Note: Descriptions are shown in the official language in which they were submitted.
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A SYNTHETIC ZEOLITE COMPRISING A CATALYTIC METAL
CROSS-REFERENCES TO RELATED APPLICATIONS
The present application claims priority to and the benefit of USSN 62/340768,
filed May 24,
2016, and European Patent Application Serial No. 16183679.6, filed August
11,2016, which
are all incorporated herein by reference.
FIELD OF THE INVENTION
[0001]
The present invention relates to a small pore synthetic zeolite comprising a
catalytic metal and to processes for making the small pore synthetic zeolite.
BACKGROUND OF THE INVENTION
[0002]
Zeolites are a class of crystalline microporous oxide materials with well-
defined
pores and cavities. Although their chemical composition was first limited to
aluminosilicate
polymorphs, many more heteroatoms such as B, P, As, Sn, Ti, Fe, Ge, Ga, Be and
Zn, among
others, can now be introduced into zeolitic frameworks in addition to Si and
Al.
[0003] Zeolites, both natural and synthetic, have been demonstrated in the
past to be
useful as adsorbents and to have catalytic properties for various types of
hydrocarbon
conversion reactions. Zeolites are ordered, porous crystalline materials
having a definite
crystalline structure as determined by X-ray diffraction (XRD). Within the
crystalline zeolite
material there are a large number of cavities which may be interconnected by a
number of
channels or pores. These cavities and pores are uniform in size within a
specific zeolite
material. Because the dimensions of these pores are such as to accept for
adsorption
molecules of certain dimensions while rejecting those of larger dimensions,
these materials
are utilized in a variety of industrial processes.
[0004]
Zeolites can be described as rigid three-dimensional framework of TO4
tetrahedra
(T = Si, Al, P, Ti, etc.). The tetrahedra are cross-linked by the sharing of
oxygen atoms with
the electrovalence of the tetrahedra containing trivalent element (e.g.,
aluminum or boron) or
divalent element (e.g., Be or Zn) being balanced by the inclusion in the
crystal of a cation, for
example, a proton, an alkali metal or an alkaline earth metal cation. This can
be expressed
wherein the ratio of the Group 13 element (e.g., aluminum or boron) to the
number of various
cations, such as Fr, Ca2+*2, 5r2+*2, Nat, K+, or Lit, is equal to unity.
[0005]
Zeolites that find application in catalysis include any of the naturally
occurring or
synthetic crystalline zeolites.
Examples of these zeolites include large pore zeolites,
intermediate pore size zeolites, and small pore zeolites. These zeolites and
their isotypes are
described in "Atlas of Zeolite Framework Types", eds, Ch. Baerlocher, L.B.
McCusker, D.H.
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Olson, Elsevier, Sixth Revised Edition, 2007, which is hereby incorporated by
reference. A
large pore zeolite generally has a pore size of at least about 6.0 A to 8 A
and includes LTL,
MAZ, FAU, OFF, *BEA, and MOR framework type zeolites (IUPAC Commission of
Zeolite Nomenclature). Examples of large pore zeolites include mazzite,
offretite, zeolite L,
zeolite Y, zeolite X, omega, and beta. An intermediate pore size zeolite
generally has a pore
size from more than 4.5 A to less than about 7 A and includes, for example,
MFI, MEL,
EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites
(IUPAC Commission of Zeolite Nomenclature). Examples of intermediate pore size
zeolites
include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2. A small
pore size
zeolite has a pore size from about 3 A to less than about 5.0 A and includes,
for example,
CHA, ER!, KFI, LEV, SOD, and LTA framework type zeolites (IUPAC Commission of
Zeolite Nomenclature). Examples of small pore zeolites include ZK-4, SAPO-34,
SAPO-35,
ZK-14, SAP0-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T,
and ALPO-
17.
[0006] Synthesis of zeolites typically involves the preparation of a
synthesis mixture
which comprises sources of all the elements present in the zeolite, often with
a source of
hydroxide ion to adjust the pH. In many cases a structure directing agent
(SDA) is also
present. Structure directing agents are compounds which are believed to
promote the
formation of zeolite frameworks and which are thought to act as templates
around which
certain zeolite structures can form and which thereby promote the formation of
the desired
zeolite. Various compounds have been used as structure directing agents
including various
types of quaternary ammonium cations.
[0007] The synthesis of zeolites is a complicated process. There are a
number of
variables that need to be controlled in order to optimize the synthesis in
terms of purity, yield
and quality of the zeolite produced. A particularly important variable is the
choice of
synthesis template (structure directing agent), which usually determines which
framework
type is obtained from the synthesis. Quaternary ammonium ions are typically
used as the
structure directing agents in the preparation of zeolite catalysts. For
example, zeolite MCM-
68 may be made from quaternary ammonium ions as is described in US 6,049,018.
Other
known zeolites that are typically produced using quaternary ammonium ions
include ZSM-
25, ZSM-48, ZSM-57, ZSM-58, and ECR-34, as described in US 4,247,416, US
4,585,747,
US 4,640,829, US 4,698,218, and US 5,455,020.
[0008] The "as-synthesized" zeolite will contain the structure directing
agent in its pores,
and is usually subjected to a calcination step to burn out the structure
directing agent and free
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up the pores. For many catalytic applications, it is also desirable to include
metal cations
such as metal cations of Groups 2 to 15 of the Periodic Table of the Elements
within the
zeolite structure. This is typically accomplished by ion exchange treatment.
10009] Zeolites are often used in industrial catalysts as supports for
catalytic metals.
.. Such catalytic metals, for example platinum and rhodium, are key components
of refinery
catalysts, as they enable the activation of C-H, H-H and C=C bonds, amongst
others. Metals
also play an important role in palliating catalyst deactivation by coke in
acid catalyzed
processes, using hydrogen to maintain the catalyst surface clean of heavy
hydrocarbons. At
the high operating temperatures of these transformations, and in the presence
of strong
reductants such as hydrogen, a major problem emerges due to gradual
reorganization of the
metal into the form of larger (thermodynamically more stable) metal particles,
which implies
a loss in the effective number of sites available for catalysis. Moreover,
hydroprocessing
catalysts often require periodic regeneration routines to eliminate residual
heavy
hydrocarbons from the catalyst surface, using air and high temperatures to
complete the
combustion process. The use of H2/02 cycles along the catalyst lifetime
aggravates the metal
sintering problem.
[0010] Currently a number of methods are available for the production of
metal catalysts
supported on zeolites. Today, most supported metal catalysts are prepared by
ion exchange
or incipient wetness impregnation of the support. In each case the goal is to
place the metal
inside the pores of the support without an agglomeration of metal particles on
the external
surface of the support. Since the metals are typically introduced as cation
precursors, they
can ion exchange with the cations associated with the ionic framework, in
particular with the
trivalent elements, such as Al in an aluminosilicate material, or tetravalent
elements such as
Si in a silicoaluminophosphate material. The association of the positively
charged metal
cation with negatively charged anionic sites within the pores and/or cavities
of the zeolite
allows for an initial high dispersion of the metal. However, if the metal
precursor is multiply
charged, then the process becomes less efficient unless the support contains a
higher density
of anionic sites to charge balance the metal cations. As a result, it becomes
more difficult to
load multiply charged metal cations into zeolites with a lower number of
anionic sites. It
would however be desirable to incorporate metals inside higher silica
supports.
[0011] It is also desirable to have new metal catalysts able to resist
common refinery
poisons such as sulphur, nitrogen or phosphorous containing contaminants.
Provision of such
poison resistant metal catalysts would allow a reduction in equipment designed
to remove
those poisons from feed streams and/or would increase the life of the
catalyst.
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SUMMARY OF THE INVENTION
[0012]
In one aspect the invention provides a small pore size synthetic zeolite
having a
degree of crystallinity of at least 80% and comprising at least 0.01 wt%,
based on the weight
of the zeolite, of at least one catalytic metal selected from the group
consisting of Ru, Rh, Pd,
Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations
thereof,
wherein at least 80% of the catalytic metal is encapsulated in the zeolite,
wherein if the
zeolite is an aluminosilicate then the aluminosilicate has a Si02:A1203 molar
ratio of greater
than 6:1, preferably greater than 12:1, in particular greater than 30:1.
[0013]
In a yet further aspect the invention provides a small pore size synthetic
aluminosilicate zeolite having a Si02:A1203 molar ratio of greater than 6:1,
preferably greater
than 12:1, in particular greater than 30:1, and a degree of crystallinity of
at least 80% which
comprises at least 0.01 wt%, based on the weight of the zeolite, of at least
one catalytic metal
selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W,
Re, Co, Ni, Zn,
Cr, Mn, Ce, Ga, and combinations thereof, wherein at least 80% of the
catalytic metal is
encapsulated in the zeolite.
[0014]
In another aspect the invention provides a small pore size synthetic zeolite
having
a degree of crystallinity of at least 80% and comprising at least 0.01 wt%,
based on the
weight of the zeolite, of at least one catalytic metal selected from the group
consisting of Ru,
Rh, Pd, Ag, Os, Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and
combinations thereof,
wherein at least a portion of the catalytic metal is encapsulated in zeolite
such that if the
zeolite is used to catalyze the conversion of a feed stream containing a first
reactant
compound which is sufficiently small that it can enter the pores of the
zeolite (e.g. ethylene)
and a second reactant compound which is sufficiently large that it cannot
enter the pores of
the zeolite (e.g. propylene), then the ratio of the rate of conversion of the
second reactant to
the rate of conversion of the first reactant is reduced by at least 80% as
compared to the same
reaction carried out under the same conditions using the same feed stream over
a catalyst
comprising the same catalytic metal supported on the surface of an amorphous
support,
wherein if the zeolite is an aluminosilicate then the aluminosilicate has a
Si02:A1203 molar
ratio of greater than 6:1, preferably greater than 12:1, in particular greater
than 30:1.
[0015] The invention also provides, in a yet further aspect, a process for
the preparation
of the small pore size synthetic zeolite of the invention comprising:
a) providing a reaction mixture comprising a synthesis mixture capable of
forming the small pore size synthetic zeolite framework and at least one
catalytic metal
precursor, wherein the catalytic metal precursor includes metal complexes
stabilized by
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ligands L selected from the group consisting of N-containing ligands, 0-
containing ligands,
S-containing ligands, and P-containing ligands;
b) heating said reaction mixture under crystallization conditions to form
crystals
of said small pore size synthetic zeolite; and
c) recovering said crystals of the small pore size synthetic zeolite from the
reaction mixture.
[0016]
The invention, in a yet further aspect, also provides a process for the
preparation
of a small pore size synthetic zeolite of the invention comprising:
a) providing a reaction mixture comprising a synthesis mixture capable of
forming the small pore size synthetic zeolite framework, at least one
anchoring agent, and at
least one catalytic metal precursor, wherein the anchoring agent includes at
least one amine
and/or thiol group and at least one alkoxysilane group and the catalytic metal
precursor
includes at least one ligand capable of being exchanged by the at least one
amine group
and/or thiol group of the anchoring agent;
b) heating said reaction mixture under crystallization conditions to form
crystals
of said small pore size synthetic zeolite; and
c) recovering said crystals of the small pore size synthetic zeolite from the
reaction mixture.
[0017]
Where the synthesis mixture comprises a structure directing agent (SDA) the
crystals of the small pore size synthetic zeolite recovered from the reaction
mixture will
include the SDA in the pores and cavities of the zeolite (that is, in "as
made" form). The
processes for the preparation of the small pore size synthetic zeolite of the
invention may
further include a step of subjecting the small pore size synthetic zeolite
recovered from the
reaction mixture to a calcination step. The calcination step removes the
structure directing
agent and provides the zeolite in calcined form. The calcination step also
removes the ligands
or anchoring agents used to stabilize the metal during the crystallization
step.
10018]
In a yet further aspect the invention provides use of an active form of the
small
pore size synthetic zeolite of the invention as a sorbent or as a catalyst. By
active form is
meant a calcined material that has been ion-exchanged with protons and is
therefore acidic.
[0019] In a yet further aspect of the invention the invention provides a
process for
converting a feedstock comprising an organic compound to a conversion product
which
comprises the step of contacting said feedstock at organic compound conversion
conditions
with a catalyst comprising a small pore size synthetic zeolite according to
the invention.
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BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 shows PXRD patterns of the metal-containing high-silica
small pore
zeolites synthesized according to Examples 1 and 4 to 10.
