Note: Descriptions are shown in the official language in which they were submitted.
^ 1 1336il7
PROCESS FOR THE PRODUC$ION OF ~MT~-S.
HYDROXYAMT~-~ AND AZIRIDINES
Field of the Invention
This invention relates to a process for the
production of amines, hydroxyamines and aziridines.
More specifically, this invention relates to a process
for converting an alkanolamine to one or more cyclic or
acyclic alkylamines, alkanolamines and aziridines by
contacting the alkanolamine with one of a selected group
of molecular sieves. By a proper choice of catalysts
and/or reaction conditions, the process of the invention
can be varied to alter its selectivity to a number of
differing and useful products, including ethylenimine.
Background of the Invention
Ethylenimine is a potential chemical
intermediate for the production of linear ethyleneamine
polymers and for the production of various other amines.
However, because of the toxicity and carcinogenicity of
ethylenimine, this material poses severe handling
difficulties, which make it highly undesirable to store
or transport the et~ylenimine, so that desirably a
process for the production of ethylenimine should begin
from in~Yp n-sive starting materials, and should provide
the ethylenimine in a form which permits its direct feed
to the ethylenea,nine production unit with~ut intervening
isolation or storage of the ethylenimine.
Various processes for the production of
ethylenimine are known. For example, ethylenimine may
D-14643
-2- 13367I7
be produced by the reaction of ethylene dichloride with
anhydrous ammonia. However, this method suffers from
the disadvantages of involving halide use and producing
a salt by-product.
One commercially attractive process for the
production of ethylenimine is the catalytic
dehydration/deamination of monoethanolamine.
Monoethanolamine is-known to convert to a mixture of
various alkanolamines, alkylamines and aziridines when
contacted with various heterogeneous catalysts. Similar
mixtures are obtained from other alkanolamines using the
same catalysts. However, typically such reactions
produce a complex mixture of products.
Most of the known catalysts for these
dehydration/deamination reactions of alkanolamines are
oxides of tungsten, tantalum or niobium, in some cases
promoted with transition metals such as iron or
chromium, the metal oxides usually being disposed upon a
support, for example silica or alumina.
For example, U.S. Patent No. 4,289,656, issued
September 15, 1981, and U.S. Patent No. 4,358,405, both
to Hayes et al., describe a dehydration catalyst and
process for making an alkylenaziridine (such as
ethylenimine) from an alkanolamine (such as
monoethanolamine); the catalyst contains oxides of
either tantalum or niobium together with the oxides of
D-14643
1336717
iron and chromium, in which the ratios of the metals
are: ~
10Fe0.5-2.9CrO.3-1.7
wherein M is tantalum or niobium.
U.S. Patent No. 4,301,036, issued November 17,
1981 to Childress et al., describes a dehydration
catalyst for the dehydration of alkanolamines to
alkylenaziridines. This dehydration catalyst is
prepared by applying a solution of a tungsten salt on to
a low surface area support (usually silicon carbide),
calcining the salt to tungsten oxide, and thereafter
applying silica to the tungsten-coated support so as to
form a coating of silica over the tungsten.
U.S. Patent No. 4,337,175, issued June 29,
1982 to Ramirez, describes a dehydration catalyst for
the dehydration of alkanolamines to alkylenaziridines.
This dehydration catalyst consists essentially of an
oxide of tantalum or niobium with an alkaline earth
metal oxide as a promoter on an inert support, for
example a low surface area, high purity alumina.
Other catalysts have been used for the
production and conversion of monoalkanolamines. For
example, U.S. Patent No. 4,524,143, issued June 18, 1985
to Vanderpool, describes a process for the production of
linear polyethylenepolyamines from ethylenediamine and
monoethanolamine using thermally activated pelleted
D-14643
- 1336717
-4-
catalyst compositions comprising zirconium silicate
having phosphorus deposited t~hereon.
The relatively complex mixtures produced by
these prior art processes pose obvious problems of
s separation. In addition, the relative proportions in
which the various products are produced are rarely
optimal with regard to the commercial demand for, and
selling prices of, the various products, and thus it
would be highly advantageous to be able to vary the
product distribution to increase the proportions of the
more valuable products produced.
Because of ~heir microporous structure, with
pores of uniform size, molecular sieves offer the
possibility of modifying the product distribution
obtained in the aforementioned dehydration/deamination
reactions of alkanolamines. However, the present
inventors are aware of only one patent (U.S. Patent No.
