Note: Descriptions are shown in the official language in which they were submitted.
F-4826
-.: :.
SYNTHETIC POROUS CRYSTALLINE MATERIAL MCM-35, - `~
rrs SYNTHESIS AND USE `~
.. ~ ~,....
This invention relates to a synthetic porous crystalline
material, designated MoM-35, to a method for its synthesis and to
its use in catalytic conversion of organic compounds.
Zeolitic materials, both natural and synthetic, have been -~
demonstrated in the past to have catalytic properties for various
types of hydrocarbon conversion. Certain zeolitic materials are -
ordered, porous crystalline aluminosilicates having a definite
crystalline structure as deter~ined by X-ray diffraction, within ~ `~
which there are a large number of cavities which may be `
interconnected by channels or pores. These cavities and pores are
uniform in size within a specific zeolitic material. Since 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 ways to take advantage of
these properties.
Such molecular sieves, both natural and synthetic, include
a wide variety of positive ion-containing crystalline
aluminosilicates. These aluminosilicates can be described as a
rigid three-dimensional framework of SiO4 and M 04 in which the
tetrahedra are cross-linked by the sharing of oxygen atoms whereby
the ratio of the total aluminum and silicon atoms to oxygen atoms is
1:2. The electrovalence of the tetrahedra containing aluminum is
balanced by the inclusion in the crystal of a cation, for example an
aIkali metal or an alkaline earth metal cation. This can be
expressed wherein the ratio of aluminum to the number of various
cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One
type of cation may be exchanged either entirely or partially with
another type of cation utilizing ion exchange techniques in a
conventional manner. By means of such cation exchange, it has been
~ .
.
.~
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F-4826 --2
possible to vary the properties of a given aluminosilicate by
suitable selection of the cation. The spaces between the tetrahedra -~
are occupied by molecules of water prior to dehydration.
Prior art techniques have resulted in the formation of a ~ -
great variety of synthetic zeolites. The zeolites have come to be ~ -~
designated by letter or other convenient symbols, as illustrated by
zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent -
2,882,244), zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S.
Patent 3,247,195), zeolite ZK-4 (U.S. Patent 3,314,752), zeolite -~
ZSM-5 (U.S. Patent 3,702,886), zeolite ZSM-ll (U.S. Patent - ` -
3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 ~ -(U.S. Patent 3,972,983), ZSM-35 (U.S. Patent 4,016,245), and zeolite
ZSM-23 (U.S. Patent 4,076,842).
The SiO2/A1203 ratio of a given zeolite is often
variable. For example, zeolite X can be synthesized with ~ ~`
SiO2/A1203 ratios of from 2 to 3; zeolite Y, from 3 to 6. In
some zeolites, the upper limit of the SiO2/A1203 ratio is
unbounded. ZSM-5 is one such example wherein the SiO2/A1203
ratio is greater than 5 and up to infinity. U.S. Patent 3,941,871
(Re. 29,948) discloses a porous crystalline silicate made from a
reaction mixture containing no deliberately added alumina in the
starting mixture and exhibiting the X-ray diffraction pattern
characteristic of ZSM-5. U.S. Patents 4,061,724; 4,073,865 and
4,104,294 describe crystalline silicates or organosilicates of
varying alumina and metal content.
In one aspect the present invention resides in a synthetic
porous crystalline material designated '~CM-35", having an X-ray
diffraction pattern including values set forth in Table 1 of the -
specification.
In a further aspect, the invention resides in a method for
synthesizing the material of said one aspect comprising preparing a
reaction mixture containing sources of alkali metal cations (M), a
trivalent element (X) oxide9 a tetravalent element (Y) oxide,
hexamethyleneimine ~R) and water, said trivalent element being
selected from aluminum, boron, iron and gallium, said tetravalent
.