[0021] Figure 2 shows TEM images and particle size distributions of the
sample
synthesized according to Example 1, after being calcined at 550 C and treated
with H2 at
400 C (Figures 2A and 2C), and after additional thermal treatment by
calcination with air at
650 C and subsequent reduction with H2 at 400 C (Figures 2B and 2D).
[0022] Figure 3 shows the XANES and EXAFS spectra of the sample
synthesized
according to Example 1. Figure 3A shows XANES spectra of the sample
synthesized
according to Example 1 (after being calcined at 550 C and treated with H2 at
400 C) (time
zero, bottom spectrum), as the sample is further treated with 5% 02 and the
temperature is
raised from 20 to 500 C. Figure 3B shows EXAFS spectra (not phase-corrected)
of the
oxidised sample after the oxidation detailed for Fig 3A (bottom line), and its
comparison with
the material of Example 1 (calcined at 550 C and treated with H2 at 400 C)
(middle line),
.. and a reference platinum foil (top line).
[0023] Figure 4 shows STEM images and particle size distributions of the
sample
synthesized according to Comparative Example 2 after being calcined at 400 C
and treated
with H2 at 400 C (Figures 4A and 4C), and after additional thermal treatment
by calcination
with air at 650 C and, finally, with H2 at 400 C (Figures 4B and 4D).
[0024] Figure 5 shows the initial reaction rates obtained for the
hydrogenation of model
alkenes (ethylene and propylene) using the materials synthesized according to
Example 1 and
Comparative Example 2 as catalysts.
[0025] Figure 6 shows TEM images of the sample synthesized according to
Example 4,
after calcination at 550 C followed by treatment with H2 at 400 C. Figure 6A
is
representative of the majority of the areas evaluated, showing small metal
nanoparticles.
Figure 6B shows an area where a big metal nanoparticle is observed in addition
to the small
metal nanoparticles (the abundance of the larger particles is < 0.1 % by
number).
[0026] Figure 7 shows TEM images and particle size =distribution of the
sample
synthesized according to Example 5, after being calcined at 600 C and treated
with H2 at 400
.. C (Figure 7A), and after additional thermal treatment by calcination with
air at 650 C and
subsequent reduction with H2 at 400 C (Figures 7B and 7C).
[0027] Figure 8 shows the Fourier-Transform EXAFS spectra (not phase-
corrected) at
the Rh K-Edge of the sample synthesized according to Example 6 after treatment
with 5% 02
at 500 C.
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[0028] Figure 9
shows TEM images of the sample synthesized according to Example 8,
after being calcined at 500 C and treated with H2 at 400 C (Figure 9A), and
after additional
thermal treatment by calcination with air at 650 C and subsequent reduction
with H2 at 400
C (Figure 9B).
[0029] Figure 10
shows TEM images and particle size distribution of the sample
synthesized according to Example 9, after being calcined at 560 C and treated
with H2 at 400
C (Figure 10A), and after additional thermal treatment by calcination with air
at 650 C and
subsequent reduction with H2 at 400 C (Figure I OB and 10C).
[0030] Figure 11
shows a STEM image and particle size distribution of a microtomed
sample synthesized according to Example 10, after being calcined at 550 C and
treated with
H2 at 400 C (Figures 11A and 11B).
[0031] Figures 12
and 13 show a STEM image and EXAFS spectra of the sample
synthesized according to Example 11, after being calcined at 550 C and
treated with H2 at
400 C. Figure 13 shows the Fourier-Transform EXAFS spectra (not phase-
corrected) at the
Pt Lill-Edge (Figure 13A top) and Pd K-Edge (Figure 13A bottom) of said sample
and the
EXAFS spectra (not phase-corrected) at the Pt LIII-Edge (Figure 13B top) and
Pd K-Edge
(Figure 13B bottom) of said sample after treatment with 502 at 500 C.
[0032] Figure 14
shows a STEM image of the sample synthesized according to Example
12, after being calcined at 550 C and treated with H2 at 400 C.
[0033] Figure 15
shows SEM (retro-dispersed electrons) images of the sample
synthesized according to Example 1 (top) and Comparative Example 13 (bottom)
after
calcination at 550 C (left) and after subsequent treatment in steam at 600 C
(right).
[0034] Figure 16 shows PXRD patterns of sample synthesized according to
Example 1
(top) and Comparative Example 13 (bottom) after calcination at 550 C (left)
and after
subsequent treatment in steam at 600 C.
DETAILED DESCRIPTION OF THE INVENTION
[0035] The
present inventors have found that it is possible to synthesize small pore size
zeolites, in particular silicates and aluminosilicates, having a catalytic
metal present in
encapsulated form inside the pores and/or cavities of the zeolite. Without
wishing to be
bound by theory, the inventors believe that the encapsulation of the catalytic
metal within the
small pore size synthetic zeolites, in particular within the pores and/or
cavities of small pore
size synthetic zeolites, limits the growth of the catalytic metal species to
small particles, for
example, catalytic metal particles having a biggest dimension of less than 4.0
nm, for
instance a biggest dimension in the range between 0.1 and 3.0 nm, such as
between 0.5 and
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1.0 nm, and prevents significant growth of those particles thereby providing
an improved
resistance to sintering. The size of the particles of catalytic metal (at
least in terms of biggest
dimension) is typically larger than the pore window size of the zeolite, and
so the metal can
be considered to be occluded within the cavities in the zeolite crystals
rather than being
present in the small pore windows of the zeolite. Conventional noble metal
catalysts on silica
supports, in contrast, generally exhibit sintering and therefore growth of the
metal particles
under high temperature cycles of reduction and oxidation which leads to a
reduction in the
number of catalytic sites and the activity of the catalyst. In addition, the
zeolites of the
invention may have advantages in selectivity in organic conversion reactions
and in
resistance to catalyst poisons.
10036] The term
"synthetic zeolite" should be understood to refer to a zeolite which has
been prepared from a synthesis mixture as opposed to being a naturally
occurring zeolite
which has been obtained by mining or quarrying or similar processes from the
natural
environment.
[0037] The term
"small pore size synthetic zeolite" as used herein refers to a synthetic
zeolite wherein the pores of the zeolite have a size in the range of from 3.0
A to less than 5.0
A. The small pore size synthetic zeolite will generally have an 8-membered
ring framework
structure but some 9- or 10-membered ring zeolites are known to have distorted
rings which
have a size in the range of from 3.0 to 5.0 A and fall within the scope of the
term "small pore
size synthetic zeolite" as used herein. Optionally, the small pore size
synthetic zeolite is an
8-membered ring zeolite. A number of 8-membered ring zeolites are listed in
the "Atlas of
Zeolite Framework Types", eds, Ch. Baerlocher, L.B. McCusker, D.H. Olson,
Elsevier, Sixth
Revised Edition, 2007.
[0038]
Optionally, the small pore size synthetic zeolite is of framework type AEI,
AFT,
AFX, CHA, CDO, DDR, EDI, ER!, IHW, ITE, ITW, KFI, MER, MTF, MWF, LEV,
LTA, PAU, PWY, RHO, SFW or UFI, more preferably of framework type CHA, AEI,
AFX, RHO, KFI or LTA. Optionally, the small pore synthetic zeolite is of
framework type
CHA or AFX. CHA is an especially preferred framework type. The zeolite
framework type
may optionally be a framework type which can be synthesized without requiring
the presence
of a structure directing agent. In an alternative embodiment the small pore
size synthetic
zeolite may be of a framework type which requires the presence of a structure
directing agent
in the synthesis mixture.
[0039]
Optionally the small pore size synthetic zeolite is one in which the zeolite
framework contains one or more elements selected from the group consisting of
Si, Al, P, As,
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Ti, Ge, Sn, Fe, B, Ga, Be and Zn; preferably in which the zeolite framework
contains at least
one tetravalent element X selected from the group consisting of Si, Ge, Sn and
Ti and/or at
least one trivalent element Y selected from the group consisting of Al, B, Fe
and Ga,
optionally one pentavalent element Z selected from the group consisting of P
and As, and
optionally one divalent element W selected from the group consisting of Be and
Zn; more
preferably in which the zeolite framework contains at least Si and/or Al and
optionally P. In a
preferred embodiment, the zeolite framework contains at least one tetravalent
element X
selected from the group consisting of Si, Ge, Sn and Ti and optionally at
least one trivalent
element Y selected from the group consisting of Al, B, Fe and Go; most
preferably the zeolite
framework contains Si and optionally Al and/or B; especially the zeolite
framework contains
Si and optionally Al. Where the zeolite framework contains a metal, such as
Fe, the catalytic
metal and transition metal will be other than the metal contained in the
framework.
Typically, the catalytic metal is extra-framework metal, that is, the
catalytic metal generally
does not form part of the framework of the synthetic zeolite, i.e. of the
three-dimensional
Is framework of tetrahedra of the
synthetic zeolite.
Optionally, the small pore size synthetic zeolite is selected from the group
consisting of
silicates, alum inos i I icates, boros i I icates, alum
inophosphates (ALP0s), and
silicoaluminophosphates (SAP0s); preferably from silicates, aluminosilicates
and
borosilicates, especially from silicates and aluminosilicates.
100401 The
small pore size synthetic zeolite may optionally be a crystalline
aluminophosphate or silicoaluminophosphate. Aluminophosphate molecular sieves
are
porous frameworks containing alternating aluminum and phosphorous tetrahedral
atoms
connected by bridging oxygen atoms. In the case of silicoaluminophosphate
molecular
sieves, some of the phosphorous, or pairs of aluminum and phosphorous atoms
can be
substituted with tetrahedral silicon atoms. Those materials may be represented
by the
formula, on an anhydrous basis:
mSDA: (SixAlyPz)02
m in the number of moles of SDA per mole of (SixAlyPz)02 and m has a value in
the as-
synthesized form from 0.01 to 0.5, preferably from 0.04 to 0.35; x, y, and z
respectively
represent the mole fraction of Si, Al and P as tetrahedral oxides, where x + y
+ z = 1, and y
and z are greater than or equal to 0.25. Preferably, x is greater than 0 in
the case of
silicoaluminophosphate molecular sieves and optionally, x is in the range of
from greater
than 0 to about 0.31. The range of y is from 0.25 to 0.5, and z is in the
range of from 0.25 to
0.5 and preferably y and z are in the range 0.4 to 0.5.
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[0041] The small pore size synthetic zeolite is preferably a silicate or
an aluminosilicate.
If the small pore size synthetic zeolite is an aluminosilicate, it contains Si
and Al and has a
Si02:A1203 molar ratio of greater than 6:1, preferably greater than 8:1, more
preferably
greater than 10:1, most preferably greater than 12:1, in particular greater
than 30:1, such as
greater than 100:1, or even greater than 150:1. If the small pore size
synthetic zeolite is a
silicate, it has an A1203:5i02 molar ratio that is 0 or a Si02:A1203 molar
ratio that is infinite
(i.e. no Al2O3). While the presence of aluminum within the zeolite framework
structure does
contribute acidic sites to the catalyst it also is associated with a reduction
in thermal stability
of the zeolite. Many industrial organic feedstock conversion processes are
carried out at
temperatures which require the use of zeolite supports having a 5i02:A1203
molar ratio of
greater than 6:1 or even greater than 10:1, such as greater than 12: 1 or
greater than 30:1 or
greater than 100:1 or greater than 150:1.
[0042] The small pore size synthetic zeolite has a degree of
crystallinity of at least 80%,
optionally at least 90%, preferably at least 95% and most preferably at least
98%. In one
embodiment the small pore size synthetic zeolite is essentially pure
crystalline material. The
degree of crystallinity may be calculated via x-ray diffraction (XRD) by
comparison with a
reference material of known 100% crystalline material of the same framework
type, the same
composition, the same or similar particle size and containing the same amount
of metals
prepared by an incipient wetness technique. The catalytic metal is primarily
extra-framework
metal and is in the form of metal particles that will tend to scatter x-rays.
Therefore in order
to obtain fully comparable results to calculate the degree of crystallinity it
is important that
the reference material contains the same amount of the same metals as present
in the small
pore size synthetic zeolite.
[0043] The small pore size synthetic zeolite comprises at least 0.01 wt%
of catalytic
metal, based on the weight of the zeolite. The amount of metal is determined
by X-ray
fluorescence (XRF) or inductively coupled plasma (ICP) and is expressed as wt%
of the
metal (based on the elemental form of the metal, and not, for example, the
oxide form) in the
total sample. Optionally, the small pore size synthetic zeolite comprises at
least 0.05 wt%,
preferably from 0.05 to 5 wt% of the catalytic metal, preferably from 0.1 to 3
wt%, more
preferably from 0.5 to 2.5 wt%, most preferably from 1 to 2 wt%.