3,956,329) describing the use of molecular sieves in
these reactions, and in this patent the moiecular sieves
used are conventional zeolite aluminosilicates produced
by direct synthesis and having silicon:aluminum ratios
less then 6.
It has now been discovered that the product
distribution obtained in the aforementioned
dehydration/deamination reactions of alkanolamines can
be improved by using as the catalyst in such reactions
certain selected molecular sieves.
D-14643
~5~ 1336717
SummarY of the Invention
This invention provides a process for the
conversion of a hydroxyalkylamine starting material to
at least one of an amine, a different hydroxyalkylamine
and an aziridine, which process comprises contacting the
starting material with a molecular sieve selected from
the group consisting of (a) non-zeolitic molecular
sieves; and (b) zeolites having a silicon:aluminum ratio
of at least about 6, the contacting of the starting
material with the molecular sieve being effected under
conditions effective to convert the starting material
into at least one of a cyclic or acyclic amine, a
different cyclic or acyclic hydroxyalkylamine and an
aziridine.
Detailed Description of the Invention
As already mentioned, the molecular sieves
used in the process of the present invention are of
three types, namely (a) non-zeolitic molecular sieves;
and (b) zeolites having a silicon:aluminum ratio of at
least about 6 (hereinafter referred to as "high-silica
zeolites"). The term "non-zeolitic molecular sieve" is
used herein to mean non-zeolitic molecular sieves of the
aluminophosphate and silicoaluminophosphate types. Such
non-zeolitic molecular sieves comprise a large number of
aluminophosphates and silicoaluminophosphates having a
variety of crystal structures, which may include one or
more other elements in addition to aluminum, phosphorus
D-14643
-6- 1336717
and silicon. Since many of the non-zeolitic molecular
sieves are not described in U.S. Patents, and some are
not described in publically-available literature, much
material describing these non-zeolitic molecular sieves
has to be repeated herein. However, for the convenience
of the reader, the manner in which the molecular sieves
are used in the process of the present invention will
first be described, and thereafter the chemical nature,
and methods for the preparation, of the molecular sieves
will be described.
PROCESS OF THE I~v~NllON
As already mentioned, in the process of the
present invention an alkanolamine starting material is
contacted with one of a selected group of molecular
sieves to produce at least one of a cyclic or acyclic
amine, a different cyclic or acyclic hydroxyalkylamine
and an aziridine. The process of the present invention
is especially useful for the conversion of
monoethanolamine to at least one of ethylenimine,
piperazine, substituted piperazines, pyrazine,
aminoethanolamine, diethanolamine, ethylenediamine,
substituted ethyleneimines, ethylamine, acetonitrile and
morpholine, but may also be used for the conversion of
other ~lk~nolamines~ for example the conversion of
propanolamine (~-hydroxypropylamine) to propylenimine
(2-methylaziridine) and other products.
D-14643
7 1336717
The products of the process of the present
invention may include both acyclic and cyclic amines and
hydroxyalkylamines. The cyclic products may include
both monocyclic materials, for example piperazine,
pyrazine and morpholine, and products containing more
tkan one ring. For example, it has been found that,
under certain conditions, when one or more of
monoethanolamine, piperazine, ethylene glycol,
aminoethylpiperazine, hydroxyethylpiperazine,
ethylenediamine and other ethyleneamines and
ethanolamines (or certain other starting materials) are
subjected to the process of the present invention the
products selectively include
1,4-diazabicyclot2,2,2]octane (DABCO). Also, it has
been found that, under certain conditions, when one or
more of piperazine, propylene glycol, isopropanolamine
and other methylated ethyleneamines and methylated
ethanolamines (or certain other starting materials) are
subjected to the process of the present invention the
products selectively include a mixture of
2-methyl-1,4-diazabicyclo~2,2,2]octane (methyl DABC0)
and 1,4-diazabicyclo[2,2,2]octane (DABCO). The
preferred catalysts for the above conversions include
Silicalite, a microporous form of silica described in
U.S. Patent No. 4,061,724 issued December 6, 1977 to
R.W. Grose et al., and Silicalite treated with
D-14643
- 8 - 1336717
phosphoric acid or phosphoric acid equivalents such
as diammonium hydrogen phosphate.
