U.S. patent application number 16/589719 was filed with the patent office on 2021-04-01 for hydrocracking catalyst comprising a beta zeolite (*bea) framework substituted with ti and zr and methods for its preparation and use.
The applicant listed for this patent is JGC CATALYST AND CHEMICALS LTD., SAUDI ARABIAN OIL COMPANY. Invention is credited to Robert Peter HODGKINS, Tomoyasu KAGAWA, Omer Refa KOSEOGLU, Koji UCHIDA, Mitsunori WATABE.
Application Number | 20210095213 16/589719 |
Document ID | / |
Family ID | 1000005459739 |
Filed Date | 2021-04-01 |
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United States Patent
Application |
20210095213 |
Kind Code |
A1 |
HODGKINS; Robert Peter ; et
al. |
April 1, 2021 |
HYDROCRACKING CATALYST COMPRISING A BETA ZEOLITE (*BEA) FRAMEWORK
SUBSTITUTED WITH Ti AND Zr AND METHODS FOR ITS PREPARATION AND
USE
Abstract
The invention relates to methods for hydrocracking or
hydrotreating hydrocarbon containing feedstocks. This is
accomplished via the use of a catalyst which comprises a .beta.
zeolite of *BEA framework, where a portion of aluminum atoms in the
*BEA framework have been substituted by from 0.1-5.0 wt % of each
of Ti and Zr, calculated on an oxide basis.
Inventors: |
HODGKINS; Robert Peter;
(Dhahran, SA) ; KOSEOGLU; Omer Refa; (Dhahran,
SA) ; UCHIDA; Koji; (Kanagawa, JP) ; KAGAWA;
Tomoyasu; (Kanagawa, JP) ; WATABE; Mitsunori;
(Kanagawa, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAUDI ARABIAN OIL COMPANY
JGC CATALYST AND CHEMICALS LTD. |
Dhahran
Kanagawa |
|
SA
JP |
|
|
Family ID: |
1000005459739 |
Appl. No.: |
16/589719 |
Filed: |
October 1, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 47/36 20130101;
C10G 47/20 20130101 |
International
Class: |
C10G 47/20 20060101
C10G047/20; C10G 47/36 20060101 C10G047/36 |
Claims
1. A method for hydrocracking or hydrotreating a hydrocarbon
containing feedstock, comprising contacting said feedstock with (i)
a catalyst, said catalyst comprising an active phase metal and a
.beta. zeolite of *BEA framework, wherein a portion of aluminum
atoms in said *BEA framework have been substituted by from 0.1 to
5.0 wt % of Ti atoms and from 0.1 to 5.0 wt % Zr atoms, said wt %
being calculated on an oxide basis, and (ii) hydrogen, to
hydrocrack or hydrotreat said feedstock.
2. The method of claim 1, wherein said catalyst further comprises
from 0.1 to 5.0 wt % of Hf atoms calculated in an oxide basis.
3. The method of claim 1, wherein said catalyst wherein said .beta.
zeolite has the following characteristics: (a) a crystal lattice
constant of a=1,260 to 1.270 nm, b=1.260 to 1,270 nm, and c=2.6200
to 2.6500 nm. (b) a specific surface area of 400 to 800 m.sup.2/g,
and (c) a molar ratio of SiO.sub.2 to Al2O.sub.3 of 10 to 200.
4. The method of claim 1, wherein said zeolite containing catalyst
support has a specific surface area of 15 to 500 m.sup.2/g; a
volume of pores having a diameter of 600 A or in the range of 0.40
to 0.75 ml/g; and an amount of an active phase metal component
ranging from 0.01 to 40 mass %.
5. The method of claim 1, further comprising: filling a reactor
vessel which is a flow reactor with the hydrocracking catalyst; and
treating a feedstock having a boiling point of 300.degree. C., to
833.degree. C. in the presence of hydrogen at a reactor temperature
of 300.degree. C. to 450.degree. C., a hydrogen pressure of 4 to 30
MPa, a liquid hourly space velocity (LHSV) of 0.1 to 10 h.sup.-1,
and a hydrogen/oil ratio of 500 to 2500 Nm.sup.3/m.sup.3.