[0044] The weight percentage of the catalytic metal which is
encapsulated in the zeolite
can be calculated by carrying out an organic conversion reaction involving a
mixed feed
having at least one feed compound which is small enough to enter the pores of
the zeolite and
at least one feed compound which is too large to enter the pores of the
zeolite and by
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comparing the results with an equivalent reaction carried out using a catalyst
having an
equivalent metal loading in which the metal is not encapsulated, for example
one in which
the metal is supported on amorphous silica. For example, for a hydrogenation
catalyst the
weight percentage of the catalytic metal which is encapsulated in the zeolite
may be
measured by hydrogenation of a mixed feed comprising a feed compound, such as
ethylene,
which is small enough to enter the pores of the zeolite and a feed compound,
such as
propylene, which is too large to enter the pores of the zeolite. In a
preferred embodiment, the
smaller compound (e.g. ethylene) and larger compound (e.g. propylene) may be
reacted
independently rather than as a mixed feed comprising both. This preferred
embodiment is
.. advantageous in that it avoids competitive adsorption and diffusion effects
that may occur
when the smaller and larger compounds are co-fed. Such a procedure is
described in detail in
Example 3 below. For the catalysts of the invention, the conversion of the
larger molecule,
for example propylene, will be slower than the conversion of the smaller
molecule, for
example ethylene, relative to the reference catalyst and the degree of
difference can be used
to calculate the percentage of catalytic metal which is encapsulated. It
should be recognized
that this method only takes into account the catalytic metal present in the
zeolite of the
invention, i.e. the extra-framework metal that has a catalytic activity. For
example, the bulk
metal inside any large metal particles present or any catalytic metal covered
under dense SiO2
layers will not take part in the reaction and so will not influence the
selectivity and the
product mix obtained. For that reason, the words "at least 80% of the
catalytic metal is
encapsulated in the zeolite" and similar expressions should be taken to mean
"at least 80% of
the catalytically active portion of the catalytic metal is encapsulated in the
zeolite", it being
understood that in many cases the catalytically active portion of the
catalytic metal will be all
or substantially all of the catalytic metal. In an especially preferred
embodiment, the
percentage of the active catalytic metal that is encapsulated in the zeolite
(a) is determined
by the following formula:
[PR SiO2 PR zeolite]
[ER SiO2 ER zeolite'
a = * 100
[PR SiO2 1
[ER SiO2J
wherein a is the percentage of catalytic metal encapsulated in the zeolite, PR
is the propylene
reaction rate expressed as mol of propylene converted per mol of catalytic
metal per second,
ER is the ethylene reaction rate expressed as mol of ethylene converted per
mol of catalytic
metal per second, "PR zeolite" and "ER zeolite" are to be understood as the
propylene and
ethylene rates of the catalyst to be tested, and "PR SiO2" and "ER SiO2" are
to be understood
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as the propylene and ethylene rates of a catalyst having an equivalent metal
loading in which
the metal is supported on amorphous silica. Because a is the percentage of
catalytic metal
encapsulated in the zeolite based on the total amount of catalytic metal
whether it is present
in the zeolite or on the zeolite surface, a is an absolute percentage number
regardless of
whether the amount of metal in the zeolite or on the zeolite surface is
expressed as amounts
in weight or mole. Based on the above-referenced formula, an a of at least 80
% corresponds
to an ethylene hydrogenation rate that is at least 5 times greater than that
of propylene for
metals that hydrogenate both ethylene and propylene at identical rates when
supported on
SiO2.
[0045] Optionally, greater than 80%, more preferably at least 90%, more
preferably at
least 95%, and most preferably at least 98% of the catalytic metal is
encapsulated in the
zeolite of the present invention. In an especially preferred embodiment, at
least 90%, more
particularly at least 95% of the catalytic metal is encapsulated in the
zeolite of the present
invention.
[0046] The catalytic metal may be selected from group consisting of Ru, Rh,
Pd, Ag, Os,
Ir, Pt, Au, Mo, W, Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof;
more
preferably from the group consisting of Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Re,
and combinations
thereof; most preferably from the group consisting of Pt, Rh, Pd and Au and
combinations
thereof, especially from the Pt, Pd and/or Rh. Pt and Rh are especially
preferred catalytic
metals.
[0047] Typically, the catalytic metal will be present in the form of
metal particles, which
includes metal clusters as well as site-isolated single metal atoms (the
catalytic metal may be
present in the particles and/or clusters as elemental metal or as the metal
oxide). Optionally,
the catalytic metal is present in the form of particles wherein at least 80%
of the particles by
number have a biggest dimension of less than 4 nm as measured by transmission
electron
microscopy (TEM). Preferably at least 80% of the particles by number have a
biggest
dimension in the range of from 0.1 to 3.0 nm, for instance from 0.5 to 1 nm,
as measured by
TEM. In the context of the present application, the expression "percentage of
the particles by
number" refers to the arithmetic average of number of particles having the
required
characteristic out of 100 particles, this value being determined on the basis
of a population of
at least one thousand particles. In the present application, the expression
"biggest dimension"
when discussing metal particle size means the biggest dimension as measured by
TEM. In the
case of substantially spherical particles, the biggest dimension of a particle
will correspond to
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its diameter. In the case of rectangular particles, the biggest dimension of a
particle will
correspond to the diagonal of the rectangle drawn by the particle. In an
especially preferred
embodiment, after thermal treatment of the small pore size synthetic zeolite
of the present
invention by calcination in air at 650 C for two hours and treatment with H2
at 400 C for two
hours, the catalytic metal will still be present in the form of particles
wherein at least 80% of
the particles by number have a biggest dimension of less than 4 nm as measured
by TEM, in
particular at least 80% of the particles by number will still have a biggest
dimension in the
range of from 0.1 to 3.0 nm, for instance from 0.5 to 1 nm, as measured by
TEM.
[0048] The small pore size synthetic zeolite may further comprise one or
more metals
other than the catalytic metal. Optionally, the small pore size synthetic
zeolite comprises at
least 0.01 wt%, optionally from 0.05 to 5 wt%, such as from 0.1 to 5 wt% of a
transition
metal selected from the group consisting of Cu, Fe, Ti, Zr, Nb, Hf, Ta and
combinations
thereof. Preferably, this transition metal is primarily extra-framework metal.
[0049] In one embodiment the small pore size synthetic zeolite is a
silicate or an
aluminosilicate having a Si02:A1203 molar ratio of greater than 6:1,
preferably greater than
12:1, in particular greater than 30:1, wherein the catalytic metal is selected
from the group
consisting of Pt, Rh, Pd and Au, and combinations thereof, in particular Pt,
Pd and/or Rh, and
wherein the zeolite is of framework type CHA, AEI, AFX, RHO, KFI or LTA, in
particular
CHA or AFX.
[0050] In one embodiment the small pore size synthetic zeolite is in as-
synthesized form
and comprises a structure directing agent (SDA), in particular an organic
structure directing
agent (OSDA), within its pores.
[0051] In an alternative embodiment the small pore size synthetic
zeolite does not
comprise a structure directing agent. For example, the small pore size
synthetic zeolite may
be in calcined form.
[0052] The inventors have found that by careful design of the synthesis
method it is
possible to produce the small pore size synthetic zeolites of the invention in
which the
catalytic metal is to a large extent encapsulated in the zeolite. In one
aspect the invention
provides a process for the preparation of the small pore synthetic zeolite of
the invention
comprising:
a) providing a reaction mixture comprising a synthesis mixture capable of
forming the small pore size synthetic zeolite framework and at least one
catalytic metal
precursor, wherein the catalytic metal precursor includes metal complexes
stabilized by
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ligands L selected from the group consisting of N-containing ligands, 0-
containing ligands,
S-containing ligands, and P-containing ligands,
b) heating said reaction mixture under crystallization conditions to form
crystals
of said small pore size synthetic zeolite, and
c) recovering said crystals of the small pore size synthetic zeolite from the
reaction mixture.
[0053] In this aspect of the process for the preparation of the small
pore size synthetic
zeolite the inventors believe, without wishing to be bound by theory, that the
ligands L
stabilize the metal complex in the synthesis mixture, which is generally
highly alkaline, such
that it does not become part of the zeolite framework or precipitate from the
solution to form
large particles which cannot be encapsulated.
[0054] The ligand L may be a 0-containing ligand, such as oxalate ion or
acetylacetonate
ion. Alternatively, the ligand L may be a S-containing ligand, such as a thiol
of the structure
HS-(CH2)-Si-(0R)3, where x = 1 to 5 and R = C1 to C4 'alkyl, preferably
methyl, ethyl,
propyl, or butyl, most preferably x = 3 and R = methyl or ethyl, or the S-
containing ligand
may be an alkyl thiol. Alternatively, the ligand L may be a P-containing
ligand, such as
phosphine, for example, triphenylphosphine. Preferably, the ligand L is a N-
containing
ligand, in particular an amine such as NH3, ethylenediamine,
diethylenetriamine,
triethylenetetramine or tetraethylene pentamine, preferably selected from the
group consisting
of NH3 and bidentate amines such as ethylene diamine and combinations thereof.
The ligand
L should be chosen such that the catalytic metal precursor is stable in the
highly alkaline
conditions of the synthesis mixture, or in a fluoride media. In particular,
the catalytic metal
precursor should be stable against precipitation at the pH of the synthesis
mixture under the
conditions used to form the small pore synthetic zeolite.
[0055] Optionally, the catalytic metal precursor is selected from the group
consisting of
[Pt(NH3)4]C12, [Pt(NH3)4](NO3)2, [Pd(NH2CH2CH2NH2)2]C12,
[Rh(NH2CH2CH2NH2)3]C13,
[Ir(NH3)5C1]C12, [Re(NH2CH2CH2NFI2)202]Cl, [Ag(NH2CH2CH2NH2)]NO3,
[Ru(NH3)6]C13,
[Ir(NH3)6]C13, [Ir(NH3)6KNO3)3, [I0H3)5NO3](NO3)2.
[0056] Advantageously, the synthesis mixture capable of forming the
small pore size
synthetic zeolite framework comprises a source of a tetravalent element X
and/or a source of
a trivalent element Y, and optionally a source of a pentavalent element Z, and
the molar ratio
of the catalytic metal precursor (in terms of metal) : (X02 + Y203 + Z205) in
the synthesis
mixture is in the range of from 0.00001 to 0.015, preferably from 0.0001 to
0.010, more
preferably from 0.001 to 0.008. In a preferred embodiment, the synthesis
mixture capable of
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forming the small pore size synthetic zeolite framework comprises a source of
a tetravalent
element X and optionally a source of a trivalent element Y, and the molar
ratio of the
catalytic metal precursor (in terms of metal) : (X02 + Y203) in the synthesis
mixture is in the
range of from 0.00001 to 0.015, preferably from 0.0001 to 0.010, more
preferably from 0.001
to 0.008.
[0057] In an alternative method the invention provides a process for the
preparation of
the small pore size synthetic zeolite of the invention comprising the steps of
a) providing a reaction mixture comprising a synthesis mixture capable of
forming the small pore size synthetic zeolite framework, at least one
anchoring agent, and at
.. least one catalytic metal precursor, wherein the anchoring agent includes
at least one amine
and/or thiol group and at least one alkoxysilane group and the catalytic metal
precursor
includes at least one ligand capable of being exchanged by the at least one
amine group
and/or thiol group of the anchoring agent,
b) heating said reaction mixture under crystallization conditions to form
crystals
5 of said small pore size synthetic zeolite; and
c) recovering said crystals of the small pore size synthetic zeolite from the
reaction mixture.
[0058] In this approach, the inventors believe, without wishing to be
bound by theory,
that the anchoring agent reacts with the catalytic metal precursor and also
with the framework
of the zeolite to anchor the catalytic metal precursor in the zeolite as the
framework forms.
[0059] Optionally, the anchoring agent is a thiol of the structure HS-
(CH2)x-Si- (OR)3,
where x = 1 to 5 and R = CI to C4 alkyl, preferably methyl, ethyl, propyl, or
butyl, most
preferably x = 3 and R = methyl or ethyl. In an alternative embodiment the
anchoring agent
is an amine of the structure H2N-(CH2).-Si- (OR)3, where x = 1 to 5 and R = C1
to C4 alkyl,
preferably methyl, ethyl, propyl, or butyl, most preferably x = 3 and R =
methyl or ethyl.
Advantageously, the synthesis mixture capable of forming the small pore size
synthetic
zeolite framework comprises a source of a tetravalent element X and/or a
source of a trivalent
element Y, and optionally a source of a pentavalent element Z, and the molar
ratio of
anchoring agent : (X02 + Y203 + Z205) is in the range of from 0.001 to 0.020,
preferably in
.. the range of from 0.002 to 0.015. In a preferred embodiment, the synthesis
mixture capable
of forming the small pore size synthetic zeolite framework comprises a source
of a tetravalent
element X and optionally a source of a trivalent element Y, and the molar
ratio of anchoring
agent : (X02 + Y203) is in the range of from 0.001 to 0.020, preferably in the
range of from
0.002 to 0.015.
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[0060]
Optionally, the molar ratio of catalytic metal precursor (in terms of metal) :
(X02
+ Y203 + Z205) or more particularly the molar ratio of catalytic metal
precursor (in terms of
metal) : (X02 + Y203) is in the range of from 0.0001 to 0.001, preferably from
0.0002 to less
than 0.001, more preferably from 0.0002 to 0.0005. The catalytic metal
precursor can be any
suitable catalytic metal complex which includes at least one ligand capable of
being
exchanged by the at least one amine group and/or thiol group of the anchoring
agent.
