) can be performed on the zeolite after
forming
what is considered the EMY zeolite herein. Unless otherwise stated herein or
in
the claims, the zeolite properties are measured and defined herein as of this
"as-
fabricated" point in the fabrication process. As is known to one of skill in
the art,
the "long-term deactivation steaming" referred to herein is generally utilized
as a
tool to test the ability of the as-fabricated zeolite to withstand
hydrothermal
conditions and is not considered as a part of the fabrication of the zeolite.
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[0051] It should
also be noted that it is obvious to those of skill in the art that
long-term deactivation steaming will tend to increase the Large Mesopore
Volume
of typical Y zeolites. However, this unusual aspect of the EMY zeolites of the
present invention of possessing such a significantly increased Large Mesopore
Volume prior to long-term deactivation steaming can be useful in processes
wherein high temperature hydrothermal conditions are not present or even more
importantly in processes wherein it is undesired for the fabricated zeolite to
be
long-term steam deactivated. The as-fabricated EMY zeolite possesses higher
BET surface areas as compared to the BET surface areas after the log-term
steam
deactivation and the as-fabricated EMY zeolite may be more stable in some
applications than that the EMY zeolite obtained alter long-term steam
deactivation.
100521 It can also
be seen from comparing Figure 1 (USY zeolite sample) and
Figure 3 (EMY zeolite sample) that the small mesopore peak in the 30 to 50 A
pore diameter range is significantly lower for the EMY zeolite than. the USY
zeolite. In a preferred embodiment, the as-fabricated EMY zeolite obtained
following the high temperature steam calcination exhibits a Small Mesopore
Peak
of less than about 0.15 cm3/g. In a more preferred embodiment, the EMY zeolite
has a Small Mesopore Peak of less about 0.13 cm3/g, and in an even more
preferred embodiment, the Small Mesopore Peak of the EMY is less than about
0.11 cm3/g. The Small M.esopore Volume Peak as defined prior is the maximum
value (or peak) of the pore volume value (dV/dlogD, y-axis) exhibited on the
BM.
N2 Desorption Plot in the 30 to 50 Angstroms (A) pore diameter range.
[0053] in addition,
the EMY materials of the present invention exhibit smaller
unit cell sizes as compared to similar USY materials that have undergone a
single
high temperature steam calcination step. As can be seen in Table 1, the USY
zeolite of Example 1 has a unit cell size of about 24.55 A, while the EMY
zeolite
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prepared from similar starting materials has a significantly lower unit cell
size of
about 24.42 A.
[0054] It has been
discovered that in preferred embodiments, these as-
fabricated EMY zeolites exhibit unit cell sizes that are less than 24.45 A.
Preferably, the as-fabricated EMY zeolitcs exhibit unit cell sizes ranging
from
about 24.37 to about 24.47 A after the first high temperature steam
calcination
step as described herein. In even more preferred embodiments, the as-
fabricated
EMY zeolites have low unit cells size from about 24.40 to about 24.45 A after
the
first high temperature steam calcination step as described herein. This
smaller unit
cell size generally results in a more stable zeolite configuration due to the
higher
framework silica/alumina ratios reflected by the lower unit cell sizes of E.MY
zeolite.
100551 The USY
zeolite sample as described in Example 1 and shown in the
13JII N2 Desorption Plot of Figure 1 as well as the E.MY zeolite sample as
described in Example 2 and shown in the BJH N2 Desorption Plot of Figure 3
were further ammonium ion-exchanged and then long-term deactivation steamed
at 1400 'F for 16 hours to determine the long-term hydrothermal stability of
the
USY and EMY zeolites.
100561 Figure 2
shows the BJH .N2 Desorption Plot of the ion-exchanged USY
zeolite of the prior art after long-term deactivation steaming. Figure 4 shows
the
BJH N2 Desorption Plot of the ion-exchanged EMY zeolite of an embodiment of
the present invention after long-term deactivation steaming. As can be seen
from
Figure 4, the Large Mesopore Peak of the EMY zeolite increased desirably from
about 0.19 cm3/g (as shown in Figure 3) to about 0.36 crn3/g (as shown in
Figure
4) after long-term deactivation steaming. Just as desirable, following long-
term
deactivation steaming of the EMY zeolite, the Small Mesopore Peak of the EMY
zeolite was not significantly increased. The Small Mesopore Peak of the EMY
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zeolite remained essentially constant at about 0.10 cm3/g (as shown in Figures
3
and 4).
[0057] In contrast,
in the comparative USY zeolite of the prior art, the Small
Mesopore Peak remained undesirably high at about 0.19 cm3/g after long-term
deactivation steaming (see Figure 2).
100581 The physical
properties of the zeolites obtained after long-term
deactivation steaming in Examples I and 2 are tabulated in Table 2 below. In
Table 2 below, are shown the "Small Mesopore Volumes", the "Large Mesopore
Volumes, the "Large-to-Small Pore Volume Ratios", and the Small Mesopore
Peaks" for the USY and EMY zeolites illustrated in Figures 2 and 4,
respectively,
as well as the associated BET surface areas and the unit cell sizes as
measured
following three ammonium ion-exchanges and long-term, deactivation steaming at
1400 '17 for 16 hours.
Table 2
Zeolite Properties after Long-Term Deactivation Steaming
Zeolite Small (30- Large Large-to- Small BET Unit
50A) (50-500A) Small Mesopore Surface Cell
Mesopore Mesopore Pore Peak, Area Size
Volume Volume Volume dV/dlogD (m2/g (A)
(cm3/g) (cm3/g) Ratio (cm3/g)
USY 0.0112 0.1211 10.85 0.19 565 24.27
(Figure 2)
EMY 0.0077 0.1224 15.97 0.10 7 24.27
(Figure 4)
100591 Another
benefit of the EMY zeolites of the present invention is surface
area stability. As can be seen in Table 2, the BET surface area for the long-
term
deactivation steamed EMY zeolite sample was greater than the BET surface area
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for the USY sample. Additionally, the EMY retained, a higher percentage of the
surface area after the three ammonium ion exchanges and long-term deactivation
steaming at 1400 al7 for 16 hours. Comparing Table 1 and Table 2, the USY
retained about 70% of its original surface area wherein the EMY retained about
95% of its original surface area, indicating the superior hydrostability of
the EMY
zeolites of the present invention. In preferred embodiments of the present
invention, the EMY zeolite has BET Surface Area of at least 500 m2/g as
measured either before long-term deactivation steaming at 1400 F for 16 hours
or
after long-term deactivation steaming at 1400 F for 16 hours.
100601 in a
preferred embodiment, the "Large-to-Small Pore Volume Ratio"
(or "LSPVR") of the EMY is at least about 10.0, more preferably at least about
12.0, and even more preferably, the I.SPVR. of the EMY is at least about 15.0
after long-term deactivation steaming at 1400 F for 16 hours.
100611 In preferred
embodiments of the hydrocracking catalysts herein, the
EMY zeolite is incorporated with a binder material to impart resistance to the
temperatures and other conditions employed in the hydrocarbon conversion
processes as well as to enable the catalyst to be formed into catalyst
particles of
suitable size and stability for the hydrocracking process apparatus and
process
conditions. In these preferred catalyst embodiments, the EMY zelolite herein
is
incorporated into a catalyst by the use of a suitable binder material.