6 ~:
F-4826 --3--
~ ': '.,:.';
element being selected from silicon and germanium, and said reaction
mixture having a composition in terms of mole ratios within the
following ranges:
Y02/X203 =30 to 200 -~
H20/Y02 =10 to 100
OH /Y02 =0.01 to 0.2
~Y2 =0.01 to 1.0
R/Y02 =O.1 to 1.0
and maintaining said reaction mixture under sufficient
crystallization conditions until crystals of said material are
formed. -
The synthetic crystalline material MCM-35 has an X-ray
diffraction pattern which is distinguished from that of other
crystalline materials by the presence of the following lines:
TABLE 1
Interplanar
d-Spacing (A) Relative Intensit~L_I/Io
15.4 ~ 0.4 w-s
9.06 + 0.20 w-s
4.99 + 0.15 w-ms
2.00 + 0.10 w-ms
These X-ray diffraction data and those of the following
specific examples were collected with a Philips diffraction system,
equipped with a graphite diffracted beam monochromator and
25scintillation counter, using copper K-alpha radiation. The
diffraction data were recorded by step-scanning at 0.04 degrees of
two-theta, where theta is the Bragg angle, and a counting time of 4
seconds for each step. The interplanar spacings, d's, were ~ -~
calculated in Angstrom units (A), and the relative intensities of
30the lines, I/Io, where Io is one-hundredth of the intensity of
the strongest line, above backgound, were derived with the use of a
profile fitting routine (or second derivative algorithm). The
intensities are uncorrected for Lorentz and polarization effects. ~
The relative intensities are given in terms of the symbols vw = very -;
,~.''`
- . ",
.
' ' ' ~ ,
,~
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F-482~ 4 _
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weak (0-5), w = weak (5-10), mw - medium weak (10-20), m = medium
(20-40), ms = medium strong (40-60), s = strong (60-80) and vs = ~ ;
very strong (80-100). It should be understood that diffraction data
listed as single lines may consist of multiple overlapping lines
which under certain conditions, such as differences in crystallite `~`
size or very high experimental resolution or crystallographic
changes, may appear as resolved or partially resolved multiplets.
Typically, crystallographic changes can include minor changes in
unit cell parameters and/or a change in crystal symmetry, without a
change in topology of the structure. These minor effects, including
changes in relative intensities, can also occur as a result of
differences in cation content, framework composition, nature and
degree of pore filling, and thermal and/or hydrothermal history.
Since MoM-35 may have a plate-like morphology, experimental
or measured intensity distortions due to preferred orientation are
possible. This was taken into account in the above analysis and is
reflected in Table 1.
The crystalline material of this invention has a
composition involving the molar relationship:
X203:(n)Y0~
wherein X is a trivalent element, such as aluminum~ boron, "
iron and/or gallium, preferably aluminum, Y is a tetravalent element
such as silicon and/or germanium, preferably silicon, and n is at
least 30, usually from 40 to 200, more usually from 60 to 150. In
the as-synthesized form, the material has a formula, on an anhydrous
basis and in terms of moles of oxides per n moles of Y02, as ~ `
follows:
(0.1 - 0.8)M20(0.5 - 4)R20:X203:nY0
wherein R is an organic and M is alkali metal.
The M and R components are associated with the material as
a result of their presence during crystallization, and are easily ~ -~
removed by conventional post-crystallization methods. Thus, the
organic component can be removed by calcination, whereas the alkali
metal cations M can be replaced, at least in part, by ion exchange -~
. . , . - ~ -
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~: : . , - , ~ ,
,. : :.: :,: , , , : ~
~ ~ . . . ~; : :
2~ s6
F-4826 --5--
with other cations. Preferred replacing cations include metal ions,
hydrogen ions, hydrogen precursor, e.g., ammonium, ions and mixtures
thereof. Particularly preferred cations are t~ose which render the
material catalytically active, especially for certain hydrocarbon
conversion reactions. These include hydrogen~ rare earth metals and
metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the
Periodic Table of the Elements. A typical ion exchange technique
would be to contact the synthetic material with a salt of the
desired replacing cation or cations. Examples of such salts include
the halides, e.g., chlorides, nitrates and sulfates.