Optionally, the catalytic metal precursor is selected from the group
consisting of H2PtC16,
H2PtBr6, Pt(NH3)4C12, Pt(NH3)4(NO3)2, RuC13=xH20, RuBr3xH20, RhC13=xH20,
Rh(NO3)3.2H20, RhBryxH20, PdC12.xH20, Pd(NH3)4C12,
Pd(NH3)41342,
io Pd(NH3)(NO3)2, AuC13, HAuBr4xH20, HAuC14, HAu(NO3)4.xH20, Ag(NO3)2, ReC13,
Re207, OsC13, Osat, IrBr3=4H20, IrC12, IrC14, IrClyxH20, and IrBra, where x is
from 1 to 18,
preferably from 1 to 6.
[0061]
In one embodiment the synthesis mixture capable of forming the small pore size
synthetic zeolite framework comprises a source of a tetravalent element X
and/or a source of
a trivalent element Y, optionally a source of a pentavalent element Z,
optionally a source of a
divalent element W, optionally a source of an alkali metal M, a source of
hydroxide ions
and/or a source of halide ions, a source of a structure directing agent (SDA)
(in particular a
source of an organic structure directing agent (OSDA)), and water. In a
preferred
embodiment, the synthesis mixture capable of forming the small pore size
synthetic zeolite
framework comprises a source of a tetravalent element X, optionally a source
of a trivalent
element Y, optionally a source of an alkali metal M, a source of hydroxide
ions and/or a
source of halide ions, a source of a structure directing agent (SDA) (in
particular a source of
an organic structure directing agent (OSDA)), and water.
[0062]
The tetravalent element X is most often one or more of Si, Ge, Sn and Ti,
preferably Si or a mixture of Si and Ti or Ge, most preferably Si. Where X=Si,
suitable
sources of silicon (Si) that can be used to prepare the synthesis mixture
include silica;
colloidal suspensions of silica, for example that sold by E.I. du Pont de
Nemours under the
tradename LudoxS; precipitated silica; alkali metal silicates such as
potassium silicate and
sodium silicate; tetraalkyl orthosilicates; and fumed silicas such as Aerosil
and Cabosil.
[0063] The trivalent element Y is most often one or more of B, Al, Fe, and
Ga,
preferably B, Al or a mixture of B and Al, most preferably Al.
[0064]
Suitable sources of trivalent element Y that can be used to prepare the
synthesis
mixture depend on the element Y that is selected (e.g., boron, aluminum, iron
and gallium).
In embodiments where Y is boron, sources of boron include boric acid, sodium
tetraborate
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and potassium tetraborate. Sources of boron tend to be more soluble than
sources of
aluminum in hydroxide-mediated synthesis systems. Optionally, the trivalent
element Y is
aluminum, and the aluminum source includes aluminum sulfate, aluminum nitrate,
aluminum
hydroxide, hydrated alumina, such as boehmite, gibbsite, and pseudoboehmite,
and mixtures
thereof. Other aluminum sources include, but are not limited to, other water-
soluble
aluminum salts, sodium aluminate, aluminum alkoxides, such as aluminum
isopropoxide, or
aluminum metal, such as aluminum in the form of chips.
[0065] Alternatively or in addition to previously mentioned sources of
Si and Al, sources
containing both Si and Al elements can also be used as sources of Si and Al.
Examples of
suitable sources containing both Si and Al elements include amorphous silica-
alumina gels,
kaolin, metal-kaolin, and zeolites, in particular aluminosilicates such as
synthetic faujasite
and ultrastable faujasite, for instance USY.
[0066] Suitable sources of pentavalent elements Z depend on the element
Z that is
selected. Preferably, Z is phosphorus. Suitable sources of phOsphorus include
one or more
sources selected from the group consisting of phosphoric acid; organic
phosphates, such as
triethyl phosphate, tetraethyl-ammonium phosphate; aluminophosphates; and
mixtures
thereof. Optionally, the synthesis mixture also contains a source of a
divalent element W.
Optionally, W is selected from the group consisting of Be and Zn.
[0067] Optionally, the synthesis mixture also contains a source of
halide ions, which may
be selected from the group consisting of chloride, bromide, iodide or
fluoride, preferably
fluoride. The source of halide ions may be any compound capable of releasing
halide ions in
the molecular sieve synthesis mixture. Non-limiting examples of sources of
halide ions
include hydrogen fluoride; salts containing one or several halide ions, such
as metal halides,
preferably where the metal is sodium, potassium, calcium, magnesium, strontium
or barium;
ammonium fluoride; or tetraalkylammonium fluorides such as tetramethylammonium
fluoride or tetraethylammonium fluoride. If the halide ion is fluoride, a
convenient source of
halide ion is HF or NH4F.
[0068] Optionally, the synthesis mixture also contains a source of
alkali metal Mt If
present, the alkali metal NI+ is preferably selected from the group consisting
of sodium,
potassium and mixtures of sodium and potassium. The sodium source may be a
sodium salt
such as NaC1, NaBr, or NaNO3; sodium hydroxide or sodium aluminate. The
potassium
source may be potassium hydroxide or potassium halide such as KC1 or NaBr or
potassium
nitrate.
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[0069] Optionally, the synthesis mixture also contains a source of
hydroxide ions, for
example, an alkali metal hydroxide such as sodium hydroxide or potassium
hydroxide.
Hydroxide can also be present as a counter ion of the (organic) structure
directing agent or by
the use of sodium aluminate or potassium aluminate as a source of Y, or by the
use of sodium
silicate or potassium silicate as the source of X. Sodium or potassium
aluminate and silicate
can also be used as the source of alkali metal M.
[0070] The synthesis mixture optionally further comprises a structure
directing agent
(SDA), in particular an organic structure directing agent (OSDA). The nature
of the SDA (or
OSDA) will depend upon the desired framework type. Many such structure
directing agents
are known to the skilled person. The structure directing agent may be present
in any suitable
form, for example as a salt of a halide such as a chloride, iodide or bromide,
as a hydroxide or
as a nitrate. The structure directing agent will generally be cationic and
preferably be an
organic structure directing agent, for example, a nitrogen-containing cation
such as a
quaternary ammonium cation. For example, the OSDA may optionally be N,N,N-
trimethy1-1-
adamantammonium hydroxide or iodide (TMAdA) where it is desired to produce a
zeolite of
framework type CHA or 1,1'-(hexane-1,6-diy1)bis(1-methylpiperidinium) where it
is desired
to produce a zeolite of framework type AFX.
[0071] The synthesis mixture can have any composition which is suitable
for preparing
the desired zeolite framework. The following ranges are given as examples of
desirable and
preferred ranges for each pair of components in the synthesis mixture.
Conveniently, the
molar ratio of X02 : Y203 in the synthesis mixture may be in the range of from
1 to infinity
(i.e. no Y), in particular from 1 to100, preferably from 4 to 50. Optionally,
in the synthesis
mixture the molar ratio of SDA : (X02 + Y203 + Z205) is in the range of from
0.04 to 0.5,
preferably from 0.08 to 0.3. Optionally, in the synthesis mixture the molar
ratio of H20 :
(X02 + Y203) is in the range of from Ito 100, preferably from 10 to 60.
Optionally, in the
synthesis mixture the molar ratio of M+ : (X02 + Y203 + Z205) is in the range
of from 0 to
0.45, preferably from 0 to 0.20. Optionally, in the synthesis mixture the
molar ratio of OH- :
(X02 + Y203 + Z205) is in the range of from 0 to 1.0, preferably from 0.2 to
0.4. Optionally,
in the synthesis mixture the molar ratio of halide- : (X02 + Y203 + Z205) is
in the range of
from 0 to 1, preferably from 0 to 0.5. In a preferred embodiment, no Z is
present and the
molar ratio of X02 : Y203 in the synthesis mixture may be in the range of from
I to infinity
(i.e. no Y when the zeolite is a silicate), in particular from 1 to100,
preferably from 4 to 50,
e.g. when the zeolite is an aluminosilicate or a borosilicate; the molar ratio
of SDA : (X02 +
Y203) is in the range of from 0.04 to 0.5, preferably from 0.08 to 0.3; the
molar ratio of H2O:
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(X02 + Y203) is in the range of from I to 100, preferably from 10 to 60; the
molar ratio of
1\4+ : (X02 + Y203) is in the range of from 0 to 0.45, preferably from 0 to
0.20; the molar ratio
of OW : (X02 + Y203) is in the range of from 0 to 1.0, preferably from 0.2 to
0.4; and the
molar ratio of halide- : (X02 + Y203) is in the range of from 0 to 1,
preferably from 0 to 0.5.
The reaction mixture may for example have a composition, expressed in terms of
mole ratios,
as indicated in the following Table:
Mole ratio Useful Preferred
X02 / Y203 Ito 100 (or 00 if no Y) 4 to 50 (or co if
no Y)
SDA / (X02 + Y203) 0.04 to 0.5 0.08 to 0.3
H20 / (X02 + Y203) 1 to 100 5 to 60
114+ / (X02 + Y203) 0 to 0.45 0 to 0.20
OH- / (X02 + Y203) 0 to 1.0 0.2 to 0.4
Halide- / (X02 + Y203) 0 to 1 0 to 0.5
[0072] The synthesis may be performed with or without added nucleating
seeds. If
nucleating seeds are added to the synthesis mixture, the seeds are suitably
present in an
amount from about 0.01 ppm by weight to about 10,000 ppm by weight, based on
the
synthesis mixture, such as from about 100 ppm by weight to about 5,000 ppm by
weight of
the synthesis mixture. The seeds can for instance be of any suitable zeolite,
in particular of a
zeolite having the same framework as the zeolite to be obtained.
[0073] Crystallization can be carried out under either static or stirred
conditions in a
suitable reactor vessel, such as for example, polypropylene jars or Teflon
lined or stainless
steel autoclaves. The crystallization is typically carried out at a
temperature of about 100 C
to about 200 C, such as about 150 C to about 170 C, for a time sufficient for
crystallization
to occur at the temperature used, e.g., from about 1 day to about 100 days, in
particular from
1 to 50 days, for example from about 2 days to about 40 days. Thereafter, the
synthesized
crystals are separated from the mother liquor and recovered.
[0074] Since the as-synthesized crystalline zeolite contains the
structure directing agent
within its pore structure, the product is typically activated before use in
such a manner that
the organic part of the structure directing agent is at least partially
removed from the zeolite.
The activation process is typically accomplished by calcining, more
particularly by heating
the zeolite at a temperature of at least about 200 C, preferably at least
about 300 C, more
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preferably at least about 370 C for at least 1 minute and generally not
longer than 20 hours.
While subatmospheric pressure can be employed for the thermal treatment,
atmospheric
pressure is usually desired for reasons of convenience. The thermal treatment
can be
performed at a temperature up to about 925 C. For instance, the thermal
treatment can be
conducted at a temperature of from 400 to 600 C, for instance from 500 to 550
C, in the
presence of an oxygen-containing gas, for example in air.
[0075] The small pore size synthetic zeolite of the present invention or
manufactured by
the process of the present invention may be used as an adsorbent or as a
catalyst to catalyze a
wide variety of organic compound conversion processes including many of
present
commercial/industrial importance. Examples of preferred chemical conversion
processes
which can be effectively catalyzed by the zeolite of the present invention or
manufactured by
the process of the present invention, by itself or in combination with one or
more other
catalytically active substances including other crystalline catalysts, include
those requiring a
catalyst with acid activity or hydrogenation activity. Examples of organic
conversion
processes which may be catalyzed by zeolite of the present invention or
manufactured by the
process of the present invention include cracking, hydrocracking,
isomerization,
polymerization, reforming, hydrogenation, dehydrogenation, dewaxing,
hydrodewaxing,
adsorption, alkylation, transalkylation, dealkylation, hydrodecylization,
disproportionation,
oligomerization, dehydrocyclization and combinations thereof. The conversion
of
hydrocarbon feeds can take place in any convenient mode, for example in
fluidized bed,
moving bed, or fixed bed reactors depending on the types of process desired.
[0076] The zeolite of the present disclosure, when employed either as an
adsorbent or as
a catalyst in an organic compound conversion process should be dehydrated, at
least partially.
This can be done by heating to a temperature in the range of about 100 C to
about 500 C,
such as about 200 C to about 370 C in an atmosphere such as air, nitrogen,
etc., and at
atmospheric, subatmospheric or superatmospheric pressures for between 30
minutes and 48
hours. Dehydration can also be performed at room temperature merely by placing
the
molecular sieve in a vacuum, but a longer time is required to obtain a
sufficient amount of
dehydration.