Also as already mentioned, the
aluminophosphate or silicoaluminophosphate
non-zeolitic molecular sieves useful in the process
of the present invention are described in detail
below. Examples of such non-zeolitic molecular
sieves which may be used in the present invention
include:
(a) the AlPO4's described and claimed in
U.S. Patent 4,310,440, issued January 12, 1982 to
Wilson et al.; illustrative AlPO4 species are
AlPO4-5, AlPO4-11, AlPO4-14, AlPO4-17 and AlPO4-31;
(b) the magnesium, manganese, cobalt and
zinc aluminophosphate molecular sieves described and
claimed in U.S. Patent 4,567,029, issued January 28,
1986 to Wilson et al.; illustrative species are
MgAPO-ll, MgAPO-34, MgAPO-35 and CoAPO-34;
(c) the iron aluminophosphate molecular
sieves described and claimed in U.S. Patent
4,554,143, issued November 19, 1985 to Messina et
al.; an illustrative species is FeAPO-ll;
(d) the silicoaluminophosphate molecular
sieves described and claimed in U.S. Patent
4,440,871 issued April 23, 1984 to Lok et al.;
illustrative species are SAPO-5 and SAPO-34;
(e) the magnesium silicoaluminophosphate
molecular sieves described and claimed in U.S.
D-14643
, ~. ;.
,,~
- 1336717
Patent No. 4,758,419; an illustrative species is
MgAPSO-34; and
(f) the cobalt silicoaluminophosphate
molecular sieves described and claimed in U.S.
Patent No. 4,744,970; an illustrative species is
CoAPSO-34.
The preferred zeolites having a
silicon:aluminum ratio of at least about 6 for use
in the process of the present invention are those
described and claimed in U.S. Patent No. 4,257,885,
issued March 24, 1981 to Grose et al. and assigned
to the same assignee as this application. These
high-silica zeolites have a structure related to the
pentasil type, and are prepared by crystallization
from a reaction mixture containing a metal cation
selected from Groups I and II of the Periodic System
of Elements, particularly lithium, barium, calcium
and strontium. A particularly preferred species of
this group of zeolites is LZ-105, manufactured by
Union Carbide Corporation.
It is well-known to those skilled in the
art of molecular sieve catalysis that many molecular
sieve catalyzed reactions operate by Bronsted acid
catalysis. Experimentally, the relative Bronsted
acidities of molecular sieves can be determined from
the rates at which they catalyze hydrocarbon
cracking; the higher the acidity, the higher the
n-butane cracking rate constant. However, there is
no significant correlation between the
D-14643
f
-lo- 1336717
n-butane cracking rate constants of the various
molecular sieves and their activities in the process of
the present invention. Moreover, some of the AlPO4
aluminophosphate molecular sieves of U.S. Patent No.
4,310, 440 (described in detail below), exhibit
relatively high activity in the process of the present
invention, despite the fact that, because of their
charge-balanced framework, these materials exhibit
virtually no Bronsted acidity.
Moreover, the activity of the catalysts in the
process of the present invention is not simply a
function of pore size, since significant activities have
been achieved with molecular sieves having pore sizes
ranging from 4.3 to 8 A.
One factor which does appear to affect the
selectivity of the catalyst to particular products is
the ability of the catalyst to adsorb these products.
For example, in the preferred process of the present
invention in which monoethanolamine is converted to
ethylenimine and other products, it has been found that
molecular sieves which strongly adsorb ethylenimine do
not produce significant amounts of ethylenimine, even
though they are active in the conversion of
monoethanolamine to other products. Similar results may
be expected in, for example, the conversion of
monopropanolamine to propylenimine.
D-14643
- 13~6717-
--11--
In their as-synthesized form, the non-zeolitic
molecular sieves contain within their internal pore
systems at least one form of the organic templating
agents used in their synthesis. Most commonly the
organic moiety is present, at least in part, as a
charge-balancing cation, and indeed this is generally
the case with as-synthesized aluminosilicate zeolites
prepared from organic-containing reaction systems. It
is possible, however, that some or all of the organic
moiety is an occluded molecular species in a particular
species of molecular sieve. As a general rule the
templating agent, and hence the occluded organic
species, is too large to move freely through the pore
system of the molecular sieve and must be removed by
calcining the molecular sieve in air at temperatures of
200- to 700-C, preferably about 350 to about 600C, to
thermally degrade the organic species. In a few
instances the pores of the molecular sieve are
sufficiently large to permit transport of the templating
agent, particularly if the latter is a small molecule,
and accordingly complete or partial removal thereof can
be accomplished by conventional desorption procedures,
such as hydrotreating or chemical treatment such as
solvent extraction, which will be familiar to those
skilled in the molecular sieve art. In some cases, the
organic templating agent may be removed in situ by
placing the molecular sieve still containing the organic
D-14643
1336717
-12-
templating agent in the reactor, so that the organic
templating agent is removed under reaction conditions.
The process of the present invention may be
conducted with the alkanolamine starting material in the
liquid phase. However, in view of the temperatures
which are needed ln practice to carry out the process of
the present invention at an economical rate, it is
preferred that the process of the present invention be
operated as a heterogeneous, gas phase reaction with the
starting material in the gaseous phase, since a gas
phase process can be run at higher temperatures under
relatively moderate pressures (typically of the order of
a few atmospheres) using comparàtively inexpensive
equipment.
In such a gas phase process, the starting
material may be mixed with a carrier gas (such as
nitrogen or ammonia), while being contacted with the
molecular sieve; the carrier gas should of course be
chosen so that it does not prevent the preparation of
the desired products. However, the use of such a
carrier gas is not essential in the process of the
present invention, which can be operated using pure
alkanolamine starting material as the gaseous feed. The
degree of dilution of the starting material with such an
inert carrier gas may vary considerably depending upon
any process constraints restricting the use of inert
diluents. (For example, in commercial production, the
D-14643
1336717
-13- -
use of very large quantities of inert carrier gas is
disadvantageous due to the-co~st of pumping large volumes
of gas and increased difficulty in isolating the
product, which increase the energy costs of the
process.) If the process of the present invention is to
be carried out using an inert gas, in general it is
recommended that the alkanolamine starting material
constitute from about 1 to about 95, and preferably
about 9 to about 30, mole percent of the starting
material/inert gas feed. Increasing the dilution of the
starting material tends to increase the selectivity of
the reaction to the particular products desired, but is
otherwise disadvantageous.
Selection of the temperature at which the
process of the present invention is to be conducted
involves a compromise between selectivity to the desired
product(s) and conversion of the alkanolamine starting
material. It is recommended that the process of the
present invention be condùcted at a temperature in the
range of about 250-C to about 500-C; below this
temperature range, the reaction tends to proceed too
slowly, while at very high temperatures, the selectivity
to the desired products decreases dramatically. At
least for monoethanolamine conversion, the preferred
temperature range is from about 350-C to about 425-C.
The process of the present invention can be
run over a wide range of pressures ranging from
D-14643
1336717
-14- -
atmospheric or sub-atmospheric pressures to looo psig.
(6.9 MPa.) or more. However, since the use of very high
pressures has not been observed to confer any
- significant advantages but increases equipment costs, it
is recommended that the process of the present invention
be carried out at a pressure of from about atmospheric
pressure to about 1000 psig. (about 7 MPa.).
The process of the present invention can also
be carried out over a wide range of weight hourly space
velocities of the alkanolamine starting material. For
example, weight hourly space velocities of from about
0.1 to about 50 may be employed, with the preferred
range of weight hourly space velocity being from about
0.5 to about 10, based on the starting material.
The molecular sieve catalysts used in the
process of the present invention enable the reaction to
be carried out at high conversions. As illustrated in
the Examples below, the process of the present invention
can be carried out at a conversion of at least about
30%-
As with some reactions catalyzed by molecular
- sieves, the conversion achieved in the process of the
present invention may tend to fall as the time for which
the molecular sieve catalyst has been used in the
process increases. If the molecular sieve catalysts
become deactivated, then the deactivated catalyst can
readily be regenerated by heating in air at an
D-14643
-15- , 1336717
appropriate temperature (typically about 500 D C) and for
an appropriate period (typically one hour). It is one
of the advantages of the process of the present
invention that at least some of the instant catalysts
can be run for at least 40 hours of operation without
the need for reactivation, whereas some of the prior art
catalysts used for the same conversions rapidly
deactivate.
The molecular sieve may be modified by
depositing or impregnating the molecular sieve with
cations, anions or salts so as to improve its efficacy
as a catalyst in the process of the present invention.
Techniques which may be employed to effect the
deposition or impregnation of a molecular sieve are
generally known in the art. Such techniques may involve
such procedures as (1) impregnating the molecular sieve
with a solution comprising a solvent or solubilizing
agent of one or more such modifying materials in an
amount sufficient to deposit the desired weight of such
materials in the molecular sieve and/or (2) exchanging
the molecular sieve with a solution containing the
modifying material. The impregnation or deposition of
the modifying materials may generally be accomplished by
heating the molecular sieve at an elevated temperature
to evaporate any liquid present to effect deposition or
impregnation of the modifying material on to the
interior and/or exterior surface of the molecular sieve,
D-14643
-16- 1336717
or by the exchange of cations present in the molecular
sieve with cations that provide for the desired
properties (provided of course that the molecular sieve
is one having a significant ion-exchange capacity).
Alternatively, the modifying material may be formed on
the molecular sieve from a solution, an emulsion or a
slurry containing the modifying materiaL
Impregnation or exchange procedures
are generally the preferred techniques because they
utilize and introduce the modifying material more
efficiently than other procedures such as coating
procedures since a coating procedure is generally not
able to effect substantial introduction of the modifying
material on to the interior surfaces of the molecular
sieve. In addition, coated materials are more generally
susceptible to the loss of the modifying materials by
abrasion.
Suitable modifying materials include alkali
metals, alkaline earth metals, transition metals and the
salts thereof including inorganic and organic salts such
- as nitrates, halides, hydroxides, sulfates and
carboxylates. Other modifying materials generally
employed in the art are also believed to be employable
in the molecular sieves.
In carrying out the process of the present
invention, the molecular sieves may be admixed (blended)
or provided sequentially to other materials which may
D-14643
- 1336717
-17-
provide some property which is beneficial under process
conditions, such as improved temperature resistance or
improved catalyst life by minimization of coking, or
which are simply inert under the process conditions
used. Such materials may include synthetic or
naturally-occurring substances as well as inorganic
materials such as clays, silicas, aluminas, metal oxides
and mixtures thereof. In addition, the molecular sieves
may be formed with materials such as silica, alumina,
silica-alumina, silica-magnesia, silica-zirconia,
silica-thoria, silica-berylia, and silica-titania, as
well as ternary compositions, such as silica-alumina-
thoria, silica-alumina-zirconia and clays present as
binders. The relative proportions of the above
materials and the-molecular sieves may vary widely with
the molecular sievé content ranging between about 1 and
about 99 percent by weight of the composite.
~ he following Examples are provided to further
illustrate the process of the present invention, but are
not limitative thereof. Unless otherwise specified, all
parts, proportions etc. are by weight.
EXAMPLES
The following Examples illustrate the use of
AlP04-5, AlP04-11, AlP04-14, AlP04-17, AlP04-31,
CoAP0-34, FeAP0-34, MgAP0-11, MgAP0-34, MgAP0-35,
SAP0-5, SAP0-34, CoAPS0-34, MgAPS0-34 and LZ-105 in the
process of the present invention. The characteristic X-
D-14643
13~6717
-18-
ray tables for AlPO4-5, AlPO4-11, AlPO4-14, and AlPO4-17
are given in U.S. Patent No. ~4,310,440 at Table 2 in
column 8, Table 8 in column 15, Table 12 in column 21,
and Table 15 in column 26 respectively. The ALPO4-31
was produced as described in U.S. Patent No. 4,310,440,
Example 54. The characteristic X-ray tables for
CoAPO-34, MgAP0-11, MgAPO-34 and MgAPO-35 are given in
U.S. Patent No. 4,567,029 at Table XLI in column 91,
Table III in column 17, Table X in column 31 and Table
XI in column 33 respectively. The characteristic X-ray
table for FeAPO-34 is given in U.S. Patent No. 4,554,143
at Table XI in column 29. The characteristic X-ray
tables for SAPO-5 and SAPO-34 are given in U.S. Patent
No. 4,440,871 at Table I in column 20 and Table XI in
column 44 respectively. The characteristic X-ray tables
for CoAPSO-34 and MgAPSO-34 are given below:
CoAPSO-34
2e d (A) Relative Intensity
9.4 - 9.8 9.41 - 9.03 s - vs
2012.86 - 13-.06 6.86 - 6.76 w
14.08 - 14.30 6.28 - 6.19 w - m
15.90 - 16.20 5.57 - 5.47 vw- m
20.60 - 20.83 4.31 - 4.26 w - vs
30.50 - 30.80 2.931 - 2.903w - m
MgAPS0-34
2~ d (A~ Relative Intensity
9.3 - 9.7 9.51 - 9.12 vs
15.8 - 16.3 5.61 - 5.44 w - m
20.25 - 21.0 4.39 - 4.23 m - vs
3025.7 - 26.3 3.466 - 3.389vw- m
30.0 - 30.8 2.979 - 2.903vw- m
30.9 - 31.4 2.894 - 2.849w - m
D-14643
-19- 1336717
Ex~erimental Conditions
The various molecul~ar sieve catalysts were
prepared as described below, calcined in air following
synthesis to remove the organic templating agent, and
then calcined for one hour under nitrogen at the
reaction temperature prior to use. Between each run,
the catalysts were regenerated by calcination at 500C
in air for 1 to 12 hours.