MCM-35, 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 200 to 595C in an inert atmosphere,
such as air or nitrogen 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 material in a vacuum, but a longer time is required to
obtain a sufficient amount of dehydration.
The crystalline material of the invention can be prepared
rom a reaction mixture containing sources of alkali metal cation,
an oxide of the trivalent element X, e.g., aluminum, an oxide of the -~
tetravalent element Y, e.g. silicon, an organic (R~ directing agent
in the form of hexamethyleneimine, and water, said reaction mixture
having a composition~ in terms of mole ratios of oxides, within the
following ranges:
Reactants Useful Preferred
YO2/X2O3 30 to 200 50 to 150
H2O/YO2 10 to 100 15 to 40
OH /YO2 0.01 to 0.20 0.02 to less than 0.10
M/YO2 0.01 to 1.0 0.05 to 0.3
R/YO2 0.1 to 1.0 0.1 to 0.5
:
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F-4826 --6--
In the above mixture, it is important to operate at low
OH /Y02 values when the Y02~X203 is low since otherwise ` `
significant quantities of crystalline phases other than MCM-35 are
produced.
Crystallization of MCM-35 can be carried out at either
static or stirred conditions in a suitable reactor vessel, such as
for example, polypropylene jars or teflon lined or stainless steel
autoclaves. Crystallizaticn is generally conducted at 80C to 250C
for 24 hours to 20 days. Thereafter, the crystals are separated
from the liquid and recovered.
Where Y02 is silica, the silica source preferably
contains at least 30 wt.% solid silica, e.g. Ultrasil (a
precipitated, spray dried silica containing 90 wt.% silica) or HiSi~
(a precipitated hydrated SiO2 containing 87 wt.% silica, 6 wt.
free H2O and 4.5 wt.% bound H20 of hydration and having a
particle size of 0.02 micron). Preferably the silica source
contains at least 80 wt.% solid silica, and more preferably at least
85 wt.% solid silica.
Synthesis of the MCM-35 is facilitated by the presence of
at least 0.01 percent, preferably 0.10 percent and still more
preferably 1 percent, seed crystals (based on total weight) of
crystalline product.
MCM-35 can be used as a catalyst in intimate combination
with a hydrogenating component such as tungsten, vanadium,
molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble
metal such as platinum or palladium where a hydrogenation- `
dehydrogenation function is to be performed. Such component can be
exchanged into the composition, e.g. to the extent aluminum is in
the structure, impregnated therein or intimately physically admixed `~
therewith. Such component can be impregnated in or on to it such
as, for example in the case of platinum, by treating the crystalline
material with a solution containing a platinum metal containing
ion. Thus~ suitable platinum compounds include chloroplatinic acid,
platinous chloride and various compounds containing the platinum ~ -~
amine complex.
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-
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. - . .
F-4826 --7--
In general, organic compounds such as, for example,
hydrocarbcns can be converted to conversion products such as, for
example, lower molecular weight hydrocarbons, over a catalyst
comprising the crystalline material of the invention by contact
under organic compound conversion conditions including a temperature
of from 100C to 800C, a pressure of lO to lO000 kPa (0.1 to lO0
atmospheres), a weight hourly space velocity of 0.08 to 20 hr
and a hydrogen/feedstock organic, e.g. hydrocarbon, compound mole
ratio of 0 tno added hydrogen) to 100.
Such conversion processes include, as ncn-limiting
examples, cracking hydrocarbons to lower molecular weight
hydrocarbons with reaction conditions including a temperature of
300C to 800C, a pressure of 10 to 3500 kPa (0.1 to 35 atmospheres)
and a weight hourly space velocity of 0.1 to 20; and dehydrogenating
hydrocarbon compounds with reaction conditions including a
temperature of 300C to 700C, a pressure of 10 to 1000 kPa (0.1 to
10 atmospheres) and a weight hourly space velocity of 0.1 to 20.
As in the case of many catalysts, it may be desirable to
incorporate MoM-3S with another material 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. Use of a material in conjunction with MCM-35,
i.e. combined there~ith, 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 economically 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. Said materials, i.e. clays,
oxides, etc., function as binders for the catalyst. It is desirable
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20~fi~ ~6
.