[0077] Once the zeolite has been synthesized, it can be formulated into a
catalyst
composition by combination with other materials, such as binders and/or matrix
materials
that provide additional hardness or catalytic activity to the finished
catalyst. These other
materials can be inert or catalytically active materials.
[0078] In particular, it may be desirable to incorporate the zeolite of
the present
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invention or manufactured by the process of the present invention with another
material that
is resistant to the temperatures and other conditions employed in organic
conversion
processes. Such materials include active and inactive materials and synthetic
or naturally
occurring zeolites as well as inorganic materials such as clays, silica and/or
metal oxides such
as alumina. The latter may be either naturally occurring or in the form of
gelatinous
precipitates or gels including mixtures of silica and metal oxides. Naturally
occurring clays
which may be used include the montmorillonite and kaolin family, which
families include the
subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and
Florida
clays or others in which the main mineral constituent is halloysite,
kaolinite, dickite, nacrite,
to or anauxite. Such clays can be used in the raw state as originally mined
or after being
subjected to calcination, acid treatment or chemical modification. These
binder materials are
resistant to the temperatures and other conditions, e.g., mechanical
attrition, which occur in
various hydrocarbon conversion processes. Thus the zeolites of the present
invention or
manufactured by the process of the present invention may be used in the form
of an extrudate
with a binder. They are typically bound by forming a pill, sphere, or
extrudate. The
extrudate is usually formed by extruding the zeolite, optionally in the
presence of a binder,
and drying and calcining the resulting extrudate.
[0079] Use of a material in conjunction with the zeolite of the present
invention or
manufactured by the process of the present invention, i.e., combined therewith
or present
during synthesis of the new crystal, which is active, tends to change the
conversion and/or
selectivity of the catalyst in certain organic conversion processes. Inactive
materials suitably
serve as diluents to control the amount of conversion in a given process so
that products can
be obtained in an economic and orderly manner without employing other means
for
controlling the rate of reaction. These materials may be incorporated into
naturally occurring
clays, e.g., bentonite and kaolin, to improve the crush strength of the
catalyst under
commercial operating conditions.
[0080] In addition to the foregoing materials, the zeolite can be
composited with a
porous matrix material such as silica-alumina, silica-magnesia, silica-
zirconia, silica-thoria,
silica-beryllia, silica-titania as well as ternary compositions such as silica-
alumina-thoria,
3() silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-
zirconia.
[0081] The relative proportions of zeolite and inorganic oxide matrix
may vary widely,
with the molecular sieve content ranging from about 1 to about 90 percent by
weight and
more usually, particularly when the composite is prepared in the form of
beads, in the range
of about 2 to about 80 weight percent of the composite.
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EXAMPLES
[0082] The following examples illustrate the present invention. Numerous
modifications
and variations are possible and it is to be understood that within the scope
of the appended
claims, the invention may be practiced otherwise than as specifically
described herein.
[0083] In the following examples, various parameters were measured in order
to define
the properties of the products that were manufactured. A suitable XRD method
involved a
Bruker D4 diffractometer using Cu Ka radiation at 35 kV/45 mA, 0.20
divergence slit, and a
Vantec detector. Data was collected from 2 to 50 2-theta, 0.018 step size,
and 0.2 sec/step
counting time using Bragg-Brentano geometry.
[0084] For every zeolite prepared according to the present invention the
degree of
crystallinity was >95%. The absence of any amorphous material was determined
by the
absence of a broad diffraction peak in the 2-theta range of 18 ¨ 25 and by
the absence of a
second amorphous phase in the SEM pictures.
EXAMPLE 1: Pt Encapsulated in High Silica CHA Zeolite using TMSH as anchoring
agent [Pt: (SiO2 + A1203) = 0.00032]
[0085] This example illustrates successful preparation of a sintering-
resistant platinum
catalyst according to the present invention.
[0086] 800 mg of sodium hydroxide (99wt%, Sigma-Aldrich) was dissolved
in 6.9 g of
water. Then, 86 mg of a 8wt% aqueous solution of chloroplatinic acid (H2PtC16,
37.50wt% Pt
basis, Sigma-Aldrich) and 52 mg of (3-mercaptopropyl)trimethoxysilane (TMSH,
95%,
Sigma-Aldrich) were added to the above solution, and the mixture was stirred
for 30 minutes.
Afterwards, 13.04 g of an aqueous solution of N,N,N-trimethy1-1-
adamantammonium
hydroxide (TMAdA, 16.2wt%) was added and maintained under stirring during 15
minutes.
At that time, 293 mg of aluminum hydroxide (58wt%, Sigma-Aldrich) was added,
and the
resultant mixture kept under stirring at 80 C for 30 minutes. Finally, 3 g of
colloidal silica
(Ludox AS40, 40wt%, Aldrich) was introduced in the synthesis mixture, and
maintained
under stirring at 80 C for 30 minutes. The final gel composition was SiO2 :
0.033 Al2O3 :
0.00033 Pt : 0.005 TMSH : 0.2 TMAdA : 0.4 NaOH : 20 H20.
100871 The gel was transferred to an autoclave with a Teflon liner, and
heated at 90 C
.. for 7 days, and later, at 160 C for 2 days under dynamic conditions. The
sample after the
hydrothermal crystallization was filtered and washed with abundant distilled
water, and
finally dried at 100 C.
[0088] The solid was characterized by Powder X-ray Diffraction (PXRD),
obtaining the
characteristic PXRD pattern of the CHA material (see Example 1 in Figure 1).
Elemental
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analysis by ICE-AES of the resultant solid indicated a Si/A1 of 8.5
(Si02:A1203 molar ratio of
17:1) and analysis by XRF gave a Pt content of 0.21wt%.
[0089] The Pt-containing CHA was calcined at 550 C in air in order to
remove the
organic moieties included inside the microporous material during the
crystallization process.
[0090] The calcined sample was treated with H2 at 400 C for 2 hours. TEM
microscopy
(see Figure 2A) reveals the formation of very small Pt nanoparticles. These Pt
nanoparticles
are substantially spherical and have a particle size (biggest dimension, i.e.
diameter) in the
range of I to 3 nm within the high-silica CHA structure. The particle size
distribution
(diameter vs. abundance expressed as a percentage of the particles by number)
for this sample
is shown in Figure 2C.
[0091] The above reduced sample was subjected to an additional thermal
treatment. It
was oxidized in air at 650 C for 2 hours (50 sccm of pure 02 at atmospheric
pressure to treat
200 mg of catalyst), followed by a 1 hour purge with N2 (50 sccm of pure N2 at
atmospheric
pressure to treat 200 mg of catalyst) and later, reduced again with H2 at 400
C for 2 hours
(50 sccm of pure H2 at atmospheric pressure to treat 200 mg of catalyst). TEM
microscopy
(see Figure 2B) reveals that the small Pt nanoparticles within the high-silica
CHA structure
remain stable and have not sintered into larger particles after the additional
thermal (or redox)
treatments. The particle size distribution (diameter vs. abundance expressed
as a percentage
of the particles by number) for this sample after the additional thermal
treatment is shown in
Figure 2D.
[0092] In order to examine the formation of oxidized platinum structures
during the 02
treatment step X-Ray Absorption Near Edge Structure (XANES) was recorded as
the sample,
previously reduced with H2 at 400 C, was treated with 5% 02 at increasing
temperatures
(from 20 to 500 C). The spectra show a gradual decrease of the first
absorption peak (white
.. line intensity), which is ascribed to gradual oxidation of the metal
nanoparticles (Figure 3A).
The observation of isosbestic point in the spectra indicate simple
stoichiometric
transformation of one species into another, consistent with a fine control of
the catalytic
structures and their uniformity. Extended X-Ray Fine Structure (EXAFS) after
completion of
the oxidation treatment shows the absence of any signal attributed to Pt
backscatterers, which
demonstrates the lack of Pt-Pt or Pt-0-Pt moieties; EXAFS clearly evidences
the presence of
oxygen bonded to these single-site platinum centers (Figure 3B ¨ bottom line).
For
comparison, Figure 3B also shows the EXAFS spectrum of a platinum foil (upper
line), and
that corresponding to the sample of Example I (calcined at 550 '0C and treated
with H2 at 400
C) (middle line in Fig 3B - note that the Pt-Pt peak intensity in the sample
is small compared
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to the reference foil, an additional proof of the smallness of the
nanoparticles).
EXAMPLE 2: Pt-Containing Amorphous SiO2¨ Comparative
[0093] A catalyst consisting of platinum nanoparticles supported on
amorphous silica
(reference material) was prepared according to the process of W02011/096999.
In this
procedure, 1.784 g of tetraammine platinum hydroxide was mixed with 12.2 g of
deionized
water. 0.6 g of arginine was added to this solution so that the arginine to Pt
molar ratio was
8:1. The solution was added by incipient wetness onto 10.0 g of Davison silica
(grade 62, 60-
200 mesh, 150 Angstrom pore diameter from Sigma-Aldrich). The sample was dried
at 120
C for 2 hrs. The dried sample was placed in a tube furnace with an active air
flow of 300
sccm of air, with the heating rates being maintained at 3 C/min to 400 C and
then
maintaining the temperature at 400 C for 16 hrs. The chemical analysis of the
resultant solid
by ICE-AES indicated a Pt content of 0.8 A wt.
[0094] The calcined sample was treated with H2 at 400 C for 2 hours.
TEM microscopy
(see Figure 4A) reveals the formation of small Pt nanoparticles on the silica
surface. The
particle size distribution (diameter vs. abundance expressed as a percentage
of the particles
by number) for this sample is shown in Figure 4C.
[0095] The above reduced sample was subjected to an additional thermal
treatment. It
was oxidized in air at 650 C for 2 hours (50 sccm of pure 02 at atmospheric
pressure to treat
200 mg of catalyst), followed by a 1 hour purge with N2 (50 sccm of pure N2 at
atmospheric
pressure to treat 200 mg of catalyst) and later, reduced again with H2 at 400
C for 2 hours
(50 sccm of pure H2 at atmospheric pressure to treat 200 mg of catalyst). TEM
microscopy
(see Figure 4B) reveals that the small Pt nanoparticles suffer from severe
sintering as a result
of the additional thermal (or redox) treatment. The particle size distribution
(diameter vs.
abundance expressed as a percentage of the particles by number) for this
sample after the
additional thermal treatment is shown in Figure 4D.
EXAMPLE 3: Shape selective hydrogenation catalysis
[0096] In a typical experiment, 40 mg of the catalyst synthesized
according to Examples
1 and 2 (after calcination and reduction but after the additional thermal
treatment) were
mixed with 1 g of neutral silica (silica gel, Davisil Grade 640, 35- 60 mesh)
and loaded in a
conventional tubular plug-flow reactor (ID = 6/16 inches 9.53 mm). High purity
hydrogen,
ethylene (or propylene), and nitrogen were fed through the catalyst bed at
atmospheric
pressure and flow rates were regulated by standard mass flow controllers. The
temperature of
the catalyst bed was controlled using a three-zone vertical furnace (ATS,
model 3210) with a
precision of 1 C.
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[0097]
The downstream reaction effluents were analyzed in a gas chromatograph
(Agilent 5975B) connected in series, and equipped with a 50 m capillary column
(Rt-
Alumina BOND/Na2SO4, 0.53 mm ID, 10 p.m) and a FID detector. The conditions of
the
analysis were: initial oven temperature = 50 C; temperature ramp = 10 C/min;
final oven
.. temperature = 180 C; injector temperature = 220 C; detector temperature =
320 C; pressure
at the head of the column = 9.7 psi. For identification purposes, the position
of the various
reactants and products within the gas chromatogram were compared with
standards
commercially available. Conversions and selectivity were calculated from the
corresponding
GC areas. Typically, the reactor was operated in the differential conversion
range (< 15 %)
allowing determination of the reaction rates directly from the GC data.
[0098]
Prior to the hydrogenation experiment, the catalyst was reduced in situ in a
flow
of hydrogen (50 mL/min) at 400 C for 4 h. The reactor was then cooled down to
the selected
reaction temperature (80 C). With the catalyst bed at 80 I C, a mixture of
ethylene (or
propylene) (4 mL/min), hydrogen (20 mL/min), and nitrogen (100 mL/min) was
flowed
Is through the reactor, and the reacted gas mixture was analyzed at various
times on stream.
[0099]
Figure 5 shows the catalytic activity of the fresh CHA-encapsulated platinum
(Example I) and the Pt/SiO2 (Example 2) catalysts for each alkene, expressed
as mol of
reactant converted per mol of platinum per second. On the encapsulated
material, the
[PR zeolite _
ethylene hydrogenation rate is at least 16 times greater than that of
propylene
ER zeolite
[PR
16] , whereas both alkenes react at similar rates on the Pt/SiO2 catalyst
Si02 = 1]. This
[ER Si02
corresponds to a percentage of Pt encapsulated in the zeolite (a) of example I
of at least 94%.