6. The method of claim 5, wherein the flow reactor is a flow
reactor selected from the group consisting of a stirred tank, an
ebullient bed reactor, a baffled slurry tank, a fixed bed reactor,
a rotating tubular reactor and a slurry-bed reactor.
7. The method of claim 5, wherein the hydrocarbon oil comprises
refined oil obtained from (1) crude oil, (2) synthetic crude oil,
(3) bitumen, (4) oil sand, (5) shale oil or (6) coal oil.
8. The method of claim 5, wherein the hydrocarbon oil comprises
refined oil obtained from crude oil, synthetic crude oil, bitumen,
oil sand, shale oil or coal oil, and said refined oil is a) vacuum
gas oil (VGO), b) deasphalted oil (DAO) obtained from a solvent
deasphalting process or demetallized oil, c) light coker gas oil or
heavy coker gas oil obtained from a coker process, d) cycle oil
obtained from a fluid catalytic cracking (FCC) process or e) gas
oil obtained from a visbraking process.
9. The method of claim 1, further comprising: filling a
hydrotreating apparatus which is a flow reactor with the
hydrocracking catalyst; and treating a feedstock having a boiling
point of 375.degree. C. to 650.degree. C. in the presence of
hydrogen at a reactor temperature of 330.degree. C. to 450.degree.
C., a hydrogen pressure of 7 to 15 MPa, a liquid hourly space
velocity (LHSV) of 0.2 to 1.5h.sup.-1, and a hydrogen/oil ratio of
1000 to 2000 Nm.sup.3/m.sup.3 to yield a middle distillate.
10. The method of claim 1, wherein said .beta. zeolite contains
from 0.1-2.0 mass % of each of Ti and Zr, on an oxide basis.
11. The method of claim 2, wherein said zeolite contains from
0.1-2.0 mass % Hf, on an oxide basis.
12. The method of claim 1, wherein said catalyst is on an inorganic
support,
13. The method of claim 12, wherein said inorganic support
comprises at least one of alumina and. silica.
14. The method of claim 1, wherein said .beta. zeolite has a molar
ratio of SiO.sub.2 to Al.sub.2O.sub.3 of 10 to 100.
15. The method of claim 14, wherein said molar ratio is 30 to
70,
16. The method of claim 3, wherein said surface area is 500-700
m.sup.2/g.
17. The method of claim 12, wherein said catalyst has a specific
surface area of 150-500 m.sup.2/g,
18. The method of claim 17, wherein said specific surface area is
150-450 m.sup.2/g.
19. The method of claim 1, wherein said active metal phase
component comprises from 0.01-40 mass % of said catalyst calculated
on an oxide basis.
20. The method of claim 19, wherein said active metal phase
comprises 10-35 mass % of said catalyst, calculated on an oxide
basis.
21. The method of claim 1, wherein said active metal phase metals
comprises Fe, Co, Ni, Rh, Pd, Ag, In, Pt, Au, Cr, Mo, or W.
22. The method of claim 1, wherein said zeolite comprises from 1-80
mass % of said catalyst.
23. The method of claim 22, wherein said zeolite comprises from
5-50 mass % of said catalyst.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a method for hydrocracking a
hydrocarbon feedstock, using a new catalytic composition.
Specifically, the catalytic composition comprises a *BEA zeolite,
where a part of the aluminum ions in the zeolite framework have
been substituted with 0.1-5 mass % of both of titanium and
zirconium, calculated on an oxide basis, and also comprises at
least one active phase metal which has hydrogenation and/or
hydrodesulfurization and/or hydrodenitrogenation functions.
BACKGROUND OF THE INVENTION
[0002] For many years, catalysts which contained zeolites, and one
or both of titanium and zirconium, where the metals were carried on
mesopores, were used for treating bottom oil. See, e.g., Japanese
Unexamined Patent Application Publication Nos. 2000-334305,
2002-255537, and 2003-226519. Also, see U.S. Pat. Nos. 10,293,332
and 9,221,036, incorporated by reference.