F-4826 ~-8--
to provide a catalyst having good crush strength because in
commercial use it is desirable to prevent the catalyst from breaking
down into powder-like materials. These clay binders have been
employed normally only for the purpose of improving the crush
strength of the catalyst.
Na~urally occurring clays which can be composited with the ~ ~
new crystal 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, `
or anauxite. Such clays can be used in the raw state as originally
mined or initially subjected to calcination, acid treatment or
chemical modification. Binders useful for compositing with the
present crystal also include inorganic oxides, notably alumina.
In addition to the foregoing materials, the new crystal can
be composited with a porous matrix material such as silica-aluminà,
silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,
silica-titania as well as ternary compositions such as silica-
alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and
silica-magnesia-zirconia.
The relative proportions of MCM-35 ~nd inorganic oxide
matrix vary widely, with the MoM-35 ranging from 1 to 90 percent by ;
weight and more usually, particularly when the composite is prepared
in the form of beads, in the range of 2 to 80 weight percent of the `
composite
In order to more fully illustrate the nature of the -
invention and the manner of practicing same~ the following examples
are presented. In the examples all percentages are by weight, and
whenever sorption data are set forth for comparison of sorptive
capacities for cyclohexane, water and/or hexane, they were
determined as follows~
A weighed sample of the calcined adsorbant was contacted
with the desired pure adsorbate vapor in an adsorption chamber,
evacuated to less than 1 mm and contacted with 40 mm Hg of of
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F-4826 ~-9--
n-hexane or cyclohexane vapor, pressures less than the vapor-liquid
equilibriwn pressure of the respective adsorbate at 90~C. The
pressure was kept constant (within ~ 0.5 mm) by addition of
adsorbate vapor controlled by a manostat during the adsorption
period, which did not exceed 8 hours. As adsorbate was adsorbed by
the absorbant, the decrease in pressure caused the manostat to open ~ ~
a valve which admitted more adsorbate vapor to the chamber to ~;
restore the above control pressures. Sorption was complete when the ;
pressure change was not sufficient to activate the monastat. The
increase in weight was calculated as the adsorption capacity of the - -
sample in g/100 g of calcined adsorbant.
When Alpha Value is examined, it is noted that the Alpha
Value is an approximate indication of the catalytic cracking
activity of the catalyst compared to a standard catalyst and it
gives the relative rate constant trate of normal hexane conversion
per volume of catalyst per unit time). It is based on the activity
of the highly active silica-alumina cracking catalyst taken as an
Alpha of 1 (Rate Constant = 0.016 sec 1). The Alpha Test is
described in U.S. Patent 3,354,078 and in The Journal of Catalysis, ~ ~"
Vol. IV, pp. 522-529 (August 1965).
Example 1
A 30g quantity of A12(S04)3.xH20 was dissolved in a
solution containing 56.8 g of 45% KOH and 1235 g of water. A 236 g
quantity o a precipitated, spray dried silica containing 90% silica
(i.e. Ultrasil) was added to the solution and the total was mixed
thoroughly. Finally, 105g of hexamethyleneimine was added t3 the
mixture with thorough agitation. The resulting reaction mixture had
the following composition, in mole ratios:
Si2/A1203 = 70.0
H20/SiO2 = 19.9
OH /S i02 = 0.043
K/Si02 = 0.13
R/SiO2 = 30
wherein R is hexamethyleneimine.
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Z~6~6
F-4826 --10--
This mixture was then crysta'Llized in a stirred reactor at
175C for 3 days. The product crysta:ls were recovered by
filtration, washed with water and then dried at 120C. A portion of .
the dried product was submitted for X ray and chemical analysis.
X-ray analysis identified the product crystals as the new
crystalline ~aterial of this invention, with the X-ray powder ~ ~ .
diffraction pattern including the lines presented in Table 2.