These results further demonstrate successful encapsulation of the metal inside
the CHA
crystals, where propylene experiences severe diffusional limitations at the
selected reaction
temperature.
EXAMPLE 4: Pt Encapsulated on High Silica CHA Zeolite using TMSH anchoring
agent [Pt: (SiO2 +A1203) = 0.00097]
[00100]
800 mg of sodium hydroxide (99wt%, Sigma-Aldrich) was dissolved in 6.9 g of
water. Then, 256 mg of a 8wt /0 aqueous solution of chloroplatinic acid
(H2PtC16, 37.50wt%
Pt basis, Sigma-Aldrich) and 52 mg of (3-mercaptopropyl)trimethoxysilane
(TMSH, 95wt%,
.. Sigma-Aldrich) were added to the above solution, and the mixture stirred
for 30 minutes.
Afterwards, 13.04 g of an aqueous solution of N,N,N-trimethy1-1 -
adamantammonium
hydroxide (TMAdA, 16.2wt%) was added and maintained under stirring during 15
minutes.
At that time, 293 mg of aluminum hydroxide (58wt%, Sigma-Aldrich) was added,
and the
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resultant mixture kept under stirring at 80 C for 30 minutes. Finally, 3 g of
colloidal silica
(Ludox AS40, 40wt%, Aldrich) was introduced in the synthesis mixture, and
maintained
under stirring at 80 C for 30 minutes. The final gel composition was SiO2 :
0.033 Al2O3 :
0.001 Pt: 0.005 TMSH : 0.2 TMAdA : 0.4 NaOH : 20 H20.
[00101] The gel was transferred to an autoclave with a Teflon liner, and
heated at 90 C
for 7 days, and later, at 160 C for 2 days under dynamic conditions. The
sample after the
hydrothermal crystallization was filtered and washed with abundant distilled
water, and
finally dried at 100 C.
[00102] The solid was characterized by Powder X-ray Diffraction (PXRD),
obtaining the
characteristic PXRD pattern of the CHA material (see Example 4 in Figure 1).
The chemical
analysis of the resultant solid indicated a Si/A1 ratio of 8 (SiO2/Al2O3 molar
ratio of 16:1) and
a Pt content of 0.46wt%.
[00103] The Pt-containing CHA was calcined at 550 C in air in order to
remove the
organic moieties included inside of the microporous material during the
crystallization
process, and subsequently reduced in flow of H2 at 400 C for 2 h. After this
two-step
thermal treatment, TEM (Figure 6) reveals the exclusive presence of small
metal
nanoparticles in approximately 95 % of the images (illustrated in Figure 6A).
Approximately
5 % of the images include at least one big nanoparticle in addition to the
small ones (as
illustrated in Figure 6B). The percentage of Pt encapsulated in the zeolite
(a) was determined
.. to be 90%.
EXAMPLE 5: Pt Encapsulated in High Silica CHA Zeolite using Amine Ligands
[00104] A synthesis gel was prepared with the composition:
2.15 SDAOH: 0.1 Pt(NH3)4(NO3)2: 7 Na20: Al2O3: 25 SiO2: 715 H20,
where SDAOH is N,N,N-trimethy1-1-adamantammonium hydroxide. In a 125 ml Teflon-
lined autoclave was added 20.82 g of sodium silicate (EMD, 28.2wt% SiO2,
9.3wt% Na2O),
39.2 g de-ionized water, 0.50 g 50wt% NaOH and 8.88 g 25wt% SDAOH. Then 2.80 g
of an
aqueous solution of Pt(NH3)4(NO3)2 (3.406wt% Pt) was added drop wise with
vigorous
stirring. Next 2.85 g of USY (Engelhard, EZ-190, SiO2/Al2O3 = 5, 17.5wt%
Al2O3) was
stirred in. The autoclave was mounted on a rotating shelf (25 rpm) in a 140 C
oven for 7
days. The product was recovered by vacuum filtration, washed with de-ionized
water and
dried in a 115 C oven. Phase analysis by powder XRD showed the sample to be
pure
chabazite (see Example 5 in Figure 1). The sample was calcined to remove the
SDA by
heating in a muffle furnace from 25 C to 400 C in two hours and 15 min. in
nitrogen and
then ramping to 600 C in air and then holding for 2 hours in air. Elemental
analysis by ICE-
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AES gave Si/A1 = 7.7 (Si02:A1203 molar ratio of 15.4:1) and Na/A1 = 0.56 and
analysis by
XRF gave 1.66wt% Pt. The calcined sample was treated with H2 at 400 C for 2
hours. The
percentage of Pt encapsulated in the zeolite (a) was determined to be 87%. TEM
microscopy
(see Figure 7A) reveals the formation of very small Pt nanoparticles within
the high-silica
CHA structure. The above reduced sample was subjected to an additional thermal
treatment.
It was oxidized in air at 650 C for 2 hours (50 sccm of pure 02 at
atmospheric pressure to
treat 200 mg of catalyst), followed by a 1 hour purge with N2 (50 sccm of pure
N2 at
atmospheric pressure to treat 200 mg of catalyst), and later, reduced again
with H2 at 400 C
for 2 hours (50 sccm of pure H2 at atmospheric pressure to treat 200 mg of
catalyst). TEM
microscopy (see Figure 7B) reveals that the small Pt nanoparticles within the
high-silica
CHA structure remain stable and have not sintered into larger particles after
the additional
thermal (or redox) treatments. The particle size distribution (diameter vs.
abundance
expressed as a percentage of the particles by number) for this sample is shown
in Figure 7C.
EXAMPLE 6: Rh Encapsulated in High Silica CHA Zeolite using Amine Ligands
[00105] A synthesis gel was prepared with the composition:
SDAOH: 0.064 Rh(C2H4N2)3C13: 10 Na20: A1203: 34 5i02: 1000 H20,
where SDAOH is N,N,N-trimethy1-1-adamantammonium hydroxide (TMAdA). In a 125
ml
Teflon-lined autoclave was added 9.49 g 25wt% SDAOH, 0.46 g 50vvt% Na0H, 23.11
g of
sodium silicate (EMD, 28.2vvt% 5i02, 9.3wt% Na20), and 43.74 g de-ionized
water. Then
1.02 g of an aqueous 10 wt% solution of Rh(C2H4N2)3C13=3H20 was added drop
wise with
vigorous stirring. Next 2.18 g of USY (Engelhard, EZ-190, Si/A1 = 2.5, 17.5wt%
A1203) was
added and stirred for 2 minutes. The autoclave was mounted on a rotating shelf
(40 rpm) in
an 140 C oven for 5 days. The product was recovered by vacuum filtration,
washed with de-
ionized water and dried in a 115 C oven. Phase analysis by powder XRD showed
the sample
to be pure chabazite (see Example 6 in Figure 1). The sample was calcined to
remove the
SDA by heating in a muffle furnace from 25 C to 560 C in two hours in air
and then
holding for 3 hours in air. Elemental analysis by ICE-AES gave Si/A1 = 8.5
(Si02:A1203
molar ratio of 17:1) and Na/A1 = 0.53 and analysis by XRF gave 0.35wt% Rh. The
percentage of Rh encapsulated in the zeolite (a) was determined to be 94%. In
order to
examine the formation of single atom rhodium species during the 02 treatment
EXAFS
spectra were recorded after treatment of the sample, previously reduced with
H2 at 400 C,
with 5% 02 at 500 C. EXAFS spectra after completion of the oxidation
treatment shows the
absence of any signal attributed to Rh backscatterers, which demonstrates the
lack of Rh-Rh
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or Rh-O-Rh moieties; EXAFS clearly evidences the presence of oxygen bonded to
these
single-site rhodium centers (Figure 8).
EXAMPLE 7: Rh on CHA Zeolite - Comparative
[00106] A mixture of composition.
1.4 K20: A1203: 5.1 SiO2: 1101-120
was prepared by adding 5.8 g of KOH=1/2H20, 14.4 g of silica alumina gel
(22.5wt% Al2O3,
67.5wt% SiO2) and 59.8 g of water to a 125 ml Teflon lined autoclave. The
mixture was
placed on a rotating shelf (25 rpm) in a 100 C oven for 3 days. The product
was recovered
by vacuum filtration, washed with de-ionized water and dried in a 115 C oven.
Phase
analysis by powder XRD showed the sample to be pure chabazite (see Example 7
in Figure
1). A portion of the chabazite was exchanged twice with lOwt% NaNO3 solution,
calcined in
air for 3 hrs. at 350 C, exchanged a third time, calcined again at 3 hrs. at
350 C and finally
exchanged a fourth time. Elemental analysis by ICE-AES gave Si/AI = 2.4
(SiO2/A1203 molar
ratio of 4.8:1), K/AI = 0.18 and Na/Al= 0.80. The sodium exchanged chabazite
was dried for
60 min at 300 C and allowed to cool down in a molecular sieve desiccator.
Then 0.441 g of
an aqueous solution of Rh(NO3)3 (10.1wt% Rh) and 2.27 g of deionized water
were placed in
100 ml beaker. The dried chabazite was quickly added and the mixture kneaded
by hand for 2
minutes with a ceramic spatula and then mixed for 4 minutes in a dual
asymmetric centrifuge
(FlackTec DAC600 SpeedMixer). The sample was dried at 115 C and then ramped
to 350
C at 0.5 C/min in air and then held at 350 C in air for two hours. The
percentage of Rh
encapsulated in the zeolite (a) was determined to be 20%.
EXAMPLE 8: Rh/Pt Encapsulated in High Silica CHA Zeolite using Amine Ligands
[00107] A 10 g sample of USY (Engelhard, EZ-190, Si02/A1203 = 5, 17.5wt%
A1203) was
exchanged with 11.7 g of an aqueous solution of Pt(NH3)4(NO3)2 (3.406wt% Pt)
in 100 mls
H20. The pH was adjusted to 9 by the addition of dilute NI-140H, and stirred
at 60-80 C for 4
hours. The product was washed with deionized water and dried in a 115 C oven.
Analysis by
XRF gave 4.8wt% Pt.
[00108] A synthesis gel was then prepared with the composition, 2.2
SDAOH: 0.15 Pt:
0.15 Rh(C2H4N2)3C13: 7 Na20: A1203: 25 SiO2: 715 H20, where SDAOH is N,N,N-
trimethyl-
I -adamantammonium hydroxide (TMAdA). In a 125 ml Teflon-lined autoclave was
added
9.5 g 25wt% SDAOH, 1.0 g 50wt% Na0H, 20.1 g of sodium silicate (EMD, 28.2wt%
SiO2,
9.3wt% Na20), and 44.6 g de-ionized water. Then 1.7 g of an aqueous 1 Owt%
solution of
Rh(C2H4N2)3C13-3H20 was added drop wise with stirring and then stirred for an
additional 10
minutes. Next 1.5 g of USY (Engelhard, EZ-190, Si/AI = 2.5, 17.5wt% A1203) and
1.6 g of
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the above Pt exchanged USY was added and stirred until well mixed. The
autoclave was
mounted on a rotating shelf (25 rpm) in a 140 C oven for 7 days. The product
was recovered
by vacuum filtration, washed with de-ionized water and dried in a 115 C oven.
Phase
analysis by powder XRD showed the sample to be pure chabazite (see Example 8
in Figure
1). The sample was calcined to remove the SDA by heating in a muffle furnace
from 25 C to
500 C in two hours in air and then holding at 500 C for 3 hours in air.
Analysis by XRF
gave 0.64wt% Rh and 1.02wt% Pt. The calcined sample was treated with H2 at 400
C for 2
hours. TEM microscopy (see Figure 9A) reveals the formation of very small Pt
nanoparticles
within the high-silica CHA structure. The above reduced sample was oxidized in
air at 650
C for 2 hours, and later, reduced again with H2 at 400 C for 2 hours. TEM
microscopy (see
Figure 9B) reveals that the small Pt nanoparticles within the high-silica CHA
structure
remain stable and have not sintered into larger particles after the redox
treatments. The
percentage of Rh/Pt encapsulated in the zeolite (a) was determined to be 95%.
EXAMPLE 9: Rh Encapsulated in AFX Zeolite using Amine Ligands
[00109] A synthesis gel was prepared with the composition, 12 SDA(OH)2:
0.25
Rh(C2H4N2)3C13: 6 Na2O: Al2O3: 40 SiO2: 1200 H20, where SDA is 1,1'-(hexane-
1,6-
diyObis(1-methylpiperidinium). In a plastic beaker was added 28.5 g of
colloidal silica
(Ludox LS-30), 57.3 g 22.6vvt% SDA(OH)2, and 6.4 g de-ionized water. Then 3.79
g of an
aqueous 10 wt% solution of Rh(C2H4N2)3C13=3H20 was added drop wise with
stirring and
then stirred for an additional 10 minutes. Next 1.45 g of sodium aluminate
(USALCO 45,
25wt% A1203, 19.3wt% Na2O) and 2.7 g of USY (Engelhard, EZ- 190, SiO2/Al2O3
=5,
17.5wt% A1203) was added and stirred with a spatula. The mixture was then
thoroughly
homogenized in a SS blender and placed in a Teflon-lined autoclave. The
autoclave was
mounted on a rotating shelf (25 rpm) in a 160 C oven for 6 days. The product
was recovered
by vacuum filtration, washed with de-ionized water and dried in a 115 C oven.
Phase
analysis by powder XRD showed the sample to be pure AFX zeolite (see Example 9
in
Figure 1). The sample was calcined to remove the SDA by heating in a muffle
furnace from
25 C to 560 C in two hours in air and then holding for 3 hours in air.
Elemental analysis by
ICE-AES gave Si/A1 = 8.5 (SiO2 : A1203 molar ratio of 17:1) and Na/A1 = 0.53
and analysis
.. by XRF gave 2.1wt% Rh. The calcined sample was treated with H2 at 400 C
for 2 hours. The
percentage of Rh encapsulated in the zeolite (a) was determined to be 95%. TEM
microscopy (see Figure 10A) reveals the formation of very small Pt
nanoparticles within the
high-silica AFX structure. The above reduced sample was subjected to an
additional thermal
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treatment. It was oxidized in air at 650 C for 2 hours (50 sccm of pure 02 at
atmospheric
pressure to treat 200 mg of catalyst), followed by a 1 hour purge with N2 (50
sccm of pure N2
at atmospheric pressure to treat 200 mg of catalyst), and later, reduced again
with H2 at 400
C for 2 hours (50 sccm of pure H2 at atmospheric pressure to treat 200 mg of
catalyst). TEM
microscopy (see Figure 10B) reveals that the small Pt nanoparticles within the
high-silica
CHA structure remain stable and have not sintered into larger particles after
the additional (or
redox) treatments. The particle size distribution (diameter vs. abundance
expressed as a
percentage of the particles by number) for this sample is shown in Figure 10C.
EXAMPLE 10: Pt Encapsulated in a Pure SiO2 CHA Zeolite using Amine Ligands
[00110] 1.04 g of a lwt% aqueous solution of chloroplatinic acid
(H2PtC16=6H20, Sigma-
Aldrich) was mixed with 4.0 mg of tetraethylenepentamine (TEPA, Sigma-
Aldrich), and the
mixture was maintained under stirring for 15 minutes. This resulted in the in
situ formation of
a Pt complex wherein Pt is stabilized by TEPA (N-containing ligands). In a
different vessel,
1.28 g of N,N,N-trimethy1-1-adamantammonium iodide (TMAdA) was dissolved in 8
g of a
Trizma hydrochloride buffer solution (pH=7.4, Sigma-Aldrich), and the
resultant solution
mixed with the previous Pt-TEPA solution. Then, 1.0 g of
tetraethylorthosilicate (TEOS,
Sigma-Aldrich) was added, and the mixture stirred for 15 minutes. At this
point, 0.31 g of
ethanolamine was added as silica mobilizing agent, to improve the dispersion
of the metal
complex in the porous Si02 matrix, and the mixture stirred at room temperature
for 7 days.
Finally, the mixture was filtered and washed with abundant distilled water,
and dried at 100
C.
[00111]
23.9 g of an aqueous solution of N,N,N-trimethy1-1-adamantammonium
hydroxide (TMAdA, 11.3wt%) was mixed with 0.6 g of an aqueous solution of
hydrofluoric
acid (HF, Sigma-Aldrich, 48wt%), and maintained under stirring during 15
minutes. Then,
3.0 g of the above prepared Pt-containing amorphous silica material and 240 mg
of crystals of
CHA as seeds were introduced in the synthesis mixture, and maintained under
stirring the
required time to evaporate the excess of water until achieving the desired gel
concentration.
The final gel composition was SiO2 : 0.3 TMAdA : 0.3 HF : 3 H20.
[00112]
The gel was transferred to an autoclave with a Teflon liner, and heated at 150
C
for 2 days under dynamic conditions. The sample after the hydrothermal
crystallization was
filtered and washed with abundant distilled water, and finally dried at 100
C.
[00113]
The solid was characterized by Powder X-ray Diffraction (PXRD), obtaining the
characteristic PXRD pattern of the CHA material (see Example 10 in Figure 1).
The
chemical analysis by XRF of the resultant solid indicates a Pt content of
0.21wt%.
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[00114] Figure 11A shows a STEM image of the solid after being calcined
at 550 C in air
and reduced with H2 at 400 C for 2 hours. The sample was microtomed prior to
acquisition of
the STEM image. The particle size distribution (diameter vs. abundance
expressed as a
percentage of the particles by number) for this sample is shown in Figure 11B.
EXAMPLE 11: Pt/Pd Encapsulated in High Silica CHA Zeolite using TMSH as
anchoring agent
[00115] 40 mg of sodium hydroxide (99wt%, Sigma-Aldrich) was dissolved in
8 g of
water. Then, 340 mg of a 1 wt% aqueous solution of chloroplatinic acid
(H2PtC16, 37.50wt%
Pt basis, Sigma-Aldrich), 347 mg of a 1 wt% aqueous solution of
tetramminepalladium (II)
chloride (Pd(NH3)C12.H20, 99.99%, Sigma-Aldrich) and 63 mg of (3-
mercaptopropyl)trimethoxysilane (TMSH, 95%, Sigma-Aldrich) were added to the
above
solution, and the mixture was stirred for 30 minutes. Afterwards, 18.13 g of
an aqueous
solution of N,N,N-trimethy1-1-adamantammonium hydroxide (TMAdA, 9.2 wt%) was
added
and maintained under stirring during 15 minutes. At that time, 234 mg of
aluminum
hydroxide (58wt%, Sigma-Aldrich) was added, and the resultant mixture kept
under stirring at
80 C for 30 minutes. Finally, 6 g of colloidal silica (Ludox AS40, 40wt%,
Aldrich) was
introduced in the synthesis mixture, and maintained under stirring at 80 C
for 30 minutes.
The mixture was then left to cool at room temperature, and maintained under
stirring for the
required time to evaporate the excess of water until achieving the desired gel
concentration.
The final gel composition was SiO2 : 0.033 A1203 : 0.00017 Pt: 0.00033 Pd :
0.005 TMSH :
0.2 TMAdA : 0.4 NaOH :20 H20.
[00116] The gel was transferred to an autoclave with a Teflon liner, and
heated at 90 C
for 7 days, and later, at 160 C for 2 days under dynamic conditions. The
sample after the
hydrothermal crystallization was filtered and washed with abundant distilled
water, and
finally dried at 100 C.
[00117] The solid was characterized by Powder X-ray Diffraction (PXRD),
obtaining the
characteristic PXRD pattern of the CHA material. Elemental analysis by ICE-AES
of the
resultant solid indicated a Si/A1 of 7.0 (Si02:A1203 molar ratio of 14:1) and
analysis by XRF
gave a Pt and Pd content of 0.09 and 0.10 wt% respectively.
[00118] The Pt/Pd-containing CHA was calcined at 550 C in air in order to
remove the
organic moieties included inside the microporous material during the
crystallization process.
[00119] The calcined sample was treated with H2 at 400 C for 2 hours.
STEM
microscopy (see Figure 12) reveals the formation of very small metallic
nanoparticles. These
metallic nanoparticles are substantially spherical and have a particle size
(biggest dimension,
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i.e. diameter) in the range of 1 to 3 nm within the high-silica CHA structure.
[00120] In order to examine the formation of a bimetallic Pt-Pd
interaction during the H2
treatment, EXAFS spectra were recorded after the first H2 treatment at 400 C.
The spectra
(Figure 13A) show the existence of Pt-Pt and Pt-Pd interactions in the Pt LIII-
edge, and the
existence of Pd-Pt and Pd-Pd interactions in the Pd K-edge, evidencing the
formation of
bimetallic nanoparticles.
[00121] On the other hand, EXAFS spectra of the preceding sample after
subsequent
treatment in 02 at 500 C shows the lack of Pt-Pt, Pt-Pd, Pt-O-Pt, Pt-O-Pd,
and Pd-Pd, Pd-Pt,
Pd-O-Pd, Pd-O-Pt moieties in the Pt and Pd edges, respectively, and the
exclusive presence
of Pt-0 and Pd-0 interaction (Figurel 38), evidencing the formation of site-
isolated single
metal atoms after the high temperature oxidative treatment.
EXAMPLE 12: Pt/Fe Encapsulated in High Silica CHA Zeolite using TMSH as
anchoring agent
[00122] 640 mg of sodium hydroxide (99wt%, Sigma-Aldrich) was dissolved
in 8 g of
water. Then, 680 mg of a 1 wt% aqueous solution of chloroplatinic acid
(H2PtC16, 37.50wt%
Pt basis, Sigma-Aldrich) and 42 mg of (3-mercaptopropyl)trimethoxysilane
(TMSH, 95%,
Sigma-Aldrich) were added to the above solution, and the mixture was stirred
for 30 minutes.
Afterwards, 18.37 g of an aqueous solution of N,N,N-trimethy1-1-
adamantammonium
hydroxide (TMAdA, 9.2wt%) was added and maintained under stirring during 15
minutes. At
that time, 234 mg of aluminum hydroxide (58wt%, Sigma-Aldrich) was added, and
the
resultant mixture kept under stirring at 80 C for 30 minutes. Then, 6 g of
colloidal silica
(Ludox AS40, 40wt%, Aldrich) was introduced in the synthesis mixture, and
maintained
under stirring at 80 C for 30 minutes. Finally, 808 mg of a 20%wt aqueous
solution of iron
(III) nitrate [Fe(NO3)3.9H20, 98%, Sigma Aldrich] was added dropwise, and the
synthesis
mixture was maintained under stirring the required time to evaporate the
excess of water until
achieving the desired gel concentration. The final gel composition was Si02 :
0.033 A1203 :
0.01 Fe : 0.00033 Pt: 0.005 TMSH : 0.2 TMAdA : 0.4 NaOH : 20 H20.
[00123] The gel was transferred to an autoclave with a Teflon liner, and
heated at 90 C
for 7 days, and later, at 160 C for 2 days under dynamic conditions. The
sample after the
hydrothermal crystallization was filtered and washed with abundant distilled
water, and
finally dried at 100 C.
[00124] The solid was characterized by Powder X-ray Diffraction (PXRD),
obtaining the
characteristic PXRD pattern of the CHA material. Elemental analysis by ICE-AES
of the
resultant solid indicated a Si/A1 of 8.0 (Si02:A1203 molar ratio of 16:1) and
a Si/Fe of 56, and
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analysis by XRF gave a Pt content of 0.15wt%.
[00125] The Fe-Pt-containing CHA was calcined at 550 C in air in order
to remove the
organic moieties included inside the microporous material during the
crystallization process.
[00126] The calcined sample was treated with H2 at 400 C for 2 hours.
STEM
microscopy (see Figure 14) reveals the formation of very small metallic
nanoparticles. These
metallic nanoparticles are substantially spherical and have a particle size
(biggest dimension,
i.e. diameter) in the range of 1 to 3 nm within the high-silica CHA structure.
EXAMPLE 13: Pt Encapsulated in a Low Si/A1 Ratio LTA Zeolite ¨ comparative
example
[00127] A Pt-containing Al-rich LTA material was synthesized following the
methodology described by M. Choi et al. ("Mercaptosilane-assisted synthesis of
metal
clusters within zeolites and catalytic consequences of encapsulation", JACS,
2010, 132,
9129-9137) for comparison purposes.
[00128] First, 0.96 g of NaOH, 1.60 g of a colloidal suspension of SiO2
(Ludox, 40%wt),
and 7.2 g of water were mixed and maintained at 80 C for 30 minutes.
Afterwards, 1.2 g of
NaA102 and 3.6 g of water were added to the above mixture, and the resultant
gel maintained
under stirring at room temperature for 2 hours. The final gel composition was:
SiO2 : 0.7
A1203 : 0.002 Pt : 0.06 TMSH : 2.2 NaOH : 60 H20.
[00129] The gel was transferred to an autoclave with a Teflon liner, and
heated at 100 C
for 24 hours under dynamic conditions. The sample after the hydrothermal
crystallization was
filtered and washed with abundant distilled water, and finally dried at 100 C.
After the
synthesis procedure, the obtained solid showed the crystalline structure of
the LTA material.
[00130] The Pt-LTA sample prepared according to the procedure described
in M. Choi et
al., and the calcined Pt-CHA material prepared according to the Example 1 of
the present
patent application, were both first subjected to a treatment with H2 at 400 C.
Then, these
reduced samples were treated with steam at various temperatures, because vapor
water is
common in many industrial streams and is often responsible for hydrothermal
degradation of
the metal and/or the zeolite framework.
[00131] The reduced metal-containing zeolites were steamed in a muffle
furnace with
100% H20 for 4 h at 600 C. After this aging procedure, the formation of large
Pt particles
was not observed on the Pt-CHA sample of Example I (Figure 15 top), and the
crystallinity
of this zeolite was retained (Figures 16 top). In contrast, the zeolitic
structure in Pt-containing
Al-rich LTA zeolite collapsed under equivalent conditions, resulting in the
formation of large
Pt particles (Figures 15 bottom and 16 bottom).
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[00132] It will be appreciated that various presently unforeseen or
unanticipated
alternatives, modifications, variations or improvements therein may be
subsequently made by
those skilled in the art, and are also intended to be encompassed by the
following claims.
[00133] The disclosures of the foregoing publications are hereby
incorporated by
reference in their entirety. The appropriate components and aspects of the
foregoing
publications may also be selected for the present materials and methods in
embodiments
thereof.
[00134] Additionally or alternately, the invention relates to:
Embodiment 1: A small pore size synthetic zeolite having a degree of
crystallinity of at least
80% and comprising at least 0.01 wt%, based on the weight of the zeolite, of
at least one
catalytic metal selected from the group consisting of Ru, Rh, Pd, Ag, Os, Ir,
Pt, Au, Mo, W,
Re, Co, Ni, Zn, Cr, Mn, Ce, Ga, and combinations thereof, wherein at least 80%
of the
catalytic metal is encapsulated in the zeolite, wherein if the zeolite is an
aluminosilicate it
has a Si02:A1203 molar ratio of greater than 6:1.
.. Embodiment 2: The small pore size synthetic zeolite according to embodiment
1 which is an
8-membered ring zeolite, preferably of framework type AEI, AFT, AFX, CHA, CDO,
DDR, EDI, ER', IHW, ITE, ITW, KFI, MER, MTF, MWF, LEV, LTA, PAU, PWY,
RHO, SFW or UFI, more preferably of framework type CHA, AEI, AFX, RHO, KFI or
LTA, most preferably CHA or AFX.
Embodiment 3: The small pore size synthetic zeolite of embodiment 1 or 2 in
which the
zeolite framework contains one or more elements selected from the group
consisting of Si,
Al, P, As, Ti, Ge, Sn, Fe, B, Ga, Be and Zn; preferably in which the zeolite
framework
contains at least one tetravalent element X selected from the group consisting
of Si, Ge, Sn
and Ti and optionally at least one trivalent element Y selected from the group
consisting of
Al, B, Fe and Ga; more preferably in which the zeolite framework contains at
least Si and
optionally Al and/or B; most preferably in which the zeolite framework
contains at least Si
and optionally Al.
Embodiment 4: The small pore size synthetic zeolite of any one of the
preceding
embodiments which is selected from the group consisting of silicates,
aluminosilicates and
borosi I icates, preferably from the group consisting of silicates and
aluminosilicates.
Embodiment 5: The small pore size synthetic zeolite of any one of the
preceding
embodiments which contains Si and Al and having a Si02:A1203 molar ratio of
greater than
8:1, preferably greater than 10:1, more greater than 12:1, in particular
greater than 30:1,
more particularly greater than 100:1, most particularly greater than 150:1.
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Embodiment 6: The small pore size synthetic zeolite of any one of the
preceding
embodiments which further comprises at least 0.01 wt%, preferably from 0.05 to
5 wt% of a
transition metal selected from the group consisting of Cu, Fe, Ti, Zr, Nb, Hf,
Ta and
combinations thereof, in particular wherein said transition metal is extra-
framework metal.
Embodiment 7: The small pore size synthetic zeolite of any one of the
preceding
embodiments having a degree of crystallinity of at least 95%.
Embodiment 8: The small pore size synthetic zeolite of any one of the
preceding
embodiments which comprises from 0.05 to 5 wt% of the catalytic metal,
preferably from 0.1
to 3 wt%, more preferably from 0.5 to 2.5 wt%, most preferably from 1 to 2
wt%.
Embodiment 9: The small pore size synthetic zeolite of any one of the
preceding
embodiments wherein at least 80%, more preferably at least 90%, preferably at
least 95%,
and most preferably at least 98% of the catalytic metal is encapsulated in
zeolite.
Embodiment 10: The small pore size synthetic zeolite of any one of the
preceding
embodiments in which the catalytic metal is selected from the group consisting
of Ru, Rh, Pd,
Ag, Os, Ir, Pt, Au, Re, and combinations thereof; most preferably from the
group consisting
of Pt, Rh, Pd and Au and combinations thereof, in particular Pt, Pd and/or Rh.
Embodiment 11: The small pore size synthetic zeolite of any one of the
preceding
embodiments wherein the catalytic metal is present in the form of particles
wherein at least
80% of the particles by number have a biggest dimension of less than 4 nm as
measured by
TEM.
Embodiment 12: The small pore size synthetic zeolite of any one of the
preceding
embodiments which is a silicate or an aluminosilicate having a Si02:A1203
molar ratio of
greater than 6:1, preferably greater than 12:1, in particular greater than
30:1, wherein the
catalytic metal is selected from the group consisting of Pt, Rh, Pd and Au and
combinations
thereof, preferably Pt, Pd and/or Rh, and wherein the zeolite is of framework
type CHA,
AEI, AFX, RHO, KFI or LTA, preferably CHA or AFX.
Embodiment 13: The small pore size synthetic zeolite of any one of the
preceding
embodiments which is in as-synthesized form and further comprises a structure
directing
agent (SDA), in particular an organic structure directing agent (OSDA).
Embodiment 14: The small pore size synthetic zeolite of any one of the
preceding
embodiments in calcined form prepared by subjecting the small pore size
zeolite of
embodiment 13 to a calcining step.
Embodiment 15: A process for the preparation of the small pore size synthetic
zeolite of any
one of the preceding embodiments comprising:
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a) providing a reaction mixture comprising a synthesis mixture capable of
forming the
small pore size synthetic zeolite framework and at least one catalytic metal
precursor,
wherein the catalytic metal precursor includes metal complexes stabilized by
ligands L
selected from the group consisting of N-containing ligands, 0-containing
ligands, S-
containing ligands, and P-containing ligands,
b) heating said reaction mixture under crystallization conditions to form
crystals of said
small pore size synthetic zeolite, and
c) recovering said crystals of the small pore size synthetic zeolite from
the reaction
mixture.
Embodiment 16: The process of embodiment 15 wherein the ligand L is a N-
containing
ligand, in particular an amine, preferably selected from the group consisting
of NH3 and
bidentate amines and combinations thereof; more particularly selected from the
group
consisting of NH3 and ethylenediamine.
Embodiment 17: The process of embodiment 15 or 16 wherein the catalytic metal
precursor
is selected from the group consisting of [Pt(NH3)4]C12, [Pt(NH3)4](NO3)2,
[Pd(NH2CH2CH2NH2)2]C12,
[Rh(NH2CH2CH2NH2)3]C13,
[Ir(NH3)5COC12, [Re(NH2CH2CH2NH2)202]Cl, [Ag(NH2CH2CH2NH2)]1\103,
[Ru(NH3)6]C13,
[Ir(NH3)6]C13, [Ir(NH3)6](NO3)3, [Ir(NH3)5NO3](NO3)2.
Embodiment 18: The process of any one of embodiments15 to 17 wherein the
synthesis
mixture capable of forming the small pore size synthetic zeolite framework
comprises a
source of a tetravalent element X and optionally a source of a trivalent
element Y, and
wherein the molar ratio of the catalytic metal precursor (in terms of metal) :
(X02 + Y203) in
the synthesis mixture is in the range of from 0.00001 to 0.015, preferably
from 0.0001 to
0.010, more preferably from 0.001 to 0.008.
Embodiment 19: A process for the preparation of the small pore size synthetic
zeolite of any
one of embodiments 1 to 14 comprising:
a) providing a reaction mixture comprising a synthesis mixture capable of
forming the
small pore size synthetic zeolite framework, at least one anchoring agent, and
at least one
catalytic metal precursor, wherein the anchoring agent includes at least one
amine and/or
thiol group and at least one alkoxysilane group and the catalytic metal
precursor includes at
least one ligand capable of being exchanged by the at least one amine group
and/or thiol
group of the anchoring agent,
b) heating said reaction mixture under crystallization conditions to form
crystals of said
small pore size synthetic zeolite, and
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c) recovering said crystals of the small pore size synthetic zeolite from the
reaction mixture.
Embodiment 20: The process of embodiment 19 wherein the anchoring agent is a
thiol of the
structure HS-(CH2)x-Si-(0R)3, where x = 1 to 5 and R = CI to C4 alkyl,
preferably methyl,
ethyl, propyl, or butyl, most preferably x = 3 and R = methyl or ethyl.
Embodiment 21: The process of embodiment 19 wherein the anchoring agent is an
amine of
the structure H2N-(CH2)x-Si-(0R)3, where x = 1 to 5 and R = CI to C4 alkyl,
preferably
methyl, ethyl, propyl, or butyl, most preferably x = 3 and R = methyl or
ethyl.
Embodiment 22: The process of any one of embodiments 19 to 21 wherein the
synthesis
mixture capable of forming the small pore size synthetic zeolite framework
comprises a
source of a tetravalent element X and optionally a source of a trivalent
element Y, in which
the molar ratio of anchoring agent : (X02 + Y203) is in the range of from
0.001 to 0.02,
preferably from 0.002 to 0.015.
Embodiment 23: The process of any of embodiments 19 to 22 wherein the
synthesis mixture
capable of forming the small pore size synthetic zeolite framework comprises a
source of a
tetravalent element X and optionally a source of a trivalent element Y, and
wherein the molar
ratio of catalytic metal precursor (in terms of metal) : (X02 + Y203) is in
the range of from
0.0001 to 0.001, preferably from 0.0002 to less than 0.001, more preferably
from 0.0002 to
0.0005.
Embodiment 24: The process of any one of embodiments 19 to 23 wherein the
catalytic
metal precursor is selected from the group consisting of H2PtC16, H2PtBr6,
Pt(NH3)4Cl2,
Pt(NH3)4(NO3)2, RuClrxH20, RuBr3xH20, RhC13=xH20, Rh(NO3)3.2H20, RhBr3=xH20,
PdC12.xH20, Pd(NH3)4C12, Pd(NH3)41342, Pd(NH3)(NO3)2, AuC13, HAuBr4xH20,
HAuC14,
HAu(NO3)4AH20, Ag(NO3)2, ReC13, Re207, OsC13, 0s04, IrBr3.41420, IrC12, IrC14,
IrC13=xH20, and IrBra, where x is from 1 to 18, preferably from 1 to 6.
Embodiment 25: The process of any one of embodiments 15 to 19 wherein the
synthesis
mixture capable of forming the small pore size synthetic zeolite framework
comprises a
source of a tetravalent element X and optionally a source of a trivalent
element Y, optionally
a source of an alkali metal M, a source of hydroxide ions and/or a source of
halide ions, a
source of an organic structure directing agent (OSDA), and water.
Embodiment 26: The process of any one of embodiments 15 to 25 in which said
synthesis
mixture has a composition including the following molar ratios:
X02 : Y203 1 to co, preferably 1 to 100
OH- : (X02 + Y203) 0 to 1.0
: (X02 + Y203) 0 to 0.45
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SDA : (X02 + Y203) 0.04 to 0.5
H20 : (X02 + Y203) 1 to 100
Halide- : (X02 + Y203) 0 to 1
Embodiment 27: The process of any one of embodiments 15 to 26 in which X is Si
and Y is
Al and/or B, preferably in which X is Si and Y is Al.
Embodiment 28: The process of any one of embodiments 15 to 27 in which the
crystallization
conditions include heating the synthesis mixture at a temperature in the range
of from 100 C
to 200 C.
Embodiment 29: A process for the preparation of a small pore size synthetic
zeolite in
calcined form according to embodiment 14 which comprises subjecting the small
pore size
synthetic zeolite in as-synthesized form of embodiment 13 or the crystals of
small pore size
synthetic zeolite recovered in the process of any of embodiments 15 to 23 to a
calcination
step.
Embodiment 30: The process of embodiment 29 in which the calcination step is
carried out at
a temperature of equal to or greater than 500 C for a period of at least 1
hour.
Embodiment 31: Use of an active form of the small pore size synthetic zeolite
of any one of
embodiments 1 to 14 as a sorbent or as a catalyst.
Embodiment 32: A process for converting a feedstock comprising an organic
compound to a
conversion product which comprises the step of contacting said feedstock at
organic
compound conversion conditions with a catalyst comprising a small pore size
synthetic
zeolite of any one of embodiments 1 to 14.
Embodiment 33: The process of embodiment 32 which is a hydrogenation process.
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