Suitable
binder materials include materials selected from metal oxides, zeolites,
aluminum
phosphates, polymers, carbons, and clays. Most preferable, the binder is
comprised of at least one metal oxide, preferably selected from silica,
alumina,
silica-alumina, amorphous aluminosilicates, boron, titania, and zirconia.
Preferably, the binder is selected from silica, alumina, and silica-alumina.
In a
preferred embodiment, the binder is comprised of pseudoboehmite alumina.
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[0062] While the
catalysts of invention can contain from 0 to 99 wt% binder
materials, in preferred embodiments, the binders levels can be about 25 to
about
80 wt%, more preferably, from about 35 to 75 wt%, or even from about 50 to
about 65 wt% of the overall final hydrocracking catalyst. In other preferred
embodiments, the hydrocracking catalyst can be less than 80 wt%, more
preferably less than. 75 wt%, and most preferably less than 65 wt% or even 50
wt% binder materials.
100631 In other
preferred embodiments, the hydrocracking catalyst may
contain additional zeolites or molecular sieves. In a preferred embodiment,
the
hydrocracking catalyst further comprises at least one of the following
zeolites or
molecular sieves. In a preferred embodiment, the hydrocracking catalyst
further
comprises at least one of the following molecular sieves: beta, ZSM-5, ZSM-11,
ZSM-57, MCM-22, MCM-49, MCM-56, ITQ-27, ZS.M-
48, mordenite,
zeolite L, ferrierite, ZSM-23, MCM-68, SSZ-26/-33, CIT-1, SAPO-37, ZSM-12,
ZSM-I8, and EMT faujasites. In more preferred embodiments, the hydrocracking
catalyst comprises at least one of the following molecular sieves: beta, ZSM-
5,
ZSM-48, mordenite, and zeolite L. The molecular sieves listed above can be
present in the as-synthesized form, or alternatively, can be post-modified
chemically, thermally, or mechanically to create a stabilized form of the
material.
100641 In preferred
embodiments, the hydrocracking catalyst of the invention
herein contains the EMY zeolite in an amount of at least 10 wt% , more
preferably
at least at least 25 wt%, and even more preferably at least 35 wt% or even at
least
50 wt% based on the finished catalyst, particularly when a binder is utilized.
[0065] In preferred
embodiments of the hydrocracking catalyst, the aggregates
of zeolite Y (Meso-Y) are combined with at least one metal oxide binder (as
described prior) and further with at least one hydrogenating metal component,
in
order to form a catalyst suitable for .hydrocracking. Examples of such
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hydrogenating metal components can include one or more noble metals or one or
more non-noble metals.
[0066] The
aggregates of zeolite Y, binder and additional components may be
extruded, spray-dried, or otherwise shaped into a catalyst particle for use in
hydroconversion processes described herein. In preferred embodiments of the
hydrocracking catalysts herein, the final catalyst contains an active Group 6
and/or Group 8/9/10 metal. Please note that the designation of Group 6 and
Group 8/9/10 herein corresponds to the modern IUPAC designation wherein the
columns of the Periodic Table of Elements corresponds to columns numbered 1
through 18. A "Group 6" metal as designated herein corresponds to any metal in
Column 6 of the modem IUPAC designated Periodic Table of Elements and
which corresponds to the old designation of "Group VIA" as shown in the
Periodic Table of Elements, published by the Sargent-Welch Scientific Company,
1979, wherein the Group 6 (old "Group VIA") elements include the column from
the periodic table of elements containing Cr, Mo, and W. Similarly, a "Group
8/9/10" metal as designated herein corresponds to any metal in Columns 8, 9 or
of the modern IUPAC designated Periodic Table of Elements and which
corresponds to the old designation of "Group VIIIA" as shown in the Periodic
Table of Elements, published by the Sargent-Welch Scientific Company, 1979,
wherein the Group 8/9/10 (old "Group VIIIA") elements include the columns
from the periodic table of elements containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir,
and
Pt.
[0067] In a
preferred embodiment, the hydrocracking catalyst is comprised of
at least one Group 6 metal selected from Mo and W, and at least one Group
8/9/10
metal selected from Ni and Co. In a preferred embodiment, the Group 6 metal is
Mo and the Group 8/9/10 metal is Co. In another preferred embodiment, the
hydrocracking catalyst is comprised at least one Group 8/9/10 metal selected
from
Pt, Pd, Rh and Ru (noble metals). In another preferred embodiment, the
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hydrocracking catalyst is comprised at least one Group 8/9/10 metal selected
from
Pt and Pd. In another preferred embodiment, the hydrocracking catalyst is
comprised of Pt. The active Group 6 or Group 8/9/10 metals may be incorporated
into the catalyst by any technique known in the art. A preferred technique for
active metal incorporation into the catalyst herein is the incipient wetness
technique.
100681 The amount
of active metal in the catalyst can be at least 0.1 wt%
based on catalyst, or at least 0.15 wt%, or at least 0.2 wt%, or at least 0.25
wt%,
or at least 0.3 wt%, or at least 0.5 wt% based on the catalyst. For
embodiments
where the Group 8/9/10 metal is Pt, Pd, Rh, :Ru, or a combination thereof, the
amount of active metal is preferably from 0.1 to 5 wt%, more preferably from
0.2
to 4 wt%, and even more preferably from 0.25 to 3.5 wt%. For embodiments
where the active metal is a combination of a non-noble Group 8/9/10 non-noble
metal with a Group 6 metal, the combined amount of active metal is preferably
from 0.25 wt% to 40 wt%, more preferably from 0.3 wt% to 35 wt%, and even
more preferably from 1 wt% to 25 wt%.
100691 Other
preferred non-noble metals and non-noble metal combinations
utilized in the hydrocracking catalysts herein can include chromium,
molybdenum, tungsten, cobalt, nickel, and combinations thereof, such as cobalt-
molybdenum, nickel-molybdenum, nickel-tungsten, cobalt-tungsten, cobalt-
nickel-molybdenum, cobalt-nickel-tungsten, nickel-molybdenum-tungsten, and
cobalt-molybdenum-tungsten. Non-noble metal components may be pre-sulfided
prior to use by exposure to a sulfur-containing gas (such as hydrogen sulfide)
or
liquid (such as a sulfur-containing hydrocarbon stream, e.g., derived from
crude
oil and/or spiked with an appropriate organosulfur compound) at an elevated
temperature to convert the oxide form to the corresponding sulfide form of the
metal.
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[0070] The present
invention also includes a method of making the
hydrocracking catalysts described herein. A preferred method of making an
embodiment of the catalysts herein comprises the steps of mixing a binder
precursor
selected from a silica, an alumina, or a combination thereof to form a
catalyst
mixture; and drying the catalyst mixture to form a catalyst; wherein the
zeolite is a Y
zeolite with a Large Mcsoporc Volume of at least about 0.03 cm3/g and a Small
Mesopore Peak of less than about 0.15 cm3/g (i.e., an embodiment of an EMY
zeolite). In preferred embodiment, the binder precuisor is a colloidal silica,
silica
gel, a silica sol, or a combination thereof In preferred embodiment, the
binder
precursor is a colloidal alumina, alumina gel, a alumina sol, or a combination
thereof.
100711 Most
preferred embodiments of the low mesoporous peak catalysts and
method of making the low mesoporous peak catalysts of the present invention
include combinations of some or all of the most preferred embodiments of the
EMY
zeolites and catalysts described herein.