: ,,
TABI,E 2 `
X-RAY DIFFRACTION PATTERN OF THE DRIED PRODUCT OF ~XAMPLE 1
Observed Relative
2 Theta d (A) Intensity ~ ~.
5.78 15.29 11
9.74 9.08 17
11.53 7.68 1 ` . ;
13.39 6.61 6 :
15.38 5.76 9
16.72 5.30
17.32 5.12 6 `:
17.81 4.98 19
18.73 4.74
19.58 4 53 2 ": -
21.25 4 18 53
22.01 4.04 39*
22.31 3.98 40
22.74 3.91 76 :
24.31 3.66 4 ~ ~
25.04 3.56 13 ":
25.59 3.48 100 -;
25.99 3.43 30 : :-
26.54 3.36 13** -.
26.97 3.31 25 : ~:
27.86 3.20 6
28.13 3.17 15
29.02 3.08 3 : :
29.57 3.03 13
30.21 2 958 11
31.31 2 856 6 ~
31.68 2.824 11 -
32.48 2.756 3
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F-4826 --11-- ~
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TABLE 2 tcont'd)
2bThetaed d (A~ Relatire
33.00 2,714 4
33.40 2,682 5 ` ::~
34.45 2,603 3
34.93 2 568 2
35,71 2 514 2
36.80 2,442 4
37.07 2.425 6 : :` :-
37.34 2.408 8
37.87 2.376 5
38,30 2.250 5 ` ` '
39,26 2.294 3
39,89 2,260 3
40.49 2 228 3
41.14 2 194 3
41.95 2.154 4
42,60 2.122 2 ;
43,46 2,082 5
43,94 2,061 3
45,23 2.005 21*
46,30 1.961 5
46,95 1,935 11
48,60 1.873 6
50.10 1.821 5
51.02 1,7gO S
51,72 1 768 5
52,46 1 744 4
53.00 1 728 7
53.87 1 702 5
55.43 1.658 4 `
57.24 1.609 4
58.16 1.586 5
59.22 1.560 4 `
In Table 2, * indicates that a shoulder appears on the low
2 Theta side of the peak, and ** indicates that a shoulder appears
on the high 2 Theta side of the peak. There was an indication of a ;
very small amount of impurity in this sample.
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2~,856
F-4826 --12-- .
The chemical composition of the product of Example 1 was as
follows, in weight percent: . : :
N 0.93
K 0,49
A1203 2.4
Si0~ 86.0 -:
Ash 94.9 ~ ~-
Si02/A1203, molar 60.9
A portion of the crystalline product of this example was
calcined at 538C for 6 hours in air and submitted for sorption and ~: ;
X-ray analysis. The X-ray powder diffraction pattern of the : --
calcined material included the lines presented in Table 3. ~-
TABLE 3
:
X-RAY DIFF CTION PATTERN OF THE DRIED PRODUCT OF EXAMPLE 1 :;~ .
Observed Relative ~:`
2 Theta d (A) Intensity
5.75 15.36 22
9'79 9 03 31 ::~
11.48 7 71 3 ~.:
12.09 7.32 3 : :
12.75 6.94 2
13.37 6.62 12*
15.40 5.75 2
17.37 5.11 3
17.79 4.99 16
. 18.73 4.74 2 : :
19.56 4.54
21,26 4.18 52
22.02 4.04 41*
22.32 3.98 32 :~
22.79 3.90 66
24.35 3.66 4
25.04 3 56 47 `
25.54 3 49 100
. ~::,:
2~ 6
F-4826 --13--
TABLE 3 tcont'd)
X-RAY DIFPRACTION PATTERN OF THE DRIED PRODUCT OF EXAMPLE 1
Observed Relative
2 Theta d (A) Intensity
26,01 3.43 30
26.54 3,35 ~2
26.95 3.31 23**
27.84 3.20 6 ~-~'
28.18 3.17 16
29.53 3.03 11
30.13 2.966 11
31.36 2.852 8
31.73 2.820 12
32.50 2.755 3
32.98 2.716 4
33.45 2.679 5
33.84 2.649 2
34.49 2.600 2
34.96 2.568 2
35.71 2.514
36.80 2.442 4
37.29 2.411 8
37.94 2.372 4
38.36 2 346 3
39.27 2 294 2
39.93 2.258 2
40.53 2,226 3
41.18 2 192 3
42.01 2 151 3
42.74 2 116
43,53 2 079 4
43.83 2.066 3 -:~
45.24 2.004 19*
46.~8 1.962 4
46.95 1.935 10
48.65 1.872 4
50.19 1.818 5
51.06 1.786 4 ::
51.65 1 770 6
52.48 1 744 4
53O03 1.727 6
53.91 1.701 6
55.52 1.655 4
57.36 1.606 5 :
58.29 1 583 5 -- .