[0003] Japanese Patent Application Publication No. 2000-334305
teaches hydrocracking catalysts which comprise an active phase
metal on a zeolite support. The support contains ultrafine
particles of titanium or zirconium oxide, which have been combined
with the inner surfaces of mesopores. The atomic ratio of Al to Si
is from 0.01-0.1, which equates to a SiO.sub.2/Al.sub.2O.sub.3
molar ratio or "SAR" of 20 to 200. These catalysts are prepared by
combining mesopore containing zeolites with an aqueous solution of
a Ti or Zr oxide, at a pH of from 0.8 to 2. The zeolite is then
washed, dried, and fired at 400-600.degree. C.
[0004] The "255537" publication teaches a zeolite with a high
mesopore content. and an atomic ratio of Al to Si of from 0.01 to
0.2 (an SAR of 10 to 200), with 30-50% of the mesopore volume
having a pore diameter of to 50 100 .ANG.. The mesopores have a
volume of 0.14 cc/g or more, with 25% or more of the Al atoms being
tetracoordinated. Ultrafine particles of Ti or Zr oxide, which are
not readily reduced, combine with. the inner surface of zeolite
mesopores. This serves as a support for active phase metals. The
process for making the catalyst is similar to that for the "334305"
application, in that the zeolite is brought into contact with an
aqueous solution of Ti or Zr oxide, at a pH of 0.8 to 2, followed
by drying at 50-200.degree. C., and firing at 350-600.degree.
C.
[0005] The "226519" application also teaches a hydrocracking
catalyst, where a zeolite of FAU (faujasite) structure, contains
Ti, Zr, or Hf. The metal content is from 0.1-10% by weight
(calculated on an elemental basis), an Al/Si atomic ratio of 0.01
to 0.1 (SAI;. of 20 to 200), and also contains active phase metals.
The FAU zeolite has a crystal lattice constant of from 24.28-24.46
.ANG.. The preparation is similar to that of the catalyst described
supra.
[0006] In these hydrocracking catalysts, however, the mesopores
become clogged with the metals which are present in the feedstock
such as vanadium and nickel, and therefore these catalysts were not
suited for hydrotreating (or hydrocracking) of heavy hydrocarbon
oil such as VGO and DAO, or other petroleum based hydrocarbon
feedstocks, without any prior protective hydrodemetallization
layer.
[0007] As disclosed in WO2007/032232, incorporated by reference in
its entirety, hydrocracking catalysts including a Y-type zeolite as
a support, contain titanium atoms incorporated into a zeolite
framework. (In other words, a Y-type zeolite in which a part of the
aluminum atoms constituting the framework are substituted with
titanium atoms) has been. developed. The above zeolite can be
prepared by treating a Y-type zeolite with an acidic aqueous
solution containing titanium at a pH of 1.5 or less, followed by
filtering, washing, and drying. Thereby, the zeolite can be made to
contain titanium atoms incorporated into a zeolite framework
structure without clogging the mesopores. The reference states
that, when the hydrocracking catalyst including the above zeolite
as a support is used to hydrocrack heavy hydrocarbon oil, yields of
middle distillates are improved because heavy hydrocarbon oil is
readily diffuses into the mesopores.
[0008] U.S. Pat. No. 10,081,009, the disclosure of which is
incorporated by reference in its entirety, teach that USY zeolites
having an FAU framework, can be treated so as to replace a portion
of the aluminum in their zeolite framework, and this aluminum can
be replaced with from 0.1 to 5.0 wt % of both of Ti and Zr, where
the weight percent is calculated on an oxide basis. The resulting
catalysts were found to be extremely useful in hydrotreating and
hydrocracking feedstocks such as hydrocarbon oil. The catalysts
provided high yields of middle distillates.
[0009] Also, see published U.S. Patent Application US 2015/0375218,
which is incorporated by reference in its entirety as well. U.S.