100721 In preferred
embodiments, the hydrocracking catalyst materials herein
(including the zeolite and binder materials) can be formed into a paste
utilizing the
components as described herein as well as are exemplified as described in the
examples herein. The paste can then be extruded into catalyst pellets. In
preferred
embodiments, the extruded catalyst pellets are further dried as about 150 to
about
300 F (66 to about 149 C) and then are further air calcined at about 600 to
about
12007 (316 to about 649T). In other embodiments, the hydrocracking catalyst
can
formed by spray drying the catalyst mixture at a temperature from about 250 F
to
about 650 F (121 to about 343 C), which can then be further optionally air
dried and
calcined.
[0073] The active
metals (such as, but not limited to, the Group 6 and/or Group
8/9/10 metals as described herein) are preferably added to the formed catalyst
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pellets alter drying and/or calcining. Preferably, the active metals are added
to the
formed catalyst pellets by incipient wetness teclmique.
[0074] The
embodiments of the hydrocracking catalysts described herein are
utilized in processes for conversion of heavy hydrocarbon feedstocks into
lighter,
more valuable hydrocarbon products (such, as gasoline, kerosene, and diesel
products). The catalysts herein have been unexpectedly found to possess very
high selectivities toward diesel production (i.e., increased yield volumes)
when
utilized under hydrocracking conditions. As is well, known, increased diesel
production is a main focus of refineries in the United States (and even more
particularly in the markets of Europe and Asia), as the vehicle pool is ever
shifting
more toward higher mileage diesel powered vehicles as compared to less
efficient
gasoline powered engines.
100751 In these
hydrocracking processes, the hydrocarbon feedstock to be
hydrocracked may include, in whole or in part, a gasoil (e.g., light, medium,
heavy, vacuum, and/or atmospheric) having an initial boiling point above about
400 F (204 C), a T50 boiling point (i.e., the point at which approximately 50
percent by weight boils, or becomes or is gaseous, under atmospheric pressure)
of
at least about 600 F (316 C), and an end boiling point of at least about 750 F
(399 C). However, as noted, the hydrocracking catalysts of invention are
particularly useful in maximizing diesel production (400 F to 700 F, i.e. 204-
371 C, boiling range products) from higher boiling point feedstocks. As such,
in
preferred embodiments of the present invention, the hydrocarbon feedstock
contains at least 25 wt%, more preferably at least 50 wt%, and even more
preferably, at least 75 wt% hydrocarbons with boiling points above 750 F
(399 C). In preferred embodiments, it is preferred that the portion the
hydrocarbon feedstock boiling above 750 F (399 C) has a T50 boiling point
above 800 F (427 C), more preferably above 825 F (441 C), and most preferably
above 850 F (454 C).
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100761 The
feedstock can include one or more of thermal oils, residual oils,
cycle stocks, whole top crudes, partial crudes, tar sand oils, shale oils,
synthetic
fuels, heavy hydrocarbon fractions derived from the destructive hydrogenation
of
coal, tar, pitches, and/or asphalts, hydrotreated feedstocks derived
therefrom, and
the like. As should be appreciated by those skilled in the art, the
distillation of
=higher boiling petroleum fractions above about 750 F (399 C) can generally be
carried out under vacuum (i.e., at subatmospheric pressure), typically to
avoid
thermal cracking. The boiling temperatures utilized herein are thus
conveniently
expressed in terms of the boiling point corrected to atmospheric pressure.
Further
additionally or alternately, resid compositions and/or deeper cut gasoils,
such as
with relatively high metals contents, can be cracked using catalysts employing
the
aggregated zeolite materials of the invention.
100771 In such
processes envisioned utilizing the hydrocracking catalysts of
invention herein, a hydrocarbon feedstock is contacted with embodiments of the
hydrocracking catalysts disclosed and described herein under hydrocracking
conditions. In the processes herein, it is desired to maximize the amount of
diesel
product (i.e., hydrocarbon with boiling points in the range of 400 to 700 F,
also
referred to as the "400-700 F Yield" or "Distillate Yield") produced in the
hydrocracking conversion process. Similarly, it is desired that the
"Distillate
Selectivity" of a hydrocracking catalyst is also high. The "Distillate
Selectivity"
is defined as the Distillate Yield divided by the "700 F- Conversion" (or
simply
"conversion") herein. The "700 F+ Conversion" is the wt% of the hydrocarbon
product from the process that boils below 700 F divided by the wt% of the
hydrocarbon feed from the process that boils above 700 F. The Distillate
Selectivity is an important measurement since although a high 700 F+
Conversion
is desired, it is desired that a high amount of the converted product is in
the
distillate range and not cracked into lighter, less valuable products. As
such, the
Distillate Selectivity is an important measurement of the catalysts'
performance.
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100781 The
contacting of the hydrocarbon feedstock with the Y-containing
hydrocracking catalysts is typically performed in a hydrocracker reactor in
the
presence of excess hydrogen gas. The hydrocracking process may contain one or
more reactor stages in series, but most preferably, there are either one or
two
reactor stages, but each stage may contain one or more reactor vessels. In
preferred embodiments of the present invention, there are at least two reactor
stages, with the first reactor stage being operated at a total pressure of at
least 250
psig, more preferably at least 500 psig, higher than the second reactor stage.
Even
more preferably, hydrocracking process comprises an intermediate vapor
separation between the first reactor stage and the second reactor stage in
which at
least a portion of the hydrogen gas from the first reactor stage effluent is
removed.
In more preferred embodiments, at least a portion of the hydrogen gas removed
in
the intermediate vapor separation step is recycled to the first reactor stage.
100791 Preferred
hydrocracking operating conditions herein include a reaction
temperature from about 550 F (about 288 C) to about 800 F (about 427"C); a
total pressure from about 300 psig (about 2.1 MPag) to about 3000 psig (about
20.7 MPag), more preferably from about 700 psig (about 4.8 MPag) to about 2500
psig (about 17.2 MPag); an ULM/ from about 0.1 hr- to about 20 hr-I,
preferably
from about 0.2 hr l to about 10 hr-1; and a hydrogen treat gas rate from about
500
scf/bbl (about 85 Nm3/m3) to about 10000 scf/bbl (about 1700 .Nm3/m3),
preferably from about 750 scf/bbl (about 130 Nm3/m3) to about 7000 scf/bbl
(about 1200 Nm3/m3), more preferably from about 1000 scf/bbl (about 170
Nm3/m3) to about 5000 scf/bbl (about 850 Nm3/m3).
100801 Figures 5
and 6 herein show the results of the "batch unit" testing
described in Example 4 including the four (4) EMY hydrocracking catalyst
samples of the present invention (Catalyst Samples 1-4) compared with the
seven
(7) USY reference catalysts from Example 3.
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[0081] As can be
seen in Figure 5, the Distillate Yields are shown for all
eleven (11) catalysts. As discussed prior, the "Distillate Yield" is the
weight
percentage of the hydrocarbon product from the testing that boils in the range
of
from 400-700 F. Here, three of the four EMY hydrocracking catalysts of
invention (Catalyst Samples 1-3) show Distillate Yields at are above the best
performing reference hydrocracking catalysts.
100821 However,
more importantly, in Figure 6, the Distillate Selectivities are
shown for all eleven (11) catalysts tested in the batch unit. Here, it can be
seen
that while all four EMY catalysts (Catalyst Samples 1-4) had very high
Distillate
Selectivities, that two of the EMY hydrocracking catalysts of invention
(Catalyst
Sample 3 and 4), significantly outperformed all of the reference catalysts for
Distillate Selectivity.
100831 Figures 7
and 8 herein show the results of the "flow unit" testing
described in Example 4 of the four (4) EMY hydrocracking catalyst samples of
the present invention (Catalyst Samples 1-4).
[0084] In Figure 7,
it can be seen EMY Catalyst Samples 1 and 2 of the
present invention have better Distillate Yields at lower hydrocracking
temperatures, while the EMY Catalyst Samples 3 and 4 of the present invention
have better distillate yields at higher hydrocracking temperatures. This
allows the
EMY catalysts of the present invention to be tailor designed to the operating
conditions of a specific hydrocracking unit or process.
[0085] In Figure 8,
it can be seen EMY Catalyst Samples 3 and 4 of the
present invention have better Distillate Selectivities at all hydrocracking
temperatures than the EMY Catalyst Samples 1 and 2 of the present invention
have better distillate yields at higher hydrocracking temperatures. Therefore,
if
distillate selectivity is the primary desired component from the hydrocracking
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process, the versions of the EMY Catalyst Samples 3 and 4 can be utilized. It
should be noted here that the superior Distillate Selectivities of EMY
Catalyst
Samples 3 and 4 from the flow unit testing (as shown in Figure 8) coincide
with
the showing of superior Distillate Selectivities of EMY Catalyst Samples 3 and
4
from the batch unit testing (as shown in Figure 6).
100861 Although the
present invention has been described in terms of specific
embodiments, it is not so limited. All suitable combinations and sub-
combinations
of preferred characteristics of the catalysts presented herein are
contemplated by the
present invention. Suitable alterations and modifications for operation under
specific conditions will be apparent to those skilled in the art. It is
therefore
intended that the following claims be interpreted as covering all such
alterations and
modifications as fall within the true spirit and scope of the invention.
100871 The Examples
below are provided to illustrate the manner in which the
zeolites and hydrocracking catalysts of the current invention were synthesized
and
tested, as well as illustrate the improved product qualities and the benefits
from
specific embodiments of the current invention thus obtained. These Examples
only
illustrate specific embodiments of the present invention and are not meant to
limit
the scope of the current invention.
100881 EXAMPLES
Example I
100891 A commercial
ammonium-exchanged Y zeolite with a low sodium
content (CBV-300 from Zeolysi", SiO2/A1203 molar ratio = 5.3, Na20 3.15 wt%
on dry basis) was steamed in a horizontal calcination oven which was at a
temperature of 1000 F and in a flow of 50% steam + 50% N2 for 1 hour. The
resulting product was an ultra-stable Y (USY) zeolite, and was analyzed with a
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Micromeritics Tristar 3000 analyzer to determine the pore size distribution
characteristics by nitrogen adsorption/desorption at 77.35 K. The BJH method
as
described in the specification was applied to the N2 adsorption/desorption
isotherms to obtain the pore size distribution of the zeolite, and a plot of
d\f/dlogD vs. Average Pore Diameter is shown in Figure 1.
100901 A copy of the pertinent data generated by the .BJ1-I method generated
from the N2 adsorption/desorption isotherms for this zeoli.te sample is
reproduced
in Table 3 below. This test method and the associated format of data generated
as
presented are familiar to one of skill in the art.
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Table 3
RIR Pore Volume Distribution of USY Sample
Pore Incremental
Diameter Average dVicilogD Cumulative Pore
Range Diameter Pore Volume Pore Volume
Volume
(nm) (nm) (nm) (cm3/g) (cm'ig)
312.8 -
104.1 124.1 0.010 0.0048 0.0043
.104 . .1.7..62.8... 73.6 0.017 000t6 0003
zaat.siiiiiiiiii 47.8 0.018 0.0117 iiii00032.ikW
41.5 -30.4 34.1 0.018 0.0142 0.0024
30.4 - 22.9 25.5 0.017 0.0162 0.0020
22.9- 18.6 20.3 0.015 0.0175 0.0014
18.6 - 16.8 17.6 0.016 0.0182 0.0007
16.8 - 15.0 15.8 0.014 0.0189 0.0007
15.0 - 13.2 14 0.0152 0.0198 0.0008
13.2- 11.7 12.4 0.0151 0.0206 0.0008
11.7 - 10.6 11.1 0.014 0.0212 0.0006
10.6- 9.3 9.8 0.014 0.0220 0.0008
9.3 - 8.2 8.6 0.016 0.0229 0.0009
8.2- 7.1 7.5 0.019 0.0241 0.0012
7.1 - 6.1 6.5 0.027 .00259 ............... 0.0019
6.1 - 5.3 5.6 0.044
..!.0:02851:::::::::::::::::::::::::::: 0 0027
53- 46 4.9 0.055 0.0317 .ii00941iiiiimm
4.6- 4.1 4.4 0.054 0.0344 0.0027
4.1 - 3.7 3.9 0.203 0.0443 0.0099
3.7- 3.3 3.5 0.075 0.0476 0.0033
3.3 - 2.9 3.1 0.036 0.0497 0.0022
2.9- 2.6 2.8 0.044 0.0517 0.0019
2.6- 2.5 2.5 0.049 0.0531 0.0014
2.5 - 2.2 2.3 0.062 0.0558 0.0028
100911 As can be
seen in Table 3, a calculated Cumulative Pore Volume
(cm3/g) is associated with a range of Pore Diameter (nm) as the test
incrementally
desorbs the nitrogen from the test sample. An Incremental Pore Volume is then
calculated for each of these ranges. A pore volume within a certain range (for
example a range from 50 to 500 A, which is equivalent to 5 to 50 nm as
presented
in Table 4) can be calculated by subtracting the Cumulative Pore Volume at 50
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nm from the Cumulative Pore Volume at 5 rim. Where necessary, the Cumulative
Pore Volume at a specific pore size can be calculated by interpolating the
data
within the range. This method was utilized for all of the Examples herein.
100921 For example,
to determine the total pore volume associated with pore
diameters between 5 nm and 50 nm, first the Cumulative Pore Volume associated
with 50 rim was calculated by interpolating the amount of the Incremental Pore
Volume (highlighted) associated with the difference between 62.8 rim and 50.0
rim in the 62.8 to 41.5 nm pore diameter range as shown in the table
(highlighted)
and adding this amount to the Cumulative Pore Volume (highlighted) from the
prior range. The calculation for the Cumulative Pore Volume associated with 50
rim pore diameter was calculated from the data in Table 4 above as follows:
062.8-50.0) / (62.8-41.5) * 0.0032) + 0.0085 0.0104 cm3/g
100931 The
calculation is then performed similarly for the Cumulative Pore
Volume associated with 5 nm pore diameter. The calculation was as follows:
05.3-5.0) / (5.3-4.6) * 0.0031) + 0.0286 = 0.0299 cm3/g
100941 The total
Pore Volume associated with the pore diameter ranges of 5
rim to 50 nm (50 A to 500 A) of the USY of this example is thus equal to the
difference in the Cumulative Pore Volumes associated with 5 nm and 50 nm
respectfully as follows:
0.0299 cm3/g - 0.0104 cm3/g = 0.0195 cm3/g
100951 This value
is the Large Mesopore Volume for this USY sample as
shown in Table I. All other pore volumes associated with specific pore
diameter
ranges can be and were calculated herein by the same basic method.
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[0096] As such, the
following properties of this USY zeolite were obtained
from the data:
Small Mesoporous Volume (Range: 3.0 nm to 5.0 nm): 0.0193 cm3/g
Large Mesoporous Volume (Range: 5.0 nm to 50.0 nm,): 0.0195 cm3/g
Ratio of (Large Mesopore Volume)/(Small Mesopore Volume): 1.01
Small Mesopore Peak (dVidlogD@J3.9nrn): 0.20 cm3/g
100971
Additionally, the USY zeolite sample exhibited a BET surface area of
811 m2/g, and a unit cell size of 24.55 angstroms.
100981 A sample of
the prepared USY zeolite above was further subjected to an
ammonium. ion-exchange consisting of adding 80 grams of the zeolite into 800
ml of
NII4NO3 (1M) solution at 70 C and agitating for 1 hour, followed by
filtration on a
funnel and washing the filter cake with 1000 ml of de-ionized water. The water
rinsed zeolite cake was dried on the funnel by pulling air through, then in an
oven at
120 C in air for over 2 hours, Chemical analysis of the dried zeolite by IC.P
showed
0.48 wt% Na20 (dry basis). .A Na2O content of about 0.50 wt% was targeted. The
dried zeolite was subjected to long-term deactivation steaming at 1400 for
16
hours, 100% steam, to determine its hydrothermal stability.
[0099] The zeolite
obtained after long-term deactivation steaming was
similarly analyzed in a Micromeritics Tristar 3000 analyzer. The BJH method
was applied to the N2 adsorption/desorption isotherms to obtain the pore size
distribution of the zeolite, and a plot of dV/dlogD vs. Average Pore Diameter
is
shown in Figure 2. The following properties of this long-term deactivation
steamed USY zeolite were obtained from the data:
Small Mesoporous Volume (Range: 3.0 nm to 5.0 nm): 0.0112 cm3/g
Large Mesoporous Volume (Range: 5.0 nm to 50.0 nm,): 0.1211 cm3/g
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Ratio of (Large Mesopore Vol ume)/(Small Mesopore Volume): 10.85
Small Mesopore Peak (dV/dlogD@3.9mn): 0.19 cm3/g
1001001 Additionally, the USY zeolite after long-term deactivation steaming
exhibited a BET surface area of 565 m2/g, and a unit cell size of 24.27
angstroms.
Example 2
1001011 In this example, an embodiment of the Extra Mesoporous Y ("EMY")
zeolite was prepared as follows:
1001021 The same commercial ammonium-exchanged Y zeolite (CI3V-300 )
with a low sodium content (SiO2/A1203 molar ratio = 5.3, Na2O 3.15 wt% on dry
basis) as in Example 1 was placed in a horizontal quartz tube, which was
inserted
into a horizontal oven pre-equilibrated at 1400 F in 100% steam at atmospheric
pressure. Utilizing this procedure, the temperature of the zeolite precursor
was
raised to within 50 of the high
temperature steam calcination temperature (i.e.,
to 1350 V) within 5 minutes. The steam was let to pass through the zeolite
powders. After 1 hour, the tube was removed from the horizontal oven and
resulting EMY zeolite powders were collected. It should be noted_that the
starting
material (i.e., the EMY precursor zeolite) selected was a low sodium content Y
zeolite. As described in the specification above, it is believed that
production of
the EMY zeolite is dependent upon the proper zeolite sodium content prior to
high
temperature steam calcination. If the sodium content is not within the
specifications as described herein, the starting Y zeolite may first require
ammonium-exchange or methods as known in the art to reduce the sodium content
of the EMY zeolite precursor to acceptable levels prior to high temperature
steam
calcination to produce the EMY zeolite.
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1001031 The resulting EMY zeolite was analyzed by a Micromeritics Tristar
3000 analyzer as used in Example 1. The BJH method as described in the
specification was applied to the N2 adsorption/desorption isotherms to obtain
the
pore size distribution of the zeolite, and a plot of dV/dlogD vs. Average Pore
Diameter is shown in Figure 3. The following properties of this EMY zeolite
wcrc obtained:
Small Mesoporous Volume (Range: 3.0 mn to 5.0 nm): 0.0109 cm3/g
Large Mesoporous Volume (Range: 5.0 nm to 50.0 nm,): 0.0740 cm3/g
Ratio of (Large .Mesopore .Volume)/(Small .Mesopore Volume): 6.79
Small Mesopore Peak (dV/dlogD@3.9nm): 0.09 cm3/g
1001041 Additionally, the .EMY zeolite sample exhibited a BET surface area of
619 m2/g, and a unit cell size of 24.42 angstroms.
1001051 A sample of the EMY zeolite above was further subjected to an
ammonium ion exchange consisting of adding 100 grams of the EMY zeolite into
1000 ml of N114NO3 (1.M) solution at 70 C and agitating for 1 hour, followed
by
filtration on a funnel and washing the filter cake with 1000 ml of de-ionized
water.
The water rinsed zeolite cake was dried on the funnel by pulling air through,
then in
an oven at 120 C in air for over 2 hours. The ammonium ion exchange was
repeated using 60 g of the washed EM Y zeolite in 600 ml of NH4NO3 (1M)
solution
at 70 C and agitating for 1 hour, followed by filtration on a funnel and
washing the
filter cake with 1000 ml of de-ionized water. The water rinsed zeolite cake
was
dried on the funnel by pulling air through, then in an oven at 120 C in air
for over 2
hours. Chemical analysis of the dried zeolite by IC:P showed 0.64 wt% Na2O
(dry
basis). A Na2O content of about 0.50 wt% was targeted. This zeolite was then
subjected to long-term deactivation steaming at 1400 F for 16 hours, 100%
steam,
to determine its hydrothermal stability.
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1001061 The EMY zeolite obtained after long-term deactivation steaming was
also analyzed by a Mieromeritiest Tristar 300e analyzer. The BJH method was
applied to the N2 adsorption/desorption isotherms to obtain the pore size
distribution of the zeolite, and a plot of dV/dlogD vs. Average Pore Diameter
is
shown in Figure 4. The following properties of the EMY zeolite after long-term
deactivation steaming were thus obtained from. the data:
Small Mesoporous Volume (Range: 3.0 nm to 5.0 nm): 0.0077 ern3/g
Large Mesoporous Volume (Range: 5.0 nm to 50.0 nm,): 0.1224 cm3/g
Ratio of (Large .Mesopore .Volume)/(Small .Mesopore Volume): 15.97
Small Mesopore Peak (dV/dlogD@3.9nm): 0.10 em3/g
1001071 Additionally, the surface area of the EMY zeolite after long-term
deactivation steaming was analyzed by a BET Test. The zeolite exhibited a BET
surface area of 587 m2/g, and a unit cell size of 24.27 angstroms.
Example 3 1-1 vd roera eking Catalyst Synthesis
1001081 In this Example, four (4) hydrocracking catalysts of invention
(labeled
herein as Catalyst Samples 1 through 4) and seven (7) reference hydrocracking
catalysts (labeled herein as Catalyst Samples 5 through I 1) were prepared.
1001091 All of the hydrocracking catalysts tested in this example (both of
Invention and Reference) have equivalent contents of zeolite (Y-zeolite) and
equivalent content of the alumina binder. Except for the differences in the
zeolite
(and zeolite preparation), each of these catalysts were prepared by identical
procedures, with the exception that the only additional difference in the
catalysts
and preparations are in the active metal loadings (i.e., in this example,
platinum,
Pt) utilized between some of the catalysts.
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1001101 For hydrocracking testing and comparison purposes, each of the
catalysts were only impregnated with a single Group 8/9/10 metal (platinum,
Pt).
Because these catalysts were made at different times, the active metal (i.e.,
Pt)
loadings differed, with some of the catalysts with 0.6 wt% Pt loading, and
some
with 2 wt% Pt loading. Although the metal loadings differed between some of
the
catalysts, it is believed that this slight difference in the metal loadings
does not
have any significant effect on the comparative data (i.e., conversions, distil
late
yields, or distillate selectivities) provided in the testing herein.
1001111 In support of this position, separate testing was performed on four
(4)
similar alumina supported zeolite-containing catalysts tested under
hydrocracking
conditions with the only difference in catalysts being the active metal
(platinum)
loading. The four catalysts had a platinum (Pt) loading of 0.3 wt% (Catalyst
Sample 12), 0.6 wt% (Catalyst Sample 13), 1.0 wt% (Catalyst Sample 14), and
2.0 wt% (Catalyst Sample 15) based on the catalyst weight, respectively. The
results of this testing of these four catalysts are shown graphically in
Figure 9
(showing the Distillate Yield for each catalyst sample) and Figure 10 (showing
the
Distillate Selectivity for each catalyst sample). As can be seen from these
figures,
while it is believed that some minimum level of active metal loading is
pertinent
to the overall catalyst performance, that the differences between 0.3 wt% to
2.0
wt% active metal loadings do not lead in themselves to any significant
differences
in the overall hydrocracking results. As such, it is the belief and position
herein
that the differences between the 0.6wt% and 2.0 wt% active metal (Pt) loadings
in
Examples 2 and 3 herein do not significantly affect the comparative
performance
data results shown in these examples.
1001121 The preparation procedures for each of the eleven (11) hydrocracking
catalysts in these examples are described as follows.
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1001131 Catalyst Sample I ¨ EMY Hydrocracking Catalyst ¨ Formulation 1
(Invention)
1001141 In this hydrocracking catalyst sample of invention, an EMY
hydrocracking catalyst was prepared by the following method.
1001151 The EMY zeolite utilized in this catalyst sample started with a
commercial USY zeolite made by Zeolyse under the name CEIV-30e. The 200g
of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
The steamed zeolite was placed in a beaker. A 3pli buffered IN NI-14NO3 ion-
exchange solution (5 ml/gm) was added to the beaker and the contents stirred
for
1 hour at ambient temperature. The zeolite sample was filtered and then the
ion-
exchange procedure was repeated for a second time with a fresh buffered
solution.
Again, the zeolite sample was filtered and then the ion-exchange procedure was
repeated for a third time with a fresh buffered solution. The zeolite sample
was
filtered and rinsed thoroughly with &ionized (DI) water and vacuum dried. The
resu king zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then steamed for 16 hours in 100% steam. The resulting zeolite
then
underwent three (3) more ion-exchange procedures (same as prior) and then was
filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The
resulting zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then calcined for approximately 6 hours at 1000 F in air.
Approximately 30g of the resulting zeolite was placed in a beaker and
underwent
two (2) more ion-exchange procedures (same as prior) and then was filtered and
rinsed thoroughly with dei.onized (DI) water and vacuum dried. The resulting
zeolite was the dried at 250 F. The resulting zeolite was then calcined for
approximately 6 hours at 1000'1F in air.
1001161 About 65 parts of the resulting EMY zeolite was mixed with about 35
parts of Versal 300 pseudoboehmite alumina binder (basis: calcined at ¨538 C)
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in a SimpsonTM muller. Tetraethylammonium Hydroxide (TEAOH) was added to
a sufficient quantity of water to produce a 2% solution, and was added to
produce
an extrudable paste on a ¨2" (--5.1 cm) diameter Bonne extruder. The mixture
of USY crystal, pseudoboehmite alumina, and TEAOH/water was extruded into
¨1/16" diameter quadnilobes, and then dried in a hotpack oven at --250 F (121
C)
overnight (for about 10-18 hours). The dried extrudate was calcined in 100%
air
at 1000 F (538 C) for six hours.
1001171 Once complete, the extrudate was then impregnated via incipient
wetness to ¨2.0 wt% Pt using tetraammineplatinumnitrate, dried in a hotpack
oven
at ¨121 C overnight (for about 3 hours), followed by calcination in air for
about 3
hours at ¨680 F (-405 C) to form Catalyst Sample 1.
1001181 In this version of the EMY hydrocracking catalyst, it is preferred
that
the starting USY undergoes at least one, preferably more than one ion
exchange,
followed by steam calcination, followed by at least one, preferably more than
one
ion exchange, followed by air calcining at a temperature of from about 800 F
to
about 1200 F, or more preferably, at a temperature of at least 1000 F. In
other
embodiments, the zeolite nay be further subjected to at least one additional
ion-
exchange, followed by a second air calcining at a temperature of from about
800 F to about 1200 F, or more preferably, at a temperature of at least 1000
F.
Preferably, the starting zeolite is a low sodium USY with a sodium content
preferably less than about 0.1 wt?/o, or even more preferably less than about
0.05
wt%. Preferably, in the steam calcination step, the steam calcination
temperature
is from about 1200 to 1500 F, or preferably at least 1200 F, more preferably
at
least 1300 F, even more preferably at least 1400 F, and the temperature of the
zeolite precursor is raised to within 50 F of the steam calcination
temperature
within 5 minutes (i.e., very fast steam calcination temperature ramp rate).
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1001191 Catalyst Sample 2 ¨ EMY Hydrocracking Catalyst ¨ Formulation 2
(Invention)
1001201 In this hydrocracking catalyst sample of invention, an EMY
hydrocracking catalyst was prepared by the following method.
1001211 The EMY zeolite utilized in this catalyst sample started with a
commercial USY zeolite made by Zeolyst under the name CEIV-300 . The 200g
of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
The steamed zeolite was placed in a beaker. A 3pli buffered IN NI-14NO3 ion-
exchange solution (5 ml/gm) was added to the beaker and the contents stirred
for
1 hour at ambient temperature. The zeolite sample was filtered and then the
ion-
exchange procedure was repeated for a second time with a fresh buffered
solution.
Again, the zeolite sample was filtered and then the ion-exchange procedure was
repeated for a third time with a fresh buffered solution. The zeolite sample
was
filtered and rinsed thoroughly with &ionized (1)1) water and vacuum dried. The
resu king zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then steamed for 16 hours in 100% steam. The resulting zeolite
then
underwent three (3) more ion-exchange procedures (same as prior) and then was
filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The
resulting zeolite was the dried for approximately 6 hours at 250 F.
Approximately 30g of the resulting zeolite was placed in a beaker and
underwent
two (2) more ion-exchange procedures (same as prior) and then was filtered and
rinsed thoroughly with dei.onized (DI) water and vacuum dried. The resulting
zeolite was the dried at 250 F. The resulting zeolite was then calcined for
approximately 6 hours at 1000 F in air.
1001221 About 65 parts of the resulting EMY zeolite was mixed with about 35
parts of Versal 300 pseudoboehmite alumina binder utilizing the same
procedure
as described for Catalyst 1 to form the extrudate.
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1001231 The extrudate was then impregnated to an active metal loading of ¨2.0
wt% Pt using the same procedure as described for Catalyst Sample I to form
Catalyst Sample 2.
1001241 In this version of the EMY hydrocracking catalyst, it is preferred
that
the starting USY undergoes at least one, preferably more than one ion
exchange,
followed by steam calcination, followed by at least one, preferably more than
one
ion exchange, followed by air calcining at a temperature of from about 800 F
to
about 1200 F, or more preferably, at a temperature of at least 1000 F.
Preferably,
the starting zeolite is a low sodium USY with a sodium content preferably less
than about 0.1 wt%, or even more preferably less than about 0.05 wt%.
Preferably, in the steam calcination step, the steam calcination temperature
is
from about 1200 to 1500 F, or preferably at least 1200 F, more preferably at
least
1300 F, even more preferably at least I400 F, and the temperature of the
zeolite
precursor is raised to within 50 F of the steam. calcination temperature
within 5
minutes (i.e., very fast steam. calcination temperature ram.p rate).
1001251 Catalyst Sample 3 ¨ EMY Flydrocracking Catalyst ¨ Formulation 3
(Invention)
1001261 in this hydrocracking catalyst sample of invention, an :EMY
hydrocracking catalyst was prepared by the following method.
1001271 The EMY zeolite utilized in this catalyst sample started with a
commercial USY zeolite made by Zeolyse under the name CBV-3001). The 200g
of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
The steamed zeolite was placed in a beaker. A 3pH buffered IN NH4NO3 ion-
exchange solution (5 ml/gm) was added to the beaker and the contents stirred
for
1 hour at ambient temperature. The zeolite sample was filtered and then the
ion-
exchange procedure was repeated for a second time with a fresh buffered
solution.
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Again, the zeolite sample was filtered and then the ion-exchange procedure was
repeated for a third time with a fresh buffered solution. The zeolite sample
was
filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The
resulting zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then steamed for 16 hours in 100% steam. The resulting zeolite
then
washed in a 1.5M oxalic acid solution for approximately 2 hours at 176 F and
then was filtered and rinsed thoroughly with deionized (DI) water and vacuum
dried. The oxalic acid wash was then repeated and the zeolite was filtered and
rinsed thoroughly with deionized (D1) water and vacuum dried. The resulting
zeolite was the dried for approximately 6 hours at 250 F. The resulting
zeolite
was then calcined for approximately 6 hours at 1000 F in air. Approximately
30g
of the resulting zeolite was placed in a beaker and underwent two (2) more ion-
exchange procedures (same as prior) and then was filtered and rinsed
thoroughly
with deionized (DI) water and vacuum dried. The resulting zeolite was the
dried at
250 F. The resulting zeolite was then calcined for approximately 6 hours at
1000 F in air.
1001281 About 65 parts of the resulting EMY zeolite was mixed with about 35
parts of Versal9 300 pseudoboehmite alumina binder utilizing the same
procedure
as described for Catalyst 1 to form the extrudate.
1001291 The extrudate was then impregnated to an active metal loading of ¨2.0
wt% Pt using the same procedure as described for Catalyst Sample 1 to form
Catalyst Sample 3.
1001301 In this version of the EMY hydrocracking catalyst, it is preferred
that
the starting IJSY undergoes at least one, preferably more than one ion
exchange,
followed by steam calcination, followed an acid wash, followed by air
calcining
at a temperature of from about 800 F to about 1200 F, or more preferably, at a
temperature of at least 1000 F. In other embodiments, the zeolite may be
further
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subjected to at least one additional ion-exchange, followed by a second air
calcining at a temperature of from about 800 F to about 1200 F, or more
preferably, at a temperature of at least 1000 F. Preferably, the starting
zeolite is a
low sodium USY with a sodium content preferably less than about 0.1 wt%, or
even more preferably less than about 0.05 wt%. Preferably, in the steam
calcination step, the steam calcination temperature is from about 1200 to 1500
F,
or preferably at least 1200 F, more preferably at least 1300 F, even more
preferably at least 1400 F, and the temperature of the zeolite precursor is
raised to
within 50 F of the steam calcination temperature within 5 minutes (i.e., very
fast
steam calcination temperature ramp rate). Preferably the acid wash is
comprised
of a carboxylic acid; more preferably, the acid wash is comprised of oxalic
acid.
1001311 Catalyst Sample 4 ¨ E.MY .Hydrocracking Catalyst ¨ Formulation 4
(Invention)
1001321 In this hydrocracking catalyst sample of invention, an EMY
hydrocracking catalyst was prepared by the following method.
1001331 The EMY zeolite utilized in this catalyst sample started with a
commercial USY zeolite made by Zeolyst under the name CBV-3001). The 200g
of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
The steamed zeolite was placed in a beaker. A 3pH buffered IN NH.4.NO3 ion-
exchange solution (5 ml/gm) was added to the beaker and the contents stirred
for
1 hour at ambient temperature. The zeolite sample was filtered and then the
ion-
exchange procedure was repeated for a second time with a fresh buffered
solution.
Again, the zeolite sample was filtered and then the ion-exchange procedure was
repeated for a third time with a fresh buffered solution. The zeolite sample
was
filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The
resulting zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then steamed for 16 hours in 100% steam. The resulting zeolite
then
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underwent three (3) more ion-exchange procedures (same as prior) and then was
filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The
resulting zeolite was the dried for approximately 6 hours at 250 F. The
resulting
zeolite was then steamed for 16 hours at 1400 F in 100% steam.
1001341 About 65 parts of the resulting EMY zeolite was mixed with about 35
parts of Versal 300 pseudoboehmite alumina binder utilizing the same
procedure
as described for Catalyst 1 to form the extrudate.
1001351 The extrudate was then impregnated to an active metal loading of ¨2.0
wt% Pt using the same procedure as described for Catalyst Sample I to form
Catalyst Sample 4.
1001361 In this version of the EMY hydrocracking catalyst, it is preferred
that
the starting USY undergoes at least one, preferably more than one ion
exchange,
followed by steam calcination, followed by at least one, preferably more than
one
ion exchange, followed by air calcining at a temperature of from about 800 F
to
about 120017, or more preferably, at a temperature of at least 1000 F. In
other
embodiments, the zeolite may be further subjected to at least one additional
ion-
exchange, followed by another steam calcination step at a temperature of at
least
1400 F. Preferably, the starting zeolite is a low sodium USY with a sodium
content preferably less than about 0.1 wt%, or even more preferably less than
about 0.05 wt%. Preferably, at least one steam calcination step, preferably
the
first steam calcination step, the steam calcination temperature is from about
1200
to 1500 F, or preferably at least 1200 F, more preferably at least 1300 F,
even
more preferably at least 1400 F, and the temperature of the zeolite precursor
is
raised to within 50 F of the steam calcination temperature within 5 minutes
(i.e.,
very fast steam calcination temperature ramp rate). In another preferred
embodiment, the starting zeolite undergoes a steam calcination step prior to
the
first ion exchange step.
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1001371 Catalyst Sample 5 - alumina supported CBV-9011 (Reference)
1001381 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001391 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Zeolyse under the name CBV-901 . Here the
zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001401 The hydrocracking catalyst was prepared from the zeolite in
essentially
the sam.e manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 641). That is, about 65 parts of the CBV-901. zeolite
was
mixed with about 35 parts of Versal 300 pseudoboehmite alumina binder
utilizing the sam.c procedure as described for Catalyst Sample 1 to form the
extrudate.
1001411 The extrudate was then impregnated to an active metal loading of ¨0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 5.
1001421 Catalyst Sample 6 - alumina supported HSZ-360- (Reference)
1001431 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001441 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Tosoh under the name HSV-3608. Here the
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zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001451 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5 and 7-11). That is, about 65 parts of the HSV-360
zeolite was mixed with about 35 parts of Vetsal 300 pseudoboehmite alumina
binder utilizing the same procedure as described for Catalyst Sample 1 to form
the
extrudate.
1001461 The extrudate was then impregnated to an active metal loading of ¨0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 6.
1001471 Catalyst Sample 7 - alumina supported CBV-72011Reference)
1001481 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001491 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Zeolyst under the name CBV-720 . Here the
zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001501 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5-6 and 8-11). That is, about 65 parts of the CBV-720
zeolite was mixed with about 35 parts of Versal 300 pseudoboehmite alumina
binder utilizing the same procedure as described for Catalyst Sample 1 to form
the
extrudate.
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1001511 The extrudate was then impregnated to an active metal loading of ¨0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 7.
1001521 Catalyst Sample 8 - alumina supported HSZ-390HUA2 (Reference)
1001531 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001541 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Tosoh under the name HSV-39011:11A . Here
the zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001551 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EM:Y sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5-7 and 9-11). That is, about 65 parts of the 11SV-
390HUA zeolite was mixed with about 35 parts of Versar 300 pseudoboehmite
alumina binder utilizing the same procedure as described for Catalyst Sample 1
to
form the extrudate.
1001561 The extrudate was then impregnated to an active metal loading of ¨0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 8.
1001571 Catalyst Sample 9 - alumina supported CBV-760 (Reference)
1001581 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
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1001591 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Zeolyst under the name CBV-760 . Here the
zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001601 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5-8 and 10-11). That is, about 65 parts of the CBV-760
zeolite was mixed with about 35 parts of Verse 300 pseudoboehmite alumina
binder utilizing the same procedure as described for Catalyst Sample 1 to form
the
extrudate.
1001611 The extrudate was then impregnated to an active metal loading of --0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 9.
1001621 Catalyst Sample 10 - alumina supported CBV-780-t (Reference)
1001631 in this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001641 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Zeolyst under the name CBV-780 . Here the
zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001651 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5-9 and 11). That is, about 65 parts of the CBV-780
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zeolite was mixed with about 35 parts of Vera' 300 pseudoboehrnite alumina
binder utilizing the same procedure as described for Catalyst Sample 1 to form
the
extrudate.
1001 661 The extrudate was then impregnated to an active metal loading of'-O.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 10.
1001 671 Catalyst Sample 11 - alumina supported HSZ-385HUAI (Reference)
1001 681 In this hydrocracking catalyst sample, a USY reference catalyst was
prepared by the following method.
1001 691 The reference USY zeolite utilized in this catalyst sample was a
commercial USY zeolite made by Tosoe under the name HSV-38511:Ug). Here
the zeolite was utilized in the reference hydrocracking catalyst in the as-
purchased
state.
1001 701 The hydrocracking catalyst was prepared from the zeolite in
essentially
the same manner as EMY sample catalysts preps 1-4 (as well as reference
Catalyst Sample preps 5-10). That is, about 65 parts of the HSV-385HUA
zeolite was mixed with about 35 parts of Versar) 300 pseudoboehmite alumina
binder utilizing the same procedure as described for Catalyst Sample 1 to form
the
extrudate.
1001 711 The extrudate was then impregnated to an active metal loading of ¨0.6
wt% Pt using essentially the same procedure as described for Catalyst Sample 1
to
form Catalyst Sample 11.
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Example 4¨ Hydracracking Catalyst Testing
1001721 In this Example, the catalysts prepared above were tested under
hydrocracking conditions in 1) a "batch unit" high-throughput microreactor,
and/or 2) a "flow unit" high-throughput microreactor.
1001731 The main difference in the manner in which these two mieroreactors
are operated is that in the "batch unit" type reactors, the catalyst and feed
are
placed in the reactor vessel and then are subjected to reaction conditions.
That is
the feed (as well as the catalyst) is stationary in the reactor during the
testing (i.e.,
testing performed under "non-flow" reactor conditions). Conversely, in the
"flow
unit" type reactors, the catalyst is placed in the reactor vessel (i.e., the
catalyst is
stationary) and then the feed is passed through the catalyst under reaction
conditions. That is the testing performed under "feed-flow" reactor
conditions.
As a result, of the two (2) different testing protocols and timing of the
tests, while
all four (4) catalyst examples of the invention (i.e., Catalyst Samples 1-4)
were
tested in both types of these high-throughput reactors, the other reference
catalysts
(Catalyst Samples 5-13) were only tested in batch unit (non-flow) microreactor
configuration.
Batch Unit Testing
1001741 All four (4) of the example EMY hydrocracking catalysts of invention
(Sample Catalysts 1-4 above) and all seven (7) of the example reference
hydrocracking catalysts (Sample Catalysts 5-11 above) were tested in a high-
throughput "batch unit" microreactor. In this example, the catalysts were
tested
under batch hydrocracking conditions as follows: 330 C (626 F), 725 psig, and
100% H2 treat gas. The feedstock utilized in the testing was a typical
hydrocracking hydrocarbon feedstock boiling substantially in the range of
about
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700 to about 1100 F (371 to 593 C), with a density at 70 C of 0.8326 g/cm3, a
sulfur content of 43 ppm, and a nitrogen content of <10 ppm.
1001751 Figures 5 and 6 graphically show the results of the batch unit testing
of
the samples for both Distillate Yield (Figure 5) and Distillate Selectivity
(Figure
6).
Flow Unit Testing
1001761 Only the four (4) of the example EMY hydrocracking catalysts of
invention (Sample Catalysts 1-4 above) were tested in a high-throughput "flow
unit" microreactor. In this example, the catalysts were tested under flow
through
hydrocracking conditions as follows: temperature conditions varied from 320 to
370 C (608 to 698 F) during testing, pressure 1275 psig, and 100% H2 treat gas
at ¨2 1.,FISV. Multiple data points were taken for each catalyst at varying
temperature conditions. The feedstock utilized in the testing was a typical
hydrocracking hydrocarbon feedstock boiling substantially in the range of
about
700 to about 1100 F (371 to 593T), with a density at 70 C of 0.8412 g/cm3, a
sulfur content of 178 ppm, and a nitrogen content of <10 ppm. The reaction
products were retrieved during various points in the process and analyzed.
1001771 Figures 7 and 8 graphically show the results of the flow unit testing
of
the samples for both Distillate Yield (Figure 7) and Distillate Selectivity
(Figure
8).