59.33 1 558 4
.:
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F-4826 --14--
:' ~
In Table 3, * indicates that a shoulder appears on the low
2 Theta side of the peak and ** indicates that a shoulder appears on ~ -
the high 2 Theta side of the peak. There was one unresolved peak
between d-spacings of 2.442 and 2.411 Angstroms, and the minor ~ ;
amount of impurity remained. ~
The sorption data obtained on the calcined product of this ;
example as follows, in weight percent:
Cyclohexane 2.0
n-Hexane 2.2
Water 4.8
A portion of the calcined product was ammonium exchanged
and calcined at 538C for 3 hours to prepare the hydrogen fonm. It
was then tested for catalytic activity by the Alpha test and found
to have an Alpha Value of 25.
Example 2-6
Table 4 presents details of additional examples, including
reaction mixture compositions, crystallization conditions, product
compositions and sorption test results of calcined ~6 hours at
538C) products. Alumina l~as provided by A12(S04)3 xH20 and
silica was prvvided by Ultrasil in each example. Alkali metal was '',"!,
potassium in Examples 2, 4 and 6 and sodium in Examples 3 and 5. In
Examples 3, 4 and 5 the product was substantially 100% the
crystalline silicate of the present invention by X-ray analysisO
The Example 2 product was found to contain trace amounts of
cristobalite in addition to the material of the present invention
whereas the Example 6 product contained trace amounts of ZSM-5.
The X-ray diffraction patterns for the as-synthesized and
calcined products of Example 2 included the values shown in Tables 5 ~ `
and 6, respectively.
~ 35
F-4826 --15--
TABLE 4
.. ; .
Example No. 2 3 4 5 6
_
Synthesis Mixture, mole ratios
Si02/A1203 140 120 100 70.1 50.1
H20/Si02 20.0 17.9 20.0 19.7 20.0
OH /Si02 0.03 0.03 0.04 0.04 0.05
M/Si02 0.05 0.08 0.10 0.13 0.17
R/Si02 0.30 0.20 0.30 0.30 0.30
Crystallization, Stirred
Temp, C/Days 175/3 160/19 175/3 175/3 175
Product Composition, Wt.%
Si02 86.7 88.7 89.5 83.8 85.5
A1203 1.2 1.4 1.8 2.3 3.5
K 0.37 -- 0.30 -- 0.76
Na -- 0.16 -- 0.18 --
N 0.88 0.96 0.92 1.21 0.95
Ash 88.7 91.0 91.6 86.8 93.9
Si02/A1203, molar 123 108 84.5 62.0 41.5
Adsorption, Wt.%
Cyclohexane 1.7 3.4 2.2 2.1 3.4
n-Hexane 4.6 4.7 3.0 3.2 3.8
Water 3.5 3.2 3.2 4.9 6.1
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F-4826 --16--
TABLE 5
:
X-RAY DIFFRACI ION PAl~RN OF AS-SYNT}I~SIZED EX~MPLE 2 PRODVCT -: `
. _ - - - : .::
Observed Relati
2 Thetad (A) IntensitY
5.7015.50 23
9~739.09 23
11.47 7.71 1
13.38 6.62 7
15.30 5.79 10
16.65 5.33
