U.S. patent application number 14/884859 was filed with the patent office on 2017-04-20 for method for making molecular sieve ssz-105.
The applicant listed for this patent is Chevron U.S.A. Inc.. Invention is credited to Christopher Michael Lew, Dan Xie.
Application Number | 20170107113 14/884859 |
Document ID | / |
Family ID | 58461681 |
Filed Date | 2017-04-20 |
United States Patent
Application |
20170107113 |
Kind Code |
A1 |
Xie; Dan ; et al. |
April 20, 2017 |
METHOD FOR MAKING MOLECULAR SIEVE SSZ-105
Abstract
A method for making a new crystalline molecular sieve designated
SSZ-105 is disclosed. SSZ-105 is synthesized using
N,N-dimethylpiperidinium cations as a structure directing agent.
SSZ-105 is a disordered aluminosilicate molecular sieve comprising
at least one intergrown phase of an ERI framework type molecular
sieve and an LEV framework type molecular sieve.
Inventors: |
Xie; Dan; (Richmond, CA)
; Lew; Christopher Michael; (Richmond, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chevron U.S.A. Inc. |
San Ramon |
CA |
US |
|
|
Family ID: |
58461681 |
Appl. No.: |
14/884859 |
Filed: |
October 16, 2015 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 29/70 20130101;
C01B 39/30 20130101; C01B 39/305 20130101; B01J 29/50 20130101;
B01J 35/1038 20130101; C01B 39/023 20130101; C01B 39/48 20130101;
B01J 2029/062 20130101 |
International
Class: |
C01B 39/48 20060101
C01B039/48 |
Claims
1. A method for preparing an aluminosilicate molecular sieve
composition comprising at least one intergrown phase comprising an
ERI framework type molecular sieve and an LEV framework type
molecular sieve, the method comprising: (a) preparing a reaction
mixture containing: (1) at least one source of silicon oxide; (2)
at least one source of aluminum oxide; (3) at least one source of a
Group 1 metal (M), wherein M is selected from the group consisting
of potassium and combinations of sodium and potassium; (4)
hydroxide ions; (5) N,N-dimethylpiperidinium cations (Q); and (6)
water; and (b) subjecting the reaction mixture to crystallization
conditions sufficient to form crystals of the molecular sieve
composition.
2. The method of claim 1, wherein the molecular sieve composition
is prepared from a reaction mixture comprising, in terms of mole
ratios, the following: TABLE-US-00009 SiO.sub.2/Al.sub.2O.sub.3 10
to 100 M/SiO.sub.2 0.05 to 1.00 Q/SiO.sub.2 0.05 to 0.70
OH/SiO.sub.2 0.10 to 1.00 H.sub.2O/SiO.sub.2 10 to 100
3. The method of claim 1, wherein the molecular sieve composition
is prepared from a reaction mixture comprising, in terms of mole
ratios, the following: TABLE-US-00010 SiO.sub.2/Al.sub.2O.sub.3 15
to 80 M/SiO.sub.2 0.10 to 0.30 Q/SiO.sub.2 0.20 to 0.45
OH/SiO.sub.2 0.30 to 0.80 H.sub.2O/SiO.sub.2 15 to 60
4. The method of claim 1, wherein the crystallization conditions
include a temperature of from 125.degree. C. to 200.degree. C.
5. The method of claim 1, wherein the ERI framework type molecular
sieve is present in the at least one intergrown phase in a
proportion to the LEV framework type molecular sieve of from 5% to
95%.
6. The method of claim 1, wherein the molecular sieve has, in its
as-synthesized and anhydrous form, a composition, in terms of mole
ratios, as follows: TABLE-US-00011 SiO.sub.2/Al.sub.2O.sub.3 10 to
50 Q/SiO.sub.2 0.02 to 0.20 M/SiO.sub.2 0.01 to 0.20
7. The method of claim 1, wherein the molecular sieve has, in its
as-synthesized and anhydrous form, a composition, in terms of mole
ratios, as follows: TABLE-US-00012 SiO.sub.2/Al.sub.2O.sub.3 15 to
40 Q/SiO.sub.2 0.05 to 0.20 M/SiO.sub.2 0.02 to 0.15
Description
TECHNICAL FIELD
[0001] This disclosure relates to a new crystalline molecular sieve
designated SSZ-105, a method for preparing SSZ-105, and uses for
SSZ-105. SSZ-105 is a disordered aluminosilicate molecular sieve
comprising at least one intergrown phase of an ERI framework type
molecular sieve and an LEV framework type molecular sieve.
BACKGROUND
[0002] Molecular sieve materials, both natural and synthetic, have
been demonstrated in the past to be useful as adsorbents and to
have catalytic properties for various types of organic conversion
reactions. Certain molecular sieves, such as zeolites,
aluminophosphates, and mesoporous materials, are ordered, porous
crystalline materials having a definite crystalline structure as
determined by X-ray diffraction. Within the crystalline molecular
sieve 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 molecular sieve
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 have come to
be known as "molecular sieves" and are utilized in a variety of
industrial processes.
[0003] Although many different crystalline molecular sieves have
been discovered, there is a continuing need for new molecular
sieves with desirable properties for gas separation and drying,
organic conversion reactions, and other applications. New molecular
sieves can contain novel internal pore architectures, providing
enhanced selectivities in these processes.
[0004] Molecular sieves are classified by the Structure Commission
of the International Zeolite Association according to the rules of
the IUPAC Commission on Zeolite Nomenclature. According to this
classification, framework type zeolites and other crystalline
microporous molecular sieves, for which a structure has been
established, are assigned a three letter code and are described in
the "Atlas of Zeolite Framework Types," Sixth Revised Edition,
Elsevier, 2007.
[0005] Molecular sieves may be ordered or disordered. Ordered
molecular sieves are built from structurally invariant building
units, called Period Building Units (PerBUs), and are periodically
ordered in three dimensions. Crystal structures built from PerBUs
are called end-member structures if periodic ordering is achieved
in all three dimensions. Disordered structures, on the other hand,
show periodic ordering in less than three dimensions. One such
disordered structure is a disordered planar intergrowth in which
the building units from more than one framework type are present.
Such intergrowths frequently have significantly different catalytic
properties from their end members. For example, zeolite ZSM-34 is
well known intergrowth of ERI and OFF framework types and exhibits
a methanol-to-olefins performance superior to that of its
individual component materials.
[0006] Disclosed herein is a unique disordered aluminosilicate
molecular sieve designated SSZ-105 which comprises at least one
intergrown phase of an ERI framework type molecular sieve and an
LEV framework type molecular sieve.
SUMMARY
[0007] The present disclosure is directed to a new family of
crystalline molecular sieves with unique properties, referred to
herein as "molecular sieve SSZ-105 " or simply "SSZ-105." Molecular
sieve SSZ-105 comprises at least one intergrown phase of an ERI
framework type molecular sieve and an LEV framework type molecular
sieve.
[0008] In its calcined form, molecular sieve SSZ-105 has a chemical
composition, in terms of mole ratios, comprising the following:
Al.sub.2O.sub.3:(n)SiO.sub.2
wherein n has a value from 10 to 50.
[0009] In one aspect, there is provided a process for preparing
molecular sieve SSZ-105 by (a) preparing a reaction mixture
containing: (1) at least one source of silicon oxide; (2) at least
one source of aluminum oxide; (3) at least one source of a Group 1
metal (M), wherein M is selected from the group consisting of
potassium and combinations of sodium and potassium; (4) hydroxide
ions; (5) N,N-dimethylpiperidinium cations; and (6) water; and (b)
subjecting the reaction mixture to crystallization conditions
sufficient to form crystals of the molecular sieve.
[0010] In its as-synthesized and anhydrous form, molecular sieve
SSZ-105 has a chemical composition, in terms of mole ratios,
comprising the following:
TABLE-US-00001 Broad Exemplary SiO.sub.2/Al.sub.2O.sub.3 10 to 50
15 to 40 Q/SiO.sub.2 0.02 to 0.20 0.05 to 0.20 M/SiO.sub.2 0.01 to
0.20 0.02 to 0.15
wherein Q comprises N,N-dimethylpiperidinium cations and M is a
Group 1 metal selected from the group consisting of potassium and
combinations of sodium and potassium.
[0011] Additionally, the molecular sieve disclosed herein is useful
in a wide range of processes, including separation processes and as
a catalyst in organic conversion reactions. In further aspect,
there is disclosed a process for converting a feedstock comprising
an organic compound to a conversion product which comprises the
step of contacting the feedstock with a catalyst at organic
compound conversion conditions, the catalyst comprising an active
form of the molecular sieve described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a powder X-ray diffraction (XRD) pattern of the
as-synthesized molecular sieve prepared in Example 1.
[0013] FIG. 2 is a Scanning Electron Micrograph (SEM) image of the
as-synthesized molecular sieve prepared in Example 1.
[0014] FIG. 3 is a plot of several DIFFaX-generated simulated XRD
patterns and a powder XRD pattern of the calcined form of the
molecular sieve prepared in Example 1.
[0015] FIG. 4 is a SEM image of the as-synthesized molecular sieve
prepared in Example 2.
[0016] FIG. 5 is a plot of several DIFFaX-generated simulated XRD
patterns and a powder XRD pattern of the calcined form of the
molecular sieve prepared in Example 2.
[0017] FIG. 6 is a SEM image of the as-synthesized molecular sieve
prepared in Example 3.
[0018] FIG. 7 is a plot of several DIFFaX-generated simulated XRD
patterns and a powder XRD pattern of the calcined form of the
molecular sieve prepared in Example 3.
[0019] FIG. 8 is a SEM image of the as-synthesized molecular sieve
prepared in Example 4.
[0020] FIG. 9 is a plot of several DIFFaX-generated simulated XRD
patterns and a powder XRD pattern of the calcined form of the
molecular sieve prepared in Example 4.
[0021] FIG. 10 is a SEM image of the as-synthesized molecular sieve
prepared in Example 5.
[0022] FIG. 11 is a plot of several DIFFaX-generated simulated XRD
patterns and a powder XRD pattern of the calcined form of the
molecular sieve prepared in Example 5.
DETAILED DESCRIPTION
[0023] Introduction
[0024] The following terms will be used throughout the
specification and will have the following meanings unless otherwise
indicated.
[0025] The term "framework type" is used in the sense described in
the "Atlas of Zeolite Framework Types," Sixth Revised Edition,
Elsevier, 2007.
[0026] As used herein, the numbering scheme for the Periodic Table
Groups is as disclosed in Chem. Eng. News, 63(5), 26-27 (1985).
[0027] Intergrown molecular sieve phases are disordered planar
intergrowths of molecular sieve frameworks. Reference is directed
to the "Catalog of Disordered Zeolite Structures," 2000 Edition,
published by the Structure Commission of the International Zeolite
Association and to the "Collection of Simulated XRD Powder Patterns
for Zeolites," Fifth Revised Edition, Elsevier, 2007, published on
behalf of the Structure Commission of the International Zeolite
Association for a detailed explanation on intergrown molecular
sieve phases.
[0028] The molecular sieves described herein are disordered planar
intergrowths of end-member structures ERI and LEV. Both of these
two framework types belong to the group that has double 6-rings
(d6r) as secondary building units. Intergrown ERI/LEV molecular
sieves comprise regions of ERI framework type sequences and regions
of LEV framework type sequences. Each change from an ERI to an LEV
framework type sequence results in a stacking fault.
[0029] In preparing molecular sieve SSZ-105, an
N,N-dimethylpiperidinium cation is used as a structure directing
agent ("SDA"), also known as a crystallization template. The SDA
useful for making SSZ-105 has the following structure (1):
##STR00001##
[0030] The SDA cation is associated with anions which may be any
anion that is not detrimental to the formation of SSZ-105.
Representative anions include elements from Group 17 of the
Periodic Table (e.g., fluoride, chloride, bromide and iodide),
hydroxide, sulfate, tetrafluoroboroate, acetate, carboxylate, and
the like.
[0031] Reaction Mixture
[0032] In general, molecular sieve SSZ-105 is prepared by: (a)
preparing a reaction mixture containing (1) at least one source of
silicon oxide; (2) at least one source of aluminum oxide; (3) at
least one source of a Group 1 metal (M), wherein M is selected from
the group consisting of potassium and combinations of sodium and
potassium; (4) hydroxide ions; (5) N,N-dimethylpiperidinium
cations; and (6) water; and (b) subjecting the reaction mixture to
crystallization conditions sufficient to form crystals of the
molecular sieve.
[0033] The composition of the reaction mixture from which the
molecular sieve is formed, in terms of mole ratios, is identified
in Table 1 below:
TABLE-US-00002 TABLE 1 Components Broad Exemplary
SiO.sub.2/Al.sub.2O.sub.3 10 to 100 15 to 80 M/SiO.sub.2 0.05 to
1.00 0.10 to 0.30 Q/SiO.sub.2 0.05 to 0.70 0.20 to 0.45
OH/SiO.sub.2 0.10 to 1.00 0.30 to 0.80 H.sub.2O/SiO.sub.2 10 to 100
15 to 60
wherein compositional variables M and Q are as described herein
above.
[0034] Sources useful herein for silicon oxide include fumed
silica, precipitated silicates, silica hydrogel, silicic acid,
colloidal silica, tetra-alkyl orthosilicates (e.g., tetraethyl
orthosilicate), and silica hydroxides.
[0035] Sources useful herein for aluminum oxide include aluminates,
alumina, and aluminum compounds (e.g., aluminum chloride, aluminum
hydroxide, and aluminum sulfate), kaolin clays, and other zeolites
(e.g., zeolite Y).
[0036] In the present synthesis method, the Group 1 metal (M) is
selected from the group consisting of potassium and combinations of
sodium and potassium. The sodium source may be sodium hydroxide.
The potassium source may be potassium hydroxide. In embodiments
when the Group 1 metal (M) is a mixture of sodium and potassium,
the molar ratio of sodium (m.sub.1) divided by the molar ratio of
potassium (m.sub.2) in the reaction mixture is less than or equal
to 2.0; or less than or equal to 1.0; preferably, in the range from
0.1 to 2.0; and conveniently, in the range from 0.1 to 0.5.
[0037] Optionally, the reaction mixture may also include seeds of a
molecular sieve material, such as SSZ-105 crystals from a previous
synthesis, in an amount of from 0.1 to 10 wt. % or from 0.5 to 5
wt. % of the reaction mixture.
[0038] For each embodiment described herein, the molecular sieve
reaction mixture can be supplied by more than one source. Also, two
or more reaction components can be provided by one source.
[0039] The reaction mixture can be prepared either batch wise or
continuously. Crystal size, morphology and crystallization time of
the molecular sieve described herein can vary with the nature of
the reaction mixture and the crystallization conditions.
[0040] Crystallization and Post-Synthesis Treatment
[0041] Crystallization of the molecular sieve disclosed herein can
be carried out under either static, tumbled or stirred conditions
in a suitable reactor vessel, such as for example polypropylene
jars or Teflon-lined or stainless steel autoclaves, at a
temperature of from 125.degree. C. to 200.degree. C. (e.g., from
140.degree. C. to 180.degree. C.) for a time sufficient for
crystallization to occur at the temperature used, e.g., from 1 day
to 28 days.
[0042] Once the molecular sieve crystals have formed, the solid
product is separated from the reaction mixture by standard
mechanical separation techniques such as centrifugation or
filtration. The crystals are water-washed and then dried to obtain
the as-synthesized molecular sieve crystals. The drying step is
typically performed at a temperature of less than 200.degree.
C.
[0043] As a result of the crystallization process, the recovered
crystalline molecular sieve product contains within its pore
structure at least a portion of the structure directing agent used
in the synthesis.
[0044] The structure directing agent is typically at least
partially removed from the molecular sieve by calcination before
use. Calcination consists essentially of heating the molecular
sieve comprising the structure directing agent at a temperature of
from 200.degree. C. to 800.degree. C. in the presence of an
oxygen-containing gas, optionally in the presence of steam. The
structure directing agent can also be removed by photolysis
techniques as described in U.S. Pat. No. 6,960,327.
[0045] To the extent desired and depending on the composition of
the molecular sieve, any cations in the as-synthesized or calcined
molecular sieve can be replaced in accordance with techniques well
known in the art by ion exchange with other cations. Preferred
replacing cations include metal ions, hydrogen ions, hydrogen
precursor, e.g., ammonium ions and mixtures thereof. Particularly
preferred cations are those which tailor the catalytic activity for
certain organic conversion reactions. These include hydrogen, rare
earth metals and metals of Groups 2 to 15 of the Periodic Table of
the Elements. As used herein, the term "as-synthesized" refers to
the molecular sieve in its form after crystallization, prior to
removal of the SDA cation.
[0046] The molecular sieve disclosed herein can be formulated with
into a catalyst composition by combination with other materials,
such as binders and/or matrix materials, which provide additional
hardness or catalytic activity to the finished catalyst. When
blended with such components, the relative proportions of the
SSZ-105 molecular sieve and matrix may vary widely with the SSZ-105
content ranging from 1 to 99 wt. % (e.g., from 10 to 90 wt. % or
from 20 to 80 wt. %) of the total catalyst.
[0047] Characterization of the Molecular Sieve
[0048] Molecular sieve SSZ-105 is an intergrowth of the ERI and LEV
crystal structures. Physical mixtures of the two phases ERI and LEV
prepared by mixing samples of two pure materials are not defined as
molecular sieve SSZ-105.
[0049] In its as-synthesized and anhydrous form, molecular sieve
SSZ-105 has a chemical composition, in terms of mole ratios, as
described in Table 2:
TABLE-US-00003 TABLE 2 Broad Exemplary SiO.sub.2/Al.sub.2O.sub.3 10
to 50 15 to 40 Q/SiO.sub.2 0.02 to 0.20 0.05 to 0.20 M/SiO.sub.2
0.01 to 0.20 0.02 to 0.15
wherein compositional variables Q and M are as described herein
above.
[0050] It should be noted that the as-synthesized form of the
molecular sieve disclosed herein may have molar ratios different
from the molar ratios of reactants of the reaction mixture used to
prepare the as-synthesized form. This result may occur due to
incomplete incorporation of 100% of the reactants of the reaction
mixture into the crystals formed (from the reaction mixture).
[0051] In its calcined form, molecular sieve SSZ-105 has chemical
composition comprising the following molar relationship:
Al.sub.2O.sub.3: (n)SiO.sub.2
wherein n has a value of at least 10 (e.g., from 10 to 50, from 10
to 45, from 10 to 40, from 10 to 35, from 10 to 30, from 10 to 25,
from 12 to 50, from 12 to 45, from 12 to 40, from 12 to 35, from 12
to 30, from 12 to 25, from 15 to 50, from 15 to 45, from 15 to 40,
from 15 to 35, from 15 to 30, or from 15 to 25).
[0052] In one embodiment, the intergrown crystalline molecular
sieve disclosed herein can have from 1% to 99% (e.g., from 5% to
95%, from 10% to 90%, from 20% to 80%, from 30% to 70%, from 40% to
60%) of the ERI crystal structure. Similarly, the intergrown
molecular sieve disclosed herein can have from 1% to 99% (e.g.,
from 5% to 95%, from 10% to 90%, from 20% to 80%, from 30% to 70%,
or from 40% to 60%) of the LEV crystal structure. The relative
proportions of each of the phases can be analyzed by X-ray
diffraction and, in particular, by comparing the observed patterns
with calculated patterns generated using algorithms to simulate the
effects of stacking disorder. DIFFaX is a computer program based on
a mathematical model for calculating intensities from faults (see
M. M. J. Treacy et al., Proc. R. Soc. Lond. A 1991, 433, 499-520).
DIFFaX is the simulation program selected by and available from the
International Zeolite Association to simulate the powder XRD
patterns for randomly intergrown phases (see "Collection of
Simulated XRD Powder Patterns for Zeolites," Fifth Revised Edition,
Elsevier, 2007).
[0053] The powder X-ray diffraction patterns presented herein were
collected by standard techniques. The radiation was CuK.sub..alpha.
radiation. The peak heights and the positions, as a function of
2.theta. where .theta. is the Bragg angle, were read from the
relative intensities of the peaks (adjusting for background), and
d, the interplanar spacing corresponding to the recorded lines, can
be calculated.
[0054] Minor variations in the diffraction pattern can result from
variations in the mole ratios of the framework species of the
particular sample due to changes in lattice constants. In addition,
sufficiently small crystals will affect the shape and intensity of
peaks, leading to significant peak broadening. Minor variations in
the diffraction pattern can also result from variations in the
organic compound used in the preparation. Calcination can also
cause minor shifts in the XRD pattern. Notwithstanding these minor
perturbations, the basic crystal lattice structure remains
unchanged.
[0055] Processes Using SSZ-105
[0056] Molecular sieve SSZ-105 can be used to dry gases and
liquids; for selective molecular separation based on size and polar
properties; as an ion-exchanger; as a chemical carrier; in gas
chromatography; and as a catalyst in organic conversion reactions.
Examples of suitable catalytic uses include catalytic conversion of
oxygenates to one or more olefins, synthesis of monoalkylamines and
dialkylamines, and catalytic reduction of nitrogen oxides.
EXAMPLES
[0057] The following illustrative examples are intended to be
non-limiting.
Example 1
[0058] 0.80 g of 45% KOH solution, 0.13 g of 50% NaOH solution,
9.56 g of deionized water and 2.00 g of CBV760 Y-zeolite powder
(Zeolyst International, SiO.sub.2/Al.sub.2O.sub.3 mole ratio=60)
were mixed together in a Teflon liner. Then, 8.45 g of 20%
N,N-dimethylpiperidinium hydroxide solution was added to the
mixture. The resulting gel was stirred until it became homogeneous.
The liner was then capped and placed within a Parr steel autoclave
reactor. The autoclave was then placed in an oven and the heated at
150.degree. C. for 4 days. The solid products were recovered by
centrifugation, washed with deionized water and dried at 95.degree.
C.
[0059] The resulting product had a SiO.sub.2/Al.sub.2O.sub.3 mole
ratio of 15.8, as determined by ICP elemental analysis.
[0060] The resulting product was analyzed by powder XRD and SEM.
The powder XRD pattern is shown in FIG. 1. The SEM image is shown
in FIG. 2 and indicates a uniform field of crystals. The list of
the characteristic XRD peaks for this as-synthesized product is
shown in Table 3 below.
TABLE-US-00004 TABLE 3 Characteristic Peaks for As-Synthesized
SSZ-105 Prepared in Example 1 2-Theta.sup.(a) d-Spacing, nm
Relative Intensity.sup.(b) 7.86 1.124 S 11.00 0.804 S 11.76 0.752 W
13.54 0.654 M 15.64 0.566 W 17.49 0.507 S 17.94 0.494 S 20.72 0.428
M 22.10 0.402 VS 23.54 0.378 S .sup.(a).+-.0.35 .sup.(b)The powder
XRD patterns provided are based on a relative intensity scale in
which the strongest line in the powder X-ray diffraction pattern is
assigned a value of 100: W = weak (>0 to .ltoreq.20); M = medium
(>20 to .ltoreq.40); S = strong (>40 to .ltoreq.60); VS =
very strong (>60 to .ltoreq.100).
[0061] A comparison between the experimental powder XRD pattern
collected from the calcined product and DIFFaX simulated powder XRD
patterns with various ERI/LEV intergrowth ratios is shown in FIG.
3. DIFFaX calculation indicates that the product is an intergrowth
material with approximately 50-60% of ERI stacking sequence and
40-50% LEV stacking sequence.
Example 2
[0062] 3.21 g of 45% KOH solution, 0.52 g of 50% NaOH solution,
32.46 g of deionized water and 8.00 g of CBV780 Y-zeolite powder
(Zeolyst International, SiO.sub.2/Al.sub.2O.sub.3 mole ratio=80)
were mixed together in a Teflon liner. Then, 41.05 g of 20%
N,N-dimethylpiperidinium hydroxide solution was added to the
mixture. The resulting gel was stirred until it became homogeneous.
The liner was then capped and placed within a Parr steel autoclave
reactor. The autoclave was then placed in an oven and the heated at
150.degree. C. for 3 days. The solid products were recovered by
centrifugation, washed with deionized water and dried at 95.degree.
C.
[0063] The resulting product had a SiO.sub.2/Al.sub.2O.sub.3 mole
ratio of 17.1, as determined by ICP elemental analysis.
[0064] The resulting product was identified by powder XRD and SEM
as pure SSZ-105. The SEM image is shown in FIG. 4. The list of the
characteristic XRD peaks for this as-synthesized product is shown
in Table 4 below.
TABLE-US-00005 TABLE 4 Characteristic Peaks for As-Synthesized
SSZ-105 Prepared in Example 2 2-Theta.sup.(a) d-Spacing, nm
Relative Intensity.sup.(b) 7.90 1.118 S 11.00 0.804 S 11.73 0.754 W
13.51 0.655 W 15.78 0.561 W 17.48 0.507 S 17.90 0.495 M 20.86 0.425
M 22.28 0.399 VS 23.52 0.378 M .sup.(a).+-.0.35 .sup.(b)The powder
XRD patterns provided are based on a relative intensity scale in
which the strongest line in the powder X-ray diffraction pattern is
assigned a value of 100: W = weak (>0 to .ltoreq.20); M = medium
(>20 to .ltoreq.40); S = strong (>40 to .ltoreq.60); VS =
very strong (>60 to .ltoreq.100).
[0065] A comparison between the experimental powder XRD pattern
collected from the calcined product and DIFFaX simulated powder XRD
patterns with various ERI/LEV intergrowth ratios is shown in FIG.
5. DIFFaX calculation indicates that the product is an intergrowth
material with approximately 50-60% of ERI stacking sequence and
40-50% LEV stacking sequence.
Example 3
[0066] 0.80 g of 45% KOH solution, 0.13 g of 50% NaOH solution,
9.56 g of deionized water and 2.00 g of CBV720 Y-zeolite powder
(Zeolyst International, SiO.sub.2/Al.sub.2O.sub.3 mole ratio=30)
were mixed together in a Teflon liner. Then, 8.45 g of 20%
N,N-dimethylpiperidinium hydroxide solution was added to the
mixture. The resulting gel was stirred until it became homogeneous.
The liner was then capped and placed within a Parr steel autoclave
reactor. The autoclave was then placed in an oven and the heated at
150.degree. C. for 4 days. The solid products were recovered by
centrifugation, washed with deionized water and dried at 95.degree.
C.
[0067] The resulting product had a SiO.sub.2/Al.sub.2O.sub.3 mole
ratio of 12.7, as determined by ICP elemental analysis.
[0068] The resulting product was identified by powder XRD and SEM
as pure SSZ-105. The SEM image is shown in FIG. 6. The list of the
characteristic XRD peaks for this as-synthesized product is shown
in Table 5 below.
TABLE-US-00006 TABLE 5 Characteristic Peaks for As-Synthesized
SSZ-105 Prepared in Example 3 2-Theta.sup.(a) d-Spacing, nm
Relative Intensity.sup.(b) 7.80 1.132 VS 9.80 0.902 M 11.76 0.752 W
13.47 0.657 S 15.56 0.569 M 16.68 0.531 W 17.90 0.495 W 19.36 0.458
S 20.65 0.430 M 21.45 0.414 W .sup.(a).+-.0.35 .sup.(b)The powder
XRD patterns provided are based on a relative intensity scale in
which the strongest line in the powder X-ray diffraction pattern is
assigned a value of 100: W = weak (>0 to .ltoreq.20); M = medium
(>20 to .ltoreq.40); S = strong (>40 to .ltoreq.60); VS =
very strong (>60 to .ltoreq.100).
[0069] A comparison between the experimental powder XRD pattern
collected from the calcined product and DIFFaX simulated powder XRD
patterns with various ERI/LEV intergrowth ratios is shown in FIG.
7. DIFFaX calculation indicates that the product is an intergrowth
material with approximately 80-90% of ERI stacking sequence and
10-20% LEV stacking sequence.
Example 4
[0070] 3.21 g of 45% KOH solution, 32.72 g of deionized water and
8.00 g of CBV760 Y-zeolite powder (Zeolyst International,
SiO.sub.2/Al.sub.2O.sub.3 mole ratio =60) were mixed together in a
Teflon liner. Then, 41.05 g of 20% N,N-dimethylpiperidinium
hydroxide solution was added to the mixture. The resulting gel was
stirred until it became homogeneous. The liner was then capped and
placed within a Parr steel autoclave reactor. The autoclave was
then placed in an oven and the heated at 150.degree. C. for 3 days.
The solid products were recovered by centrifugation, washed with
deionized water and dried at 95.degree. C.
[0071] The resulting product had a SiO.sub.2/Al.sub.2O.sub.3 mole
ratio of 19.7, as determined by ICP elemental analysis.
[0072] The resulting product was analyzed by powder XRD and SEM. It
was identified as pure SSZ-105 molecular sieve. The SEM image is
shown in FIG. 8. The list of the characteristic XRD peaks for this
as-synthesized product is shown in Table 6 below.
TABLE-US-00007 TABLE 6 Characteristic Peaks for As-Synthesized
SSZ-105 Prepared in Example 4. 2-Theta.sup.(a) d-Spacing, nm
Relative Intensity.sup.(b) 7.84 1.126 W 8.62 1.025 W 10.92 0.809 S
11.73 0.754 W 13.55 0.653 S 15.69 0.564 W 17.56 0.505 VS 17.92
0.495 S 21.06 0.421 M 22.28 0.399 VS .sup.(a).+-.0.35 .sup.(b)The
powder XRD patterns provided are based on a relative intensity
scale in which the strongest line in the powder X-ray diffraction
pattern is assigned a value of 100: W = weak (>0 to .ltoreq.20);
M = medium (>20 to .ltoreq.40); S = strong (>40 to
.ltoreq.60); VS = very strong (>60 to .ltoreq.100).
[0073] A comparison between the experimental powder XRD pattern
collected from the calcined product and DIFFaX simulated powder XRD
patterns with various ERI/LEV intergrowth ratios is shown in FIG.
9. DIFFaX calculation indicates that the product is an intergrowth
material with approximately 20-30% of ERI stacking sequence and
70-80% LEV stacking sequence.
Example 5
[0074] 0.80 g of 45% KOH solution, 8.18 g of deionized water and
2.00 g of CBV780 Y-zeolite powder (Zeolyst International,
SiO.sub.2/Al.sub.2O.sub.3 mole ratio=80) were mixed together in a
Teflon liner. Then, 10.26 g of 20% N,N-dimethylpiperidinium
hydroxide solution was added to the mixture. The resulting gel was
stirred until it became homogeneous. The liner was then capped and
placed within a Parr steel autoclave reactor. The autoclave was
then placed in an oven and the heated at 150.degree. C. for 4 days.
The solid products were recovered by centrifugation, washed with
deionized water and dried at 95.degree. C.
[0075] The resulting product had a SiO.sub.2/Al.sub.2O.sub.3 mole
ratio of 21.6, as determined by ICP elemental analysis.
[0076] The resulting product was analyzed by powder XRD and SEM and
indicated that the product was pure SSZ-105 molecular sieve. The
SEM image is shown in FIG. 10. The list of the characteristic XRD
peaks for this as-synthesized product is shown in Table 7
below.
TABLE-US-00008 TABLE 7 Characteristic Peaks for As-Synthesized
SSZ-105 Prepared in Example 5 2-Theta.sup.(a) d-Spacing, nm
Relative Intensity.sup.(b) 7.95 1.111 W 8.63 1.024 W 10.97 0.806 M
11.62 0.761 W 13.54 0.654 M 16.00 0.554 W 17.46 0.507 VS 17.88
0.496 M 21.06 0.421 S 22.22 0.400 VS .sup.(a).+-.0.35 .sup.(b)The
powder XRD patterns provided are based on a relative intensity
scale in which the strongest line in the powder X-ray diffraction
pattern is assigned a value of 100: W = weak (>0 to .ltoreq.20);
M = medium (>20 to .ltoreq.40); S = strong (>40 to
.ltoreq.60); VS = very strong (>60 to .ltoreq.100).
[0077] A comparison between the experimental powder XRD pattern
collected from the calcined product and DIFFaX simulated powder XRD
patterns with various ERI/LEV intergrowth ratios is shown in FIG.
11. DIFFaX calculation indicates that the product is an intergrowth
material with approximately 10-20% of ERI stacking sequence and
80-90% LEV stacking sequence.
Example 6
Calcination of SSZ-105
[0078] The as-synthesized molecular sieve products were calcined
inside a muffle furnace under a flow of air heated to 540.degree.
C. at a rate of 1.degree. C./minute and held at 540.degree. C. for
5 hours, cooled and then analyzed by powder XRD.
[0079] FIG. 3, FIG. 5, FIG. 7, FIG. 9 and FIG. 11 show the XRD
patterns of calcined SSZ-105 molecular sieve products 1, 2, 3, 4
and 5, respectively, and indicate that the material remains stable
after calcination to remove the organic SDA.
Example 7
Micropore Volume Analysis
[0080] The calcined material from Example 6 was treated with 10 mL
(per g of molecular sieve) of a 1N ammonium nitrate solution at
90.degree. C. for 2 hours. The solution was cooled, decanted off
and same process repeated.
[0081] The ammonium-exchanged molecular sieve product
(NH.sub.4-SSZ-105) was subjected to a micropore volume analysis
using N.sub.2 as adsorbate and via the BET method. The molecular
sieve exhibited a micropore volume of 0.25 cm.sup.3/g and indicates
that SSZ-105 has microporous character.
[0082] As used herein, the term "comprising" means including
elements or steps that are identified following that term, but any
such elements or steps are not exhaustive, and an embodiment can
include other elements or steps.
[0083] Unless otherwise specified, the recitation of a genus of
elements, materials or other components, from which an individual
component or mixture of components can be selected, is intended to
include all possible sub-generic combinations of the listed
components and mixtures thereof.
[0084] All documents cited in this application are herein
incorporated by reference in their entirety to the extent such
disclosure is not inconsistent with this text.
* * * * *