Published Patent Application US 2013/0319910 is also incorporated
by reference. These published patent applications all employ the
USY catalyst with framework substitution discussed supra.
[0010] Beta zeolites are known in the catalytic art, although not
in the context of hydrotreating or hydrocracking. U.S. Pat. No,
4,826,586, e.g., teaches the possibility of using beta zeolites in
fluidized catalytic cracking (FCC) processes. The conditions under
which FCC processes are carried out are very unlike those used in
hydrocracking/hydrotreating, and the artisan does not treat these
processes as equivalent. The FCC process also does not use
hydrogen, in contrast to hydrocracking/hydrotreating. Also see CN
106145136, teaching modification of beta zeolites, as well as CN
104549543 and CN 106140289. in each case, the preparation
methodology makes clear that ion exchange, rather than framework
substitution, is the process by which metals are included in the
zeolite, resulting in a catalyst that is not equivalent to one
where framework substitution takes place.
[0011] U.S. Pat. No. 6,063,944, teaches insertion of titanium into
a beta zeolite, but does not mention Zr. Also, see U.S. Pat. No.
6,017,840, teaching impregnation of metals into a beta zeolite
without framework substitution. Also to this point are Reddy, et
al., Studies in Surface Science and Catalysts, 94:309-316 (1995)
and Hamdy, et al., Mol. Catalysts, 441:140-149 (2017), and Rakshe,
et al., J. Catalysis, 188:252-260 (1999), discussing modification
with. Zr, but not Ti.
[0012] It is an aim of the present invention to provide a
hydrocracking or hydrotreating methodology which improves the yield
of desired products, such as middle distillates, This is
accomplished by replacing the USY zeolite, of U.S. Pat. No.
10,081,009, which has an FAU framework, with a beta zeolite having
a *BEA framework.
BRIEF DESCRIPTION OF THE FIGURES
[0013] FIG. 1 presents XRD data to show structural integrity of the
catalists of the invention.
[0014] FIG. 2 depicts UV-Vis spectra for the base zeolite and the
final catalyst of the invention.
[0015] FIG. 3 shows, graphically, differences in total acidity and
acidity strength between USY based catalysts, and the *BEA
catalysts of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0016] The invention is a method for hydrocracking a petroleum
based, hydrocarbon feedstock under hydrocracking conditions with a
catalyst, said catalyst comprising an active phase metal compound
carried on a support which comprises a beta zeolite having a *BEA
framework, wherein a portion of aluminum atoms in said framework
have been substituted/replaced by from 0.1-5 wt % of each of Ti and
Zr, wherein the weights are calculated on an oxide basis.
Optionally, 0.1-5 wt % of Hf can be used to substitute Al as well.
Active phase metal comprises one or more of Fe, Co, Ni, Rh, Pd, Ag,
In, Pt, Au, Cr, Mo, or W. In some embodiments, the amount of Ti and
Zr is 0.1-2.0 mass % on an oxide basis. In further embodiments, the
amount of Hf present is from 0.1-2.0 mass % on an oxide basis.
[0017] The modified beta zeolite framework containing Ti and Zr
atoms of the invention preferably possesses one or more, and most
preferably all, of the following characteristics: [0018] (a) a
crystal lattice constant of a=1.260 to 1.270 nm, h=1,260 to 1.270
mu, and c=26,200 to 26.500 nm; [0019] (b) a specific surface area
of 400 to 800 m.sup.2/g, preferably 500-700 m.sup.2.g, and [0020]
(c) a molar ratio of 10 to 200 (preferably 10-100, and more
preferably, 30-70) in terms of SiO.sub.2 to Al.sub.2O.sub.3.
[0021] The "specific surface area" referred to supra relates to the
modified zeolite itself, as do all of the other properties listed.
The zeolite containing catalyst support has a specific surface area
of 15-500 m.sup.2/g, and more preferably 150-450 m.sup.2/g.
[0022] In the hydrocracking catalyst for hydrocarbon oil according
to the present invention, a specific surface area thereof which
falls preferably in a range of 15-500 m.sup.2/g, preferably 150 to
400 m.sup.2/g; a volume of pores having a diameter of 600 .ANG. or
less, which falls preferably in a range of 0,40 to 0.75 ml/g; and
an amount of the active phase metal component in a range of 0.01 to
40% by mass, preferably from 10-35 mass % on an oxide basis. The
amount of TiZr beta zeolite in the catalyst ranges from 1-80 wt %
of the catalyst weight, and preferably 5-50 wt %. In some
embodiments, the catalyst is on an inorganic support, preferably
one which contains alumina and silica.
[0023] The method for producing the hydrocracking catalyst of the
invention comprises substituting a part of aluminum atoms of the
Beta zeolite with *BEA framework with zirconium atoms and titanium
atoms, followed by firing the zeolite at a temperature of from
55-700.degree. C. The Beta zeolite with *BEA framework with
zirconium and titanium atoms of the invention has a. crystal
lattice constant falling in a range of a=1.260 to 1,270 nm, b=1.260
to 1.270 nm, and c=2.6.200 to 26,500 nm, a specific surface area of
400 to 800 m.sup.2/g and a molar ratio of SiO.sub.2 to
Al.sub.2O.sub.3 of 10 to 200, preferably 10-100, and more
preferably 30-70, preparing a suspension having a mass ratio of 5
to 15 in terms of liquid/solid from the above fired zeolite, adding
an inorganic acid or an organic acid thereto so that a pH of the
above suspension is less than 2.0, subsequently adding a zirconium
compound and/or a titanium compound and mixing them and then
neutralizing the suspension.
[0024] In another method for producing a hydrocracking catalyst of
the invention, a zeolite as described supra, is used to prepare a
suspension having a mass ratio of 5 to 15 in terms of liquid/solid
zeolite, adding an inorganic acid or an organic acid thereto so
that the pH of the suspension is less than 2.0, adding a zirconium
compound and titanium compound, mixing, and then neutralizing the
mixed solution to secure the catalyst.
[0025] A third aspect of the present invention is a method for
hydrocracking a petroleum based hydrocarbon feedstock, such as
hydrocarbon oil with the hydrocracking catalyst described above, in
the presence of hydrogen and appropriate reaction conditions.
[0026] Preferably, the method for hydrocracking a petroleum based
hydrocarbon feedstock according to the invention comprise placing a
reactor vessel of a hydrocracking apparatus which is a flow reactor
with the catalyst of the invention., and treating the feedstock
having a boiling point of 300.degree. C. to 833.degree. C. in the
presence of hydrogen at a reactor temperature of 300.degree. C. to
450.degree. C., a hydrogen pressure of 4 to 30 MPa, a liquid hourly
space velocity (LHSV) of 0.1 to 10 h and a Hydrogen/oil ratio of
500 to 2500 Nm.sup.3/m.sup.3.
[0027] Preferably, the method for hydrocracking hydrocarbon oil
according to the invention involves treating a feedstock with a
boiling point of 375-650.degree. C. with the catalyst, and in the
presence of hydrogen at a reactor temperature of 330.degree. C. to
450'' C., a hydrogen pressure of 7 to 15 MPa, a liquid hourly space
velocity (LHSV) of 0.2 to 1.5 h.sup.-1, and a hydrogen/oil ratio of
1000 to 2000 Nm.sup.3/m.sup.3 to yield a middle distillate.
Preferably this middle distillate is rich in kerosene and gas
oil.
[0028] In the method for hydrocracking hydrocarbon oil according to
the present invention, the flow reactor described above is
preferably a flow reactor selected from the group consisting of a
stirring bath type reactor, a. boiling bed type reactor, a
baffle-equipped slurry bath type reactor, a fixed bed type reactor,
a rotary tube type reactor and a slurry bed type reactor.
[0029] In the method for hydrocracking a petroleum feedstock
according to the invention, the hydrocarbon feedstock described
above preferably contains refined oil obtained from (1) crude oil,
(2) synthetic crude oil, (3) bitumen, (4) oil sand, (5) shell oil
or (6) coal liquid.
[0030] In the method for hydrocracking hydrocarbon oil according to
the present invention, the hydrocarbon oil described above contains
refined oil obtained from crude oil, synthetic crude oil, bitumen,
oil sand, shell oil or coal liquid, and the above refined oil is
preferably any of a) vacuum gas oil (VGO), b) deasphalted oil (DAO)
obtained from a solvent deasphalting process or demetalized oil, c)
light coker gas oil or heavy coker gas oil obtained. from a coker
process, d) cycle oil obtained from a fluid catalytic cracking
(FCC) process or e) gas oil obtained from a visbraking process.
[0031] The hydrocracking catalyst for hydrocarbon oil according to
the present invention comprises a hydrogenative metal component
carried on a support containing a Beta zeolite of *BEA type, which
a part of aluminum atoms constituting the framework thereof is
substituted with zirconium atoms and titanium ions.
[0032] Accordingly, the hydrocracking catalyst of the present
invention makes it easy to diffuse heavy hydrocarbons such as VGO,
DAO and the like into mesopores thereof as compared with
conventional hydrocracking catalysts.
[0033] FIG. 3 shows the results of tests to determine the acidity
of catalysts of the invention and the prior art.
EXAMPLE 1
[0034] A beta zeolite of *BEA framework, having a silica/alumina
ratio ("SAR" hereafter) of 28.5 was used. A total of 51.4 g of this
zeolite was suspended in 450 g of deionized water, and heated to
40.degree. C. A total of 14.8 g of H.sub.2SO.sub.4 (25 wt %) was
added, together with 10.0 g of an aqueous solution of titanium
sulfate (equivalent to 5 wt % TiO.sub.2). The solution contained
8.48 g deionized water and 1.52 g titanium sulfate (equivalent to
33 wt % TiO.sub.2). An additional. aqueous zirconium sulfate
solution (2.8 g, constituting 18 wt % ZrO.sub.2) was added, and the
mixture was stirred for 4 hours, then filtered and washed with 1.5
liters of deionized water. This took place at 60.degree. C. The
resulting zeolite was dried at 110.degree. C. to yield a framework
substituted, Ti/Zr beta zeolite.
[0035] The XRD data for the *BEA zeolite before framework
substitution, and after, are shown in FIG. 1. It can be seen that
the structural integrity of the zeolite remained.
EXAMPLE 2
[0036] The *BEA zeolite and framework substituted *BEA zeolite were
analyzed, and the results follow in Table 1.
TABLE-US-00001 TABLE 1 Compositional analysis of zeolite Beta
before and after Ti/Zr treatment. SiO.sub.3/Al.sub.2O.sub.3 ratio
TiO.sub.2 ZrO.sub.2 Surface Area Zeolite mol/mol % % m.sup.2/g
.beta.-Zeolite 28.5 -- -- 623 .beta.-Zeolite + Ti/Zr 53.5 0.84 0.31
614
[0037] Additional data are shown in FIG. 2, which presents UV-Vis
spectra of the original .beta. zeolite, and the framework
substituted .beta. zeolite. One sees a Ti 4-coordinated species and
a wavelength of about 250 nm. If 6-coordinated species were
present, one would expect a shift to a higher wavelength, at about
285 nm, This did not occur, as shown by FIG. 2.
EXAMPLE 3
[0038] Experiments were carried out to determine what impact
substitution of alumina framework by Ti and Zr would have on the
acidity of the zeolite.
[0039] Both USY and *BEA zeolites were tested for acidity,
unmodified, and modified by substitution of Ti & Zr.
[0040] FIG. 3 presents these results where total acidity is shown
by the height of the bars, while the horizontal bars show weak
(100-200.degree. C.), medium (200-400.degree. C.), and strong
(400-500.degree. C.) acid site content.
[0041] Other features of the invention will be clear to the skilled
artisan and need not be reiterated here.
[0042] The terms and expression which have been employed are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expression of excluding any
equivalents of the features shown and described or portions
thereof, it being recognized that various modifications are
possible within the scope of the invention.
* * * * *