17.32 5.12 7
17.76 4.99 21
18.65 4.76
lg .49 4.55 2
21.17 4.20 60
21.94 4.05 45
22.24 4.00 32
22,74 3.91 71
24.26 3.67 2
24,95 3.57 44
25.52 3.49 100
25.95 3.43 25
26,48 3,37 12
26.90 3. 32 20
27.69 3.22 6
28.06 3. 18 ~4
28.94 3.08 3
29.48 3.031 11
30.15 2.964 9
32.95 2.718 3
31.24 2.863 5
31.61 2.831 10
32.28 2.765 2
33.38 2.684 5
34.46 2.610 2
34.89 2.572
35.93 2.500 3
36.70 2.449 4
37.27 2.413 7
37.86 2. 376 4
38.2:1 1.356 2
39.82 2.264 2
40.43 2.231 2
41.12 2.195 2
41.8~ 2.157 4
43.37 2.086 4
45.15 2.000 20
46.24 1.963 4
46.91 1.937 10
48.53 1.876 4
50.03 1.821 4
50.9~ 1.792 3
.:
F-4826 --17--
TABLE 5 (cont'd)
Observed Relative
2 Theta d (A) Intensity
52.41 1.746 4
52,96 1.729 6
53.85 1.703 5
55.39 1.659 4
57.28 1.608 5
58.13 1.587 5
59.22 1.560 4
TABLE 6
X-RAY DIFFRACrION PATTERN OF CALCINED EXAMPLE 2 PRODUCT ~;
Observed Relative
2 Theta d (A) Inten3S6itY-
9-77 9.05 40
11.44 7.73 4
12,08 7,33 4
12,69 6,98 4
13,40 6,61 17
15,33 5,78 25
17,25 5,14 3
17,78 4,99 16
18,70 4.75 2
19,54 4,10 1
21,23 4,18 60
21,75 4.09 21
21~99 4~04 43
22,32 3,98 32
22,77 3,91 61
24,31 3.66 2
24.99 3.56 45
25,58 3.48 100
25.96 3.43 24
26.51 3.36 12
26.98 3.31 25
27.73 3.22 7
28.11 3.17 16
28.99 3.08 2
29.55 3,02 13
30,09 2.969 9
31,26 2,861 7
31,66 2.826 13
32,51 2,754 4
32,99 2.715 4
36~56
,~
F-4826 --18
. :. -
_ABLE 6 tcont'd)
Obserred Relative
2 Theta d (A) Intens4ity ; ;
33.81 2.651 2
34.46 2.603 2 -
34.97 2.566 2
35.99 2.496 4
36.80 2.442 4
37.12 2.422 6
37.35 2.407 8
37.86 2.376 4 -
3~.34 2.348 3
39.26 2.294 2 ~
39.87 2.261 2 ~: -
40.50 2.227 3
41.03 2.200 2
42.01 2.150 3
43,66 2.073 4 ~ .
45.25 2.004 19
46.33 1.960 4
~6.98 1.934 9
48.63 1.872 5
50.13 1.820 4
51.10 1.787 4
51.75 1.767 5
52.~5 1.726 6
53.92 1.700 5
55.48 1.656 4
57.37 1.606 5
58.21 1.585 6
59.33 1.558 4
In Table 5, the * indicates that a shoulder appears on the
low Theta side of the peak. In the X-ray pattern of the
as-synthesized Example 2 product, there were unresolved peaks
between d-spacings of 2.572 and 2.500 Angstroms and between 2.449
and 2.413 Angstroms. In the X-ray patterns of the calcined EXample
2 product, there was an unresolved peak between d-spacings of 2.073 -~
and 2.004 Angstroms. -~
Portions of the calcined products of Examples 2, 5 and 6 ;~
were ammonium exchanged and then calcined at 538C for three hours
to generate the hydrogen form. The resultant products gave alpha
values of 2 (EXample 2), 38 (Example 5) and 67 (Example 6). ~ ~ :
. ~ .- .
:: : ,-..
,.'
-: :: . : -: ':.' :: :
.. , ~ , ... : .
' ' :: -:.- ~ .:
