Note: Descriptions are shown in the official language in which they were submitted.
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CATALYST FOR SELECTIVE OPENING OF CYCLIC PARAFFINS AND PROCESS FOR USING THE
CATALYST
BACKGROUND OF THE INVENTION
[0001] This invention relates to a catalyst for the selective opening of
cyclic
paraffins which comprises a Group VIII metal component, a molecular sieve, a
refractory oxide and optionally a modifier. This invention also relates to a
process for
selective ring opening using the catalyst.
[0002] Olefins are used in various reactions to produce important chemical
compounds. Accordingly, demand for olefins is ever increasing and therefore
new
processes or increased efficiencies in existing processes are required. One of
the main
processes used in preparing light olefins is naphtha steam cracking. It is
known that
the efficiency of steam cracking depends on the specific composition of the
naphtha
feed. Specifically it has been demonstrated that converting naphthenes to
acyclic
paraffins, e.g. n-paraffins significantly improves olefin yield from the steam
cracker.
There is, therefore, a need for an improved ring opening catalyst.
[0003] Improved ring opening catalysts are also necessary because of
increasing
demand for environmentally friendly products and clean burning high
performance
fuels. In this case naphthene rings are opened to give acyclic paraffins which
in turn
can be isomerized. These isomerized paraffins have improved characteristics
than the
corresponding naphthenes.
[0004] An increased amount of paraffins is also required in providing
reformulated gasoline. Reformulated gasoline differs from the traditional
product in
having a lower vapor pressure, lower final boiling point, increased content of
oxygenates, and lower content of olefins, benzene and aromatics.
[0005] Reduction in gasoline benzene content often has been addressed by
changing the cut point between light and heavy naphtha, directing more of the
potential benzene formers to isomerization instead of to reforming. No benzene
is
formed in isomerization, wherein benzene is converted to C6 naphthenes and C6
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naphthenes are isomerized toward an equilibrium mixture of cyclohexane and
methylcyclopentane or converted to paraffins through ring opening. It is
believed that
such C6 cyclics are preferentially adsorbed on catalyst sites relative to
paraffins, and
the cyclics thus have a significant effect on catalyst activity for
isomerization of
paraffins. Refiners thus face the problem of maintaining the performance of
light-
naphtha isomerization units which process an increased concentration of
feedstock
cyclics.
[0006] Catalysts which are useful for ring opening are known and include a
high
chloride platinum component dispersed on a refractory inorganic oxide which is
described in US-A-5,463,155. US-A-5,811,624 describes a catalyst for the
selective
opening of 5 and 6 membered rings which consists of a transition metal
catalyst
selected from the group consisting of carbides, nitrides, oxycarbides,
oxynitrides, and
oxycarbonitrides. The transition metal is selected from the group consisting
of metals
from Group IVA, VA, VIA of the Periodic Table of the Elements. US-A-6, 235,962
B1 discloses a catalyst for ring opening which comprises a carrier consisting
of
alumina, a metal modifier selected from the group consisting of scandium,
yttrium and
lanthanum, and at least one catalytically active metal selected from the group
consisting of platinum, palladium, rhodium, rhenium, iridium, ruthenium, and
cobalt.
US-A-5,382,730 discloses a process for ring opening and isomerization of
hydrocarbons where the catalyst comprises an aluminosilicate zeolite such as
Zeolite
Y or Zeolite Beta and a hydrogenation component. US-A-5,345,026 discloses a
process for conversion of cyclic hydrocarbons to non-cyclic paraffin
hydrocarbons
where the catalyst comprises a hydrogenation-dehydrogenation component and an
acidic solid component comprising a group IVB metal oxide modified with an
oxyanion of a group VIB metal. US-A-3,617,511 discloses a catalyst for
conversion
of cyclic hydrocarbons to paraffins where the catalyst comprises rhodium or
ruthenium on a halogen promoted refractory oxide. US-A-6,241,876 discloses a
ring
opening catalyst which comprises a large pore crystalline molecular sieve
component
with a faujasite structure and an alpha acidity of less than one and a Group
VIII noble
metal. U.S. Publication No. 2002/43481 Al discloses a catalyst for naphthalene
ring
opening which comprises at least one Group VIII metal selected from iridium,
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platinum, rhodium and ruthenium on a refractory inorganic oxide substrate
containing
at least one of an alkali metal and alkaline earth metal. Finally U.S.
Publication No.
2002/40175 Al discloses a naphthene ring opening catalyst comprising a Group
VIII
metal selected from iridium, platinum, palladium, rhodium, ruthenium and
combinations thereof. With the metal being supported on the substrate
comprising at
least one of a Group IB, BB, and IVA metal.
DETAILED DESCRIPTION OF THE INVENTION
[0007] One aspect of the present invention is a catalyst which is useful for
opening or cleaving naphthenic rings. The catalyst of the present invention
comprises
a Group VHI metal component an optional modifier component, a molecular sieve
and
a refractory inorganic oxide. The molecular sieves which can be used in the
present
invention are any of those which have 8, 10 or 12 ring pores and which have
weak to
medium acidity. Acidity of the molecular sieves can be determined by one of
several
techniques. One method involves measuring the ability of the molecular sieves
to
crack heptane, i.e. heptane cracking test. The cracking test involves placing
a sample
(250 mg) of the molecular sieve to be tested into a microreactor and drying
the
catalyst for 30 minutes at 200 C using flowing hydrogen. The sample is then
reduced
by heating for one hour at 500 C in flowing hydrogen. After cooling to 450 C a
feedstream comprising hydrogen gas saturated with heptane at 0 C is flowed
over the
sample. Online analysis of the effluent gas is carried out using gas
chromatography
after holding for 20 minutes at a temperature from 450-550 C. A weakly acidic
molecular sieve will have a heptane conversation of no more that 20% and
preferably
no more than 10%, while a moderately acidic molecular sieve will have a
cracking
conversion of no more than 40% and preferably no more than 30%. Another test
method is ammonia temperature programmed desorption or NH3-TPD. This test
basically involves contacting a molecular sieve sample with ammonia and then
measuring the amount of ammonia desorbed over a temperature range of 200 C to
500 C. Details of this test procedure are provided in US-A-4,894,142.
Molecular sieves with moderate acidity will desorb less than 0.4mmol of NH3/g
total over the 200 C to 500 C range, while a weakly
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acidic molecular sieve will desorb a total of less than 0.2mmol of NH3/g over
the
200 C to 500 C temperature range. Finally, acidity can be measured by pyridine
infrared (IR). Specific examples of molecular sieves with weak to moderate
acidity,
include but are not limited to MAPSOs, SAPOs, UZM-4, UZM-4M, UZM-5, UZM-
5P, UZM-5HS, UZM-6, UZM-8, UZM-8HS, UZM-15, UZM-15HS, UZM-16, UZM-
16HS and mixtures thereof. MAPSO molecular sieves are disclosed in US-A-
4,758,419. A preferred MAPSO is MAPSO-31. SAPO molecular sieves are
disclosed in US-A-4,440,871. Preferred SAPOs are SAPO-11, SAPO-34 and SM-3
(US-A-4,943,424). UZM-4 is described in US-A-6,419,895 B 1 while UZM-5, UZM-
5P and UZM-6 are described in US-A-6,388,157 B1. The other UZM molecular
sieves are described in the following U.S. Patent Applications.
U.S.
Zeolite Application No.
UZM-4M 6,776,975
UZM-5HS 6,982,074
UZM-8 6,756,030
UZM-8HS 7,713,513
UZM-15 and UZM-15HS 6,890,511
UZM-16 and UZM-16HS 6,752,980
[0008] Further, all the molecular sieves identified by a UZM designation will
collectively be referred to as UZM zeolites. For completeness, the following
brief
description of the UZM zeolites described in the patent applications above
will be
provided below.
[0009] All of the UZM zeolites have a microporous crystalline structure of at
least
A102 and SiO2 tetrahedral units. UZM-8, UZM-15 and UZM-16 have a composition
on an as-synthesized and anhydrous basis expressed by an empirical formula of:
Mm+Rp+AIl-XEXSiYOZ M.
M is at least one exchangeable cation selected from the group consisting of
alkali and
alkaline earth metals, "m" is the mole ratio of M to (A] + E) and, "n" is the
weighted
average valence of M. R is defined as follows:
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1) UZM-8: R is at least one organoammonium cation selected from the group
consisting of quaternary ammonium cations, diquaternary ammonium cations,
protonated amines, protonated diamines, protonated alkanolamines and
quaternized alkanolammonium cations, "r" is the mole ratio of R to (Al + E).
2) UZM-15: R is at least one first quaternary organoammonium cation
comprising at least one organic group having at least two carbon atoms, and
optionally a second organoammonium cation selected from the group
consisting of quaternary ammonium cations, protonated amines, protonated
diamines, protonated alkanolamines, diquaternaryammonium cations,
quaternized alkanolamines and mixtures thereof, "r" is the mole ratio of R to
(Al + E); and
3) UZM-16: R is benzyltrimethylammonium (BzTMA) cation or a combination
of BzTMA and at least one organoammonium cation selected from the group
consisting of quaternary ammonium cations, protonated amines, protonated
diamines, protonated alkanolamines, diquaternaryammonium cations,
quaternized alkanolamines and mixtures thereof, "r" is the mole ratio of R to
(Al + E).
[0010] E is an element selected from the group consisting of Ga, Fe, In, Cr,
B, and
mixtures thereof. The other variables are defined as "p" is the weighted
average
valence of R; "x" is the mole fraction of E, "y' is the mole ratio of Si to
(Al + E) and
"z" is the mole ratio of 0 to (Al + E). The values of "m", "n", "r", "p", "x",
"y" and
"z" are presented in Table A.
Table A
Variable UZM-8 UZM-15 UZM-16
in Oto2.0 Oto2.0 Oto0.75
n l to 2 l to 2 l to 2
r 0.05 to 5.0 0.25 to 5.0 0.25 to 5.0
p l to 2 l to 2 1 to 2
x 0 to 1.0 0 to 1.0 0 to 1.0
y 6.5 to 35 7 to 50 3 to 2.5
z (m=n+r=p+3+4=y)/2 (m=n+r=p+3+4=y)/2 (m=n+rp+3+4=y)/2
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[0011] These zeolites are also characterized by x-ray diffraction patterns
having at
least the d-spacings and relative intensities set forth in Table B (UZM-8),
Table C
(UZM-15) and Table D (UZM-16).
Table B (UZM-8)
a
2-0 d(A) VIA
6.40-6.90 13.80-12.80 w - s
6.95-7.42 12.70- 11.90 m- s
8.33-9.11 10.60-9.70 w-vs
19.62 - 20.49 4.52-4.33 m - vs
21.93 - 22.84 4.05-3.89 m - vs
24.71-25.35 3.60-3.51 w-m
25.73 - 26.35 3.46-3.38 m - vs
Table C (UZM-15)
0
2-0 d(A) I/10%
8.35-9.30 10.58-9.50 w-m
12.30 - 13.30 7.19-6.65 w-m
16.60 - 17.20 5.34-5.15 w-m
19.00 - 19.80 4.67-4.48 w-m
20.80 - 22.30 4.27-3.98 w
23.55 - 23.95 3.77-3.71 w-m
24.03 - 24.47 3.70-3.63 w-m
25.50 - 26.25 3.49-3.39 vs
48.30 - 49.10 1.88-1.85 w
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Table D (UZM-16)
2-0 d(A) 1/10%
3.86-4.22 22.87 - 20.92 w-m
7.60-7.84 11.62 - 11.27 s-vs
11.58-11.86 7.64-7.46 w-m
13.29-13.54 6.65-6.53 m
13.90-14.20 6.36-6.23 w
15.34-15.68 5.77-5.65 m
19.30-19.65 4.60-4.51 m
20.37-20.73 4.35-4.28 m-s
23.18-23.54 3.83-3.78 m-s
23.57-23.89 3.77-3.72 s-vs
24.68-25.03 3.60-3.55 m-s
26.84-27.23 3.32-3.27 m
28.15-28.58 3.17-3.12 m
31.25-31.71 2.86-2.82 vs
33.37-33.76 2.68-2.65 w
35.89-36.36 2.50-2.47 m
48.05-48.52 1.89-1.87 w-m
51.38-51.90 1,78-1.76 w-m
55.35-56.04 1.66-1.64 w-m
58.08-58.64 1.59-1.57 w
[0012] The UZM-8, UZM-15 and UZM-16 zeolites are prepared by a hydrothermal
crystallization of a reaction mixture prepared by combining reactive sources
of R,
aluminum, silicon and optionally M and E. The sources of aluminum include but
are not
limited to aluminum alkoxides, precipitated aluminas, aluminum metal, sodium
aluminate, organoammonium aluminates, aluminum salts and alumina sols.
Specific
examples of aluminum alkoxides include, but are not limited to aluminum ortho
sec-
butoxide and aluminum ortho isopropoxide. Sources of silica include but are
not limited
to tetraethylorthosilicate, colloidal silica, precipitated silica, alkali
silicates and
organoammonium silicates. A special reagent consisting of an organoammonium
aluminosilicate solution can also serve as the simultaneous source of Al, Si,
and R.
Sources of the E elements include but are not limited to alkali borates, boric
acid,
precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric
chloride,
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chromium nitrate and indium chloride. Sources of the M metals include the
halide salts,
nitrate salts, acetate salts, and hydroxides of the respective alkali or
alkaline earth
metals. R can be introduced as an organoammonium cation or an amine. When R is
a
quaternary ammonium cation or a quaternized alkanolammonium cation, the
sources
include but are not limited to the hydroxide, chloride, bromide, iodide and
fluoride
compounds. Specific examples include without limitation DEDMA hydroxide, ETMA
hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide,
hexamethonium bromide, tetrapropylammonium hydroxide, methyl tri ethyl
ammonium
hydroxide, tetramethylammonium chloride, propylethyldimethylammonium hydroxide
(PEDMAOH), trimethylpropyl ammonium hydroxide, trimethylbutylammonium
hydroxide (TMBAOH), N,N,N,N',N',N' hexamethyl 1,4 butanediammonium hydroxide
(DQ4), and choline chloride. The source of R may also be neutral amines,
diamines,
and alkanolamines that subsequently hydrolyzes to form an organoammonium
cation.
Specific examples are triethanolamine, triethylamine, and N,N,N',N'tetramethyl-
1,6-
hexanediamine. Preferred sources of R without limitation are ETMAOH, DEDMAOH,
and HM(OH)2.
[0013] In a special case, a reagent in the form of an aluminosilicate stock
solution
may be used. These solutions consist of one or more organoammonium hydroxides
and
sources of silicon and aluminum that are processed to form a clear homogenous
solution
that is generally stored and used as a reagent. The reagent contains
aluminosilicate
species that typically don't show up in zeolite reaction mixtures derived
directly from
separate sources of silicon and aluminum. The reagent is generally alkali-free
or
contains alkali at impurity levels from the silicon, aluminum, and
organoammonium
hydroxide sources. One or more of these solutions may be used in a zeolite
synthesis. In
the case of substitution of Al by E, the corresponding metallosilicate
solution may also
be employed in a synthesis.
[0014] As shown above, not all the R cations can produce all of the three UZM
structures. Thus the preparation of UZM-15 requires at least one first
organoammonium
cation having at least one organic group with at least two carbon atoms, e.g.
DEDMA,
ETMA, TMBA, DQ4 and PEDMA and optionally (in addition to the first
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organoammonium cation) a second organoammonium compound. The preparation of
UZM-16 requires benzyltrimethylammonium (BzTMA) or a combination of BzTMA
and at least one organoammonium cation as described above.
[0015] The reaction mixture containing reactive sources of the desired
components
can be described in terms of molar ratios of the oxides by the formula:
aM2iõO:bR2/pO: (1-c)A12O3:cE2O3: dSiO2: eH2O .
[0016] The values of the variables for the UZM-8, 15 and 16 are presented in
Table
E along with general and preferred reaction conditions. The reaction mixtures
are
reacted at the stated conditions in a sealed reaction vessel under autogenous
pressure.
Table E
Reaction Mixture Compositions and Reaction Conditions for UZM Zeolites
Variable UZM-8 UZM-15 UZM-16
a 0to25 Oto5 Oto5
b 1to80 1.5 to 80 1to120
c 0 to 1.0 0 to 1.0 0 to 1.0
d 10 to 100 10 to 100 5 to 100
e 100 to 1500 100 to 1500 50 to 1500
Temp( C)- broad 85 C to 225 C 85 C to 225 C 80 C to 160 C
range
Temp( C)-preferred 125 C to 150 C 140 C to 175 C 95 C to 125 C
range
Time- broad range 1 day to 28 days 12 hrs. to 20 days 2 days to 30 days
Time- preferred 5 days to 14 days 2 days to 10 days 5 days to 15 days
range
[0017] After crystallization is complete, the solid product is isolated from
the
heterogeneous mixture by means such as filtration or centrifugation, and then
washed
with de-ionized water and dried in air at ambient temperature up to 100 C.
[0018] As-synthesized, the zeolites will contain some of the exchangeable or
charge
balancing cations in its pores. These exchangeable cations can be exchanged
for other
cations, or in the case of organic cations, they can be removed by heating
under
controlled conditions. Ion exchange involves contacting the zeolites with a
solution
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containing the desired cation (at molar excess) at exchange conditions.
Exchange
conditions include a temperature of 15 C to 100 C and a time of 20 minutes to
50 hours.
Calcination conditions include a temperature of 300 C to 600 C for a time of 2
to 24
hours.
[0019] A special treatment for removing organic cations which provides the
ammonium form of the zeolite is ammonia calcination. Calcination in an ammonia
atmosphere can decompose organic cations, presumably to a proton form that can
be
neutralized by ammonia to form the ammonium cation. The resulting ammonium
form
of the zeolite can be further ion-exchanged to any other desired form. Ammonia
calcination conditions include treatment in the ammonia atmosphere at
temperatures
between 250 C and 600 C and more preferably between 250 C and 450 C for times
of
10 minutes to 5 hours. Optionally, the treatments can be carried out in
multiple steps
within this temperature range such that the total time in the ammonia
atmosphere does
not exceed 5 hours. Above 500 C, the treatments should be brief, less than a
half hour
and more preferably on the order of 5-10 minutes. Extended calcination times
above
500 C can lead to unintended dealumination along with the desired ammonium ion-
exchange and are unnecessarily harsh as most organoammonium templates easily
decompose at lower temperatures.
[0020] The UZM-4M, UZM-5HS, UZM-8HS, UZM-I5HS and UZM-16HS
zeolites are prepared from their respective parent zeolite by a number of
various
techniques and are represented by the empirical formula:
M1 +A1(,-,)EXSiy,OZ,, (2).
[0021] In formula (2), E and "x" are as defined above except for UZM-4M and
UZM-5HS where "x" varies from 0 to 0.5. MI is at least one exchangeable cation
selected from the group consisting of alkali metals, alkaline earth metals,
rare earth
metals, ammonium ion, hydrogen ion and mixtures thereof, a is the mole ratio
of M1 to
(Al + E), n is the weighted average valence of M1, y' is the mole ratio of Si
to (Al + E)
and z" is the mole ratio of 0 to (Al + E). The values of the variables for the
zeolites are
presented below in Table F.
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Table F
Variable UZM-4M UZM-5HS UZM-8HS UZM-15HS UZM-16HS
a 0.15 to 1.5 0.15 to 50 0.05 to 50 0.01 to 50 0.01 to 50
n lto3 lto3 lto3 lto3 1to3
y 1.75 to 500 greater than 5 greater than greater than 7 greater than 3
6.5
z (a=n+3+4 (a=n+3+4 (a=n+3+4 (a=n+3+4 (a=n+3+4
y')/2 y')/2 y')/2 y')/2 y')/2
[0022] The value of y' is greater than the specific value set forth in Table F
to
virtually pure silica. By virtually pure silica is meant that virtually all
the aluminum
and/or the E metals have been removed from the framework. It is well know that
it is
virtually impossible to remove all the aluminum and/or E metal. Numerically, a
zeolite is virtually pure silica when y' has a value of at least 3,000,
preferably 10,000
and most preferably 20,000. Thus, ranges for y' are from 3, 5, 6.5 or 7 to
3,000
preferably greater than 10 to 3,000; 3, 5, 6.5 or 7 to 10,000 preferably
greater than 10
to 10,000 and 3, 5, 6.5 or 7 to 20,000 preferably greater than 10 to 20,000.
[0023] The zeolites UZM-4M, UZM-5HS, UZM-8HS, UZM-15HS and UZM-
16HS are further characterized by an x-ray diffraction pattern having at least
the d-
spacings and relative intensities set forth in Tables G, H, I, J and K
respectively.
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Table G
UZM-4M
20 d(A) JJJ %
6.55 -6.83 13.49 - 12.93 m
7.63-7.91 11.58- 11.17 vs
13.27 -13.65 6.67-6.48 m-s
14.87 - 15.25 5.95-5.81 m-vs
15.35 - 15.74 5.77-5.63 m
18.89 - 19.31 4.69-4.59 m
20.17 - 20.50 4.40-4.33 w-m
20.43 - 20.85 4.34-4.26 m
21.51- 21.97 4.13-4.04 m-vs
24.14 - 24.67 3.68-3.60 m-s
24.47 - 24.98 3.63-3.56 m-s
27.73 - 28.27 3.21-3.15 w-m
30.11 - 30.73 2.97-2.90 m-s
31.13 - 31.75 2.87-2.81 w-m
Table H
UZM-5HS
20 d(A) 1/10%
< 6.79 > 13.0 w-m
8.26-7.52 10.70- 11.75 m-vs
10.65 - 10.04 8.30-8.80 m-vs
12.32- 11.79 7.18-7.50 s-vs
16.56 - 15.53 5.35-5.70 m-vs
19.71 - 18.78 4.50-4.72 w-m
23.58 - 22.72 3.77-3.91 w-m
24.37 - 23.64 3.65-3.76 m-vs
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Table I
UZM-8HS
20 d(A) UIo%
6.90-7.40 12.8-11.94 w-vs
8.15-8.85 10.84-9.98 m-vs
14.10 - 14.70 6.28-6.02 w-vs
19.40 - 20.10 4.57-4.41 w-s
22.00 - 22.85 4.04-3.89 m-vs
24.65 - 25.40 3.61-3.50 w-m
25.70 - 26.50 3.46-3.36 w-vs
Table J
UZM-15HS
0
20 d(A) UIo%
8.75 - 10.30 10.12-8.60 w-vs
12.70 - 13.40 6.98-6.62 m-s
19.00 - 20.30 4.68-4.38 w
25.50 - 26.50 3.50-3.37 m-vs
Table K
UZM-16HS
0
20 d(A) UIo%
7.70-8.40 11.47- 10.52 m - vs
11.70- 12.10 7.56-7.31 w
13.35 - 14.56 6.63-6.08 s - vs
20.60 - 21.70 4.31 -4.09 w
24.60 - 25.65 3.62-3.47 m - s
[0024] The UZM-4M, UZM-5HS, UZM-8HS, 15HS and 16HS are prepared by
removing aluminum and optionally inserting silicon into the structure thereby
increasing the Si/Al ratio and thus modifying the acidity and ion exchange
properties
of the zeolites. These treatments include: a) contacting with a fluorosilicate
solution
or slurry; b) calcining or steaming followed by acid extraction or ion-
exchange; c)
acid extraction or d) any combination of these treatments in any order.
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[0025] Fluorosilicate treatment is known in the art and is described in US-A-
6,200,463 B 1, which cites US-A-4,711,770 as describing a process for treating
a
zeolite with a fluorosilicate salt. General conditions for this treatment are
contacting
the zeolite with a solution containing a fluorosilicate salt such as ammonium
fluorosilicate (AFS) at a temperature of 20 C to 90 C.
[0026] The acids which can be used in carrying out acid extraction include
without limitation mineral acids, carboxylic acids and mixtures thereof.
Examples of
these include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid
(EDTA), citric
acid, oxalic acid, etc. The concentration of acid which can be used is not
critical but
is conveniently between I wt-% to 80 wt-% acid and preferably between 5 wt-%
and
40 wt-% acid. Acid extraction conditions include a temperature of 10 C to 100
C for
a time of 10 minutes to 24 hours. Once treated with the acid, the treated UZM
zeolite
is isolated by means such as filtration, washed with deionized water and dried
at
ambient temperature up to 100 C.
[0027] The extent of dealumination obtained from acid extraction depends on
the
cation form of the starting UZM as well as the acid concentration and the time
and
temperature over which the extraction is conducted. For example, if organic
cations
are present in the starting UZM zeolite, the extent of dealumination will be
slight
compared to a UZM zeolite in which the organic cations have been removed. This
may be preferred if it is desired to have dealumination just at the surface of
the UZM
zeolite. As stated above, convenient ways of removing the organic cations
include
calcination, ammonia calcination, steaming and ion exchange. Calcination,
ammonia
calcination and ion exchange conditions are as set forth above. Steaming
conditions
include a temperature of 400 C to 850 C with from 1% to 100% steam for a time
of
10 minutes to 48 hours and preferably a temperature of 500 C to 600 C, steam
concentration of 5 to 50% and a time of 1 to 2 hours.
[0028] It should be pointed out that both calcination and steaming treatments
not
only remove organic cations, but can also dealuminate the zeolite. Thus,
alternate
embodiments for dealumination include: a calcination treatment followed by
acid
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extraction and steaming followed by acid extraction. A further embodiment for
dealumination comprises calcining or steaming the starting UZM zeolite
followed by
an ion-exchange treatment. Of course an acid extraction can be carried out
concurrently with, before or after the ion exchange.
[0029] The ion exchange conditions are the same as set forth above, namely a
temperature of 15 C to 100 C and a time of 20 minutes to 50 hours. Ion
exchange can
be carried out with a solution comprising a cation (MI') selected from the
group
consisting of alkali metals, alkaline earth metals, rare earth metals,
hydrogen ion,
ammonium ion, and mixtures thereof. By carrying out this ion exchange, the M1
cation is exchanged for a secondary or different M1' cation. In a preferred
embodiment, the UZM composition after the steaming or calcining steps is
contacted
with an ion exchange solution comprising an ammonium salt. Examples of
ammonium salts include but are not limited to ammonium nitrate, ammonium
chloride, ammonium bromide, and ammonium acetate. The ammonium ion containing
solution can optionally contain a mineral acid such as but not limited to
nitric,
hydrochloric, sulfuric and mixtures thereof. The concentration of the mineral
acid is
that amount necessary to give a ratio of H+ to NH4' of 0 to 1. This ammonium
ion
exchange aids in removing any debris present in the pores after the steaming
and/or
calcination treatments.
[0030] It is apparent from the foregoing that, with respect to effective
process
conditions, it is desirable that the integrity of the zeolite crystal
structure be
substantially maintained throughout the dealumination process, and that the
zeolite
retains at least 50%, preferably at least 70% and more preferably at least 90%
of its
original crystallinity. A convenient technique for assessing the crystallinity
of the
products relative to the crystallinity of the starting material is the
comparison of the
relative intensities of the d-spacing of their respective X-ray powder
diffraction
patterns. The sum of the peak intensities, in arbitrary units above the
background, of
the starting material is used as the standard and is compared with the
corresponding
peak intensities of the products. When, for example, the numerical sum of the
peak
heights of the molecular sieve product is 85 percent of the value of the sum
of the
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peak intensities of the starting zeolite, then 85 percent of the crystallinity
has been
retained. In practice it is common to utilize only a portion of the peaks for
this
purpose, as for example, five or six of the strongest peaks. Other indications
of the
retention of crystallinity are surface area and adsorption capacity. These
tests may be
preferred when the substituted metal significantly changes, e.g., increases,
the
absorption of x-rays by the sample or when peaks experience substantial shifts
such as
in the dealumination process.
[0031] After having undergone any of the dealumination treatments as described
above, the UZM zeolite is usually dried and can be used as discussed below.
The
properties of the modified UZM zeolite can be further modified by one or more
additional treatment. These treatments include steaming, calcining or ion
exchanging
and can be carried out individually or in any combination. Some of these
combinations include but are not limited to:
steam calcine ion exchange;
calcine steam ion exchange;
ion exchange calcine steam
ion exchange steam -- calcine;
steam calcine;
[0032] The dealumination treatment described above can be combined in any
order to provide the zeolites of the invention although not necessarily with
equivalent
result. It should be pointed out that the particular sequence of treatments,
e.g., AFS,
acid extraction, steaming, calcining, etc can be repeated as many times as
necessary to
obtain the desired properties. Of course one treatment can be repeated while
not
repeating other treatments, e.g., repeating the AFS two or more times before
carrying
out steaming or calcining, etc. Finally, the sequence and/or repetition of
treatments
will determine the properties of the final UZM-4M, UZM-5HS, UZM-8HS, 15HS or
16HS composition.
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[0033] In specifying the proportions of the zeolite starting material or
adsorption
properties of the zeolite product and the like herein, the "anhydrous state"
of the
zeolite will be intended unless otherwise stated. The term "anhydrous state"
is
employed herein to refer to a zeolite substantially devoid of both physically
adsorbed
and chemically adsorbed water.
[0034] A second component of the catalyst of the invention is a catalytic
metal
component which is selected from the metals of Group VIII (Groups 8, 9 and 10
of the
IUPAC designation) of the Periodic Table of the Elements and preferably from
the
noble metals. The group of noble metals are ruthenium, rhodium, palladium,
platinum, iridium and osmium. Preferred catalytic metals are platinum,
palladium,
rhodium, ruthenium, iridium and mixtures thereof.
[0035] The catalytic metal component can be deposited either on the molecular
sieve or on a refractory inorganic oxide component. Inorganic oxides which can
be
used are any of those well known in the art and include but are not limited to
aluminas, silica/alumina, silica, titania, calcium oxide, magnesium oxide,
clays and
zirconia. In order to avoid confusion it is pointed out that the term
silica/alumina does
not mean a physical mixture of silica and alumina but means an acidic and
amorphous
material that has been cogelled or coprecipitated. The term is well known in
the art,
see e.g. US-A-3,909,450; US-A-3,274,124 and US-A-4,988,659. The aluminas which
can be used include gamma alumina, theta alumina, delta and alpha alumina.
[0036] The catalytic metal component is deposited onto either the zeolite or
inorganic oxide by means well known in the art such as spray impregnation or
evaporative impregnation. Both spray or evaporative impregnation use a
solution
containing a decomposable compound of the desired metal. By decomposable is
meant
that upon heating the compound decomposes to provide the catalytic metal or
catalytic
metal oxide. Non-limiting examples of decomposable compounds which can be used
include chloroplatinic acid, palladic acid, chloroiridic acid, rhodium
trichloride,
ruthenium tetrachloride, osmium trichloride, iron chloride, cobalt chloride,
nickel
chloride, iron nitrate, cobalt nitrate, nickel nitrate, rhodium nitrate,
ammonium
chloroplatinate, platinum tetrachloride hydrate, palladium chloride, palladium
nitrate,
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tetraamine platinum chloride and tetraamminepalladium (II) chloride. The
solvent
which is used to prepare the solution is usually water although organic
solvents such as
alcohols, dimethyl formamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran
(THF) and amines, e.g., pyridine can be used.
[0037] Spray impregnation involves taking a small volume of the solution and
spraying it over the support (zeolite or oxide) while the support is moving.
When the
spraying is over, the wetted support can be transferred to other apparatus for
drying or
finishing steps.
[0038] One particular method of evaporative impregnation involves the use of a
steam jacketed rotary dryer. In this method the support is immersed in the
impregnating
solution which has been placed in the dryer and the support is tumbled by the
rotating
motion of the dryer. Evaporation of the solution in contact with the tumbling
support is
expedited by applying steam to the dryer jacket. The impregnated support is
then dried
at a temperature of 60 C to 300 C and then calcined at a temperature of 300 C
to 850 C
for a time of 30 minutes to 8 hours to give the calcined catalyst.
[0039] When the molecular sieve is the support, the catalytic metal component
can also be deposited thereon by ion-exchange. Ion-exchange is carried out by
contacting the molecular sieve with a solution containing a compound of the
desired
metal at ion-exchange conditions which include a temperature of 20 C to 100 C
for a
time from 5 minutes to 6 hours.
[0040] When the catalytic metal component is deposited on the refractory
inorganic oxide component, the catalyst comprises separate particles. One
configuration is a loose mixture of the two particles (refractory oxide and
zeolite
particles) or the particles are mixed and then formed into shaped articles
such as
cylinders, pellets, pills, spheres, irregularly shaped particles, etc. Methods
of
preparing such shaped articles are well known in the art. In the case where
the
catalytic metal is deposited on the molecular sieve, then the inorganic oxide
acts as a
binder so that the resultant mixture can be formed into any of the shapes
described
above.
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[0041] In another embodiment, the molecular sieve and inorganic oxide are
first
mixed and formed into a shaped article and then the catalytic metal is
deposited onto
the composite article by any of the means described above. In this case, the
catalytic
metal is believed to be deposited on both the inorganic oxide and zeolite
supports.
Regardless of how and where the catalytic metal is deposited, it is present in
the final
catalyst in an amount from 0.01 to 10 weight percent of the catalyst expressed
as the
metal. It should also be pointed out that the metal component can be present
on the
catalyst in its elemental (zero valent) state or as the oxide.
[0042] The catalyst can also contains a modifier which modifies the activity
of the
catalytic metal. The modifier is selected from the group consisting of
titanium,
niobium, rare earth elements, tin, rhenium, zinc, germanium and mixtures
thereof.
Preferred rare earth elements are cerium, ytterbium, lanthanum, dysprosium and
mixtures thereof. The modifier component is deposited by the same techniques
as
described above for the catalytic metals. Further, the modifier can be
deposited on the
support before, after or simultaneously with the catalytic metal, although not
necessarily with equivalent results. It is preferred to deposit the modifier
with the
catalytic metal. The amount of modifier can vary substantially but is usually
in the
range of 0.1 to 50 wt.-%, preferably 1 to 10 wt.-% of the catalyst as the
element.
[0043] The catalyst described above is used in a process where cyclic
paraffins are
opened or cleaved to acyclic paraffins. The feeds which can be used in the
ring
opening process are any of those which comprises C5 - C6 aliphatic rings, i.e.
naphthenic rings. Naphtha feeds can vary considerably in the amount of
aromatic,
naphthene and paraffin components which they complain. Depending on the
source,
feeds can contain from 15% to 55% naphthenes. One example of naphtha feed was
found to contain 17 wt.-% aromatics, 44 wt.-% naphthenes and 39 wt.-%
aromatics.
[0044] The feedstream is contacted with the catalyst at ring opening
conditions
which include a temperature of 200 C to 600 C, a pressure of atmospheric to
20,684
kPag, and preferably from 1379 kPag to 13790 kPag, a liquid hourly space
velocity
of 0.1 to 30 hr -1 and preferably 2 to 10 hr -1 and H2/HC (hydrocarbon) ratio
from 0.1 to
30 and preferably from 1 to 10.
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[0045] The following examples are presented in illustration of this invention
and are
not intended as undue limitations on the generally broad scope of the
invention as set out
in the appended claims.
EXAMPLE 1
[0046] An aluminum sol was prepared by dissolving aluminum metal in HCI. In a
container 822.4g of the Al-sol, containing 105.32g Al (as A1203) and 94g Cl
were
blended with 2.91g of NbCl5 at 60 C for 12 hours. To this there were added
302.1g of
hexamethylene tetraamine (HMT) and 15.4g-of water. Droplets of the resulting
mixture were formed and dropped into a hot oil tower which formed gelled
spheres.
The spheres were then aged at 140 C for 1.5 hours, washed with 20 liters of
0.25%
NH3 solution for 2 hours at 95 C, dried at 100 C for 16 hours and then
calcined at
550 C for 2 hours in air with 3% steam.
[0047] In a rotary impregnator, 50 cc of the above spheres were impregnated
with
a 50 cc aqueous solution containing 8.89 cc of chloroplatinic acid (CPA) (Pt
concentration was 28.08 mg Pt/cc) and 2g of HC1 (37%). The excess solution was
evaporated at 100 C and the catalyst was then calcined at 525 C in flowing air
(3600
cc/min.) and 45 cc/min. of 1.OM HCl for 30 minutes. Finally, the calcined
catalyst
was reduced at 500 C with 3000 cc/min. of H2 for one hour. Analysis of the
catalyst
showed it contained 0.93 wt-% Pt and 0.49 wt-% Nb. This catalyst was
identified as
catalyst A.
EXAMPLE 2
[0048] In a container 766.2g of alumina was mixed with 27g HNO3 (70%)
followed by the addition of 71.4g TiO2 and 563.9g of water and mixed for 30
minutes
to form a dough. The dough was extruded through a 0.073" dieplate and the
extrudates calcined in air at 550 C for two hours.
[0049] In a rotary evaporator, 72.26g of the above extrudates were combined
with
100 ml of an aqueous solution containing 4.92 ml of HCl (37%) and 12.8 ml of
CPA.
The solution was evaporated and the catalyst was calcined and then reduced as
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described in Example 1. Analysis of the catalyst showed it contained 0.49 wt-%
Pt.
This catalyst was identified as catalyst B.
EXAMPLE 3
[0050] In a rotary evaporator 148.24g of gamma alumina extrudates were
impregnated with 200 ml of an aqueous solution containing 26.03 mL of CPA,
1.60 g
La(N03)3 and 9.99mL HCl (44%). The wet powder was dried, calcined and reduced
as described in Example 1. Analysis of the catalyst showed it contained 0.5wt-
% Pt
and 0.32wt-% La. This catalyst was identified as catalyst C.
EXAMPLE 4
[0051] In a rotary evaporator 148.24g of gamma alumina extrudates were
impregnated with 200 mL of an aqueous solution containing 26.68 mL of CPA,
1.11 g
of NbC15 and 9.99mL HC1 (44%). The wet extrudates were dried, calcined and
reduced as described in Example 1. Analysis of the catalyst showed it
contained 0.48
wt-% Pt and 0.16 wt-% Nb. This catalyst was identified as catalyst D.
EXAMPLE 5
[0052] In a rotary evaporator 63.63g of theta alumina oil dropped spheres were
impregnated with 100 mL of an aqueous solution containing11.45mL of CPA, 0.62
g
of YbC13, 6H2O and 4.29mL HCl (44%). The wet spheres were dried, calcined and
reduced as described in Example 1. Analysis of the catalyst showed it
contained 0.49
wt-% Pt and 0.46 wt-% Yb. This catalyst was identified as catalyst E.
EXAMPLE 6
[0053] In a rotary evaporator 148.24g of gamma alumina extrudates were
impregnated with 200mL of an aqueous solution containing 26.68 mL of CPA, and
9.99mL HCl (44%). The wet extrudates were dried, calcined and reduced as
described in Example 1. Analysis of the catalyst showed it contained 0.52 wt-%
Pt.
This catalyst was identified as catalyst F.
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EXAMPLE 7
[0054] In a rotary evaporator 148.28g of gamma alumina extrudates were
impregnated with 200 mL of an aqueous solution containing 26.68 mL of CPA,
1.45 g
YbCl3 , 6H20 and 9.99 mL HC1 (44%). The wet extrudates were dried, calcined
and
reduced as described in Example 1. Analysis of the catalyst showed it
contained 0.51
wt-% Pt and 0.40 wt-% Yb. This catalyst was identified as catalyst G.
EXAMPLE 8
[0055] In a rotary evaporator 95.73g of theta alumina oil dropped spheres were
impregnated with 150 mL of an aqueous solution containing 17.41 mL of CPA and
6.52mL HCl (44%). The wet spheres were dried, calcined and reduced as
described in
Example 1. Analysis of the catalyst showed it contained 0.50 wt-% Pt . This
catalyst
was identified as catalyst H.
EXAMPLE 9
[0056] In a rotary evaporator 148.24g of alumina extrudates were impregnated
with an aqueous solution containing 200 mL of CPA, 1.62 g Dy(N03)3 and 9.99mL
HCl (44%). The wet extrudates were dried, calcined and reduced as described in
Example 1. Analysis of the catalyst showed it contained 0.50 wt-% Pt and 0.39
wt-%
Dy. This catalyst was identified as catalyst I.
EXAMPLE 10
[0057] Catalysts B to I were tested for methylcyclopentane ring opening
activity
and selectivity as follows. The catalysts were tested by placing 35mg of 250-
450 um
meshed particles into a microreactor and pretreated at 450 C for 4 hours using
dry
hydrogen floured at 45 cm3/min. The samples were then tested using a feed of
2.7%
methylcyclopentane in hydrogen as a carrier gas at temperatures of 200 C to
350 C at
weight hourly space velocities (w 2/sv) of 0.5 to 6hr'. The results of the
testing at
350 C and WHSV of 0.5hr' are presented in Table 1.
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Table 1
Effect of Modifiers on Ring Opening Activity
Catalyst I.D. MCP Conv. % RO Yield %
B 80 72
C 74 71
D 82 75
E 73 70
F 68 60
G 65 60
H 62 57
I 59 55
[0058] The results provided in Example 10 show that modifiers such as Nb, Ti,
and
Yb improve both the activity and selectivity of platinum for ring opening.
EXAMPLE 11
[0059] Samples of catalysts A, B and H were mixed with a sample of UZM-16
(70% UZM-16/30% catalyst) and tested for methylcyclohexane ring opening
activity
and selectivity as follows. In an Incollog 800 HTM tube reactor there were
placed 2.0 g
of 40-60 mesh crushed extrudates of A,B or H and 1.0 g of UZM-16. The reactor
was
heated using an infrared furnace. Inert spacers were placed before the
catalyst bed to
minimize dead volume and pre-heat the feed. The feed consisted of
methylcyclohexane
(>98% purity) which was mixed with hydrogen carrier gas (>99% pure) in a
heated
mixing chamber and then downflowed through the catalyst bed at a weight hourly
space
velocity of 1.5 hr'. Measurements were taken at temperatures of 260-400 C and
a
pressure of 5516 kPag (800 psig). The reactor effluent was analyzed by an on-
line gas
chromatograph and the results are presented in Table 2.
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Table 2
Effect of Molecular Sieves on Ring Opening Activity
Catalyst ID Temperatures MCH Conversion C7 Paraffin C7 Paraffin
(wt-%) Select. (wt-%) Yield %
UZM-16 + Cat 383 86 52 45
H
UZM-16 + Cat 391 93 59 55
A
UZM-16 + Cat 401 96 54 52
B
EXAMPLE 12
[0060] Aluminum tri-sec-butoxide (95%), 46.32g, was added to 626.31g
diethyldimethylammonium hydroxide (20%) and dissolved with vigorous stirring.
To
this mixture, 142.5g precipitated silica, UltrasilTM VNSP3 (85% Si02), was
added
with continuous stirring. In a separate beaker, 21.47g TMACI (97%) and 5.22g
NaCl
were dissolved in 58.18g de-ionized H2O. This solution was then added to the
previous reaction mixture. The resulting mixture was homogenized for 20 min
and
the final reaction mixture was then distributed among several autoclaves
including
one 0.6L stainless steel stirred autoclave. The 0.6L autoclave was heated to
and held
at 150 C for 120 hr. after which the solids were collected by centrifugation,
washed
with de-ionized water and dried at 95 C.
[0061] The products isolated from the 0.6L reaction exhibited an x-ray
diffraction
pattern consistent with the characteristic lines for the zeolite designated
UZM-15. A
sample of the UZM-15 (60 g) was then mixed with 120 ml of 1.57 M HCl solution
and heated to 95 C for 1 hour to remove a good portion of organic templates
The
slurry was then filtered while still hot and washed with 500 ml of de-ionized
H20-
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The filter cake was air dried overnight, treated with HCl as described above,
washed
using two 500 ml portions of de-ionized H2O and dried at 95 C.
[0062] Extrudates of 70 wt-% zeolite (UZM-15) and 30% alumina were prepared
by first mulling 19.1 grams of Condea SBTM alumina with 29.0 grams of 20%
HNO3.
The HCI extracted UZM-15 (37.0 grams), Solka Floc (1.5 grams) extrusion aid
and
additional de-ionized H2O were then added to the peptized alumina and mulled
for
additional time until a consistent dough texture was obtained. The dough was
then
pushed through a die plate with 0.16 cm die holes to form green extrudate,
which was
then activated first in N2 and then air at 500 C for 2 hours. This catalyst
was
identified as sample J.
EXAMPLE 13
[0063] An aluminosilicate reaction mixture was prepared by adding 35.2 grams
of
Al (Osec-Bu)3 (95+%) to 927.5 grams BzTMAOH (40%), and then stirring for 20
minutes, followed by the slow addition of 416.5 grams of colloidal silica
(LUDOXTM
AS-40, 40% SiO2). The resulting mixture was then reacted in an autoclave at
125 C for
120 hours. The solid product was recovered and washed, and showed an x-ray
pattern
consistent with that of UZM-16. The powder was then calcined at 500 C and then
NH4NO3 exchanged, filtered, washed with de-ionized H2O and dried at 90 C. The
catalyst comprising 70 wt-% UZM-16 and 30 wt-% A1203 was prepared using a
procedure similar to that described in Example 12. This catalyst was
identified as
sample K.
EXAMPLE 14
[0064] An aluminosilicate reaction mixture was prepared in the following
manner.
Al(Osec-Bu)3 (97%), 804.4g, was added to 7330g of DEDMAOH, (20% aq) with
vigorous stirring. To this mixture, 2530g precipitated silica, (UltrasilTM VN
SP3, 89%
Si02) was added with continuous mixing. A solution of 127g NaOH in 3115g
deionized
H2O was prepared and added to the previous mixture and homogenized for 30 min.
The
resulting mixture was reacted in an autoclave at 150 C for 185 hours. The
solid product
was collected by filtration, washed with de-ionized water, and dried at 95 C.
The
product was identified as UZM-8 by powder x-ray diffraction analysis. The
zeolite was
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first NH4NO3 exchanged to remove sodium, then prepared into a catalyst of 70
wt-%
UZM-8 and 30 wt-% A1203 using a procedure similar to that described in Example
12.
This catalyst was identified as sample L.
EXAMPLE 15
[0065] An aluminosilicate reaction mixture was prepared in the following
manner.
Al(Osec-Bu)3 (97%), 66.51g, was added to 918.29g of DEDMAOH, (20% aq) with
vigorous stirring. To this mixture, 208.95g precipitated silica, (UltrasilTM
VN SP3,
89% Si02) was added with continuous mixing. A solution of 37.2g Na2SO4 in
169.05g deionized H2O was prepared and added to the previous mixture and
homogenized for 10 min. A 1.7g portion of UZM-8 seed was added to the mixture,
followed by an additional 20 min of mixing. A 1077.3g portion of this final
reaction
mixture was transferred to a 2-L Teflon-lined autoclave. The autoclave was
placed in
an oven set at 150 C and the mixture was reacted quiescently for 10 days. The
solid
product was collected by filtration, washed with de-ionized water, and dried
at 95 C.
The product was identified as UZM-8 by powder x-ray diffraction analysis. The
zeolite was first NH4NO3 exchanged to remove sodium, then prepared into a
catalyst
of 70 wt-% UZM-8 and 30 wt-% A1203 using a procedure similar to that described
in
Example 12. This catalyst was identified as sample M.
EXAMPLE 16
[0066] In a container 219.3g of alumina were mixed with 12.9g of HNO3 (70%)
and to this peptized mixture there were added 109.6g of alumina, 84.3g of SM-3
molecular sieve (prepared according to US-A-4,943,424) , 1.5g of methacel A4M
and
197.4g water. The resulting dough was mixed for 35 minutes and then extruded
through a 0.16 cm die. The extrudates were dried at 300 C for 1 hour and then
550 C
for 2 hours in flowing air. This catalyst was identified as sample N.
EXAMPLE 17
[0067] A catalyst containing SAPO-11 and alumina was prepared per Example 5.
The SAPO-11 was prepared according to US-A-4,440,871. This catalyst was
identified as sample 0.
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EXAMPLE 18
[0068] Platinum was dispersed on samples J to 0 by taking 8.35g of each sample
and contacting it with 15m1 of a solution containing 2.97cc chloroplatinic
acid
(28.08mg Pt/ml) and 0.569ml HCl (37%) in a rotary evaporator. The solution was
impregnated at 100 C and the impregnated base was calcined at 525 C in flowing
air
(3600cc/miri) and 45cc/min HC1 for 30 minutes. The calcined catalyst was
reduced
in flowing hydrogen 3000cc/min H2 at 500 C for 1 hour. The amount of platinum
on
the finished catalyst was found to be 1 wt-%. The catalysts were labeled
catalysts J to
0 respectively.
EXAMPLE 19
[0069] Catalysts J to 0 were tested for methylcyclohexane ring opening
activity
and selectivity as follows. In on IncolloyTM tube reactor there were placed 3g
of 40-60
mesh crushed extrudates of each sample. The reactor was heated using an
infrared
furnace. Inert spacers were placed before the catalyst bed to minimize dead
volume
and pre-heat the feed. The feed consisted of methylcyclohexane (>98% purity)
which
was mixed with hydrogen carrier gas (>99% pure) in a heated mixing chamber and
then flowed through the catalyst bed at a weight hourly space velocity of 5
hr'.
Measurements were taken at various temperatures and a pressure of 5516 kPa
(800
psi). The reactor effluent was analyzed by an on-line gas chromatograph and
the
results are presented in Table 3 below.
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Table 3
Methylcyclohexane Activity for Several Catalysts
Temperature MCH C7 Paraffin C7 C7 C6- Yield
Catalyst ID Paraffin Naphthene
( C): Conversion Selectivity Yield Yield (no methane)
Catalyst J 384 88 46% 41.0 26.2 17.9
Catalyst K 412 89 46% 40.6 16.1 23.0
Catalyst L 369 91 28% 25.5 29.9 15.4
Catalyst M 393 95 4% 4.3 10.7 77.7
Catalyst N 386 89 61% 54.3 13.9 18.7
Catalyst 0 410 92 62% 56.7 6.6 23.4
28