Two separate microreactors were used. The
first micro reactor consisted of a 1/4 inch (6 mm.)
diameter stainless steel U-tube heated in a fluidized
sand bath. Approximately l gram of catalyst as the
powder was dispersed among several grams of 20-30 U. S.
mesh quartz chips and placed in the heated zone of the
reactor. Connected to the inlet of the reactor were a
source of nitrogen or ammonia carrier gas and a liquid
feed line containing monoethanolamine connected to a
high pressure liquid chromatography (HPLC) type solvent
pump. To the outlet of the U-tube was connected a room
temperature liquids trap, followed by a heated port for
gas sampling. It was determined that ethylenimine was
not being collected in the liquids trap to any
appreciable extent. The gases from the heated port were
analyzed by gas chromatography on a 6 foot by 1/8 inch
(1829 by 3 mm.) column containing Chromosorb 101. The
liquid samples from the liquids trap were analyzed by
amine derivatization with N-methylbistrifluoroacetamide.
D-14643
- 20 - 1336717
Because of the difficulties of quantitative
analysis in two different phases, later experiments
used a second microreactor consisting of a 3/8 inch
(9 mm.) diameter stainless steel tube encased in a 1
inch (25 mm.) diameter sheath of stainless steel
heated with an electric split furnace.
Approximately 1 gram of catalyst as the powder was
dispersed among about 5 grams of 20-30 U. S. mesh
quartz chips and placed in the heated zone of the
reactor. The reactor tube was disposed vertically
with a downward flow of reactants and products. The
same feed line and source of flow gas were employed
as in the first microreactor. Immediately below the
reactor was disposed a cold trap kept at 0C. Gas
chromatographic analysis of the outlet gas indicated
that all of the ethylenimine produced was retained
in the cold trap and ammonia and only very small
amounts of a material with a retention time similar
to that of ethylene passed the trap. The products
of the reaction collected in the cold trap were
analyzed by gas chromatography on a 12 foot by 1/8
inch (3658 by 3 mm.) column containing TERGITOL*
non-ionic TMN (a polyether liquid phase) and 3
percent sodium methylate on 60/80 Chromasorb W-NAW,
or on a 10 foot by 1/8 inch (3048 by 3 mm.) column
containing 8 percent TERGITOL* non-ionic E68 and 2
percent potassium hydroxide.
Several experiments were run using both
microreactors, and these experiments confirmed that no
* Registered Trademark
D~14643
-21- 133671~ -
appreciable difference in results were produced by the
change in reactors.
Examle 1
The first microreactor described above was
charged with 1.0 g. of AlPO4-14 and heated to 400C.
Nitrogen carrier gas was passed through the reactor at a
rate of 40 ml/min. at atmospheric pressure, and liquid
monoethanolamine was fed into the nitrogen stream at a
rate of 1.6 ml/hour. Analysis of the products of the
reaction showed a conversion of approximately 70
percent, with a product distribution (based on converted
monoethanolamine) as follows:
Product Percentage
Piperazine 40
Aminoethylpiperadine 14
Diethanolamine 4
Triethanolamine 10
Aminoethylethanolamine 4
Diethylenetriamine 4
Ethylenimine 3,
together with minor amounts of other amines and
Alk~nolamines.
Examle 2
The first microreactor described above was
charged with 1.0 g. of SAPO-5 and heated to 400C.
Nitrogen carrier gas was passed through the reactor at a
rate of 40 ml/min. at atmospheric pressure, and liquid
D-14643
-22- 1336717
monoethanolamine was fed into the nitrogen stream at a
rate of 0.4 ml/hour. Analysis of the products of the
reaction showed a conversion of approximately 30
percent, with a product distribution (based on converted
5 monoethanolamine) as follows: -
Product Percentage
Piperazine 45
Aminoethylpiperazine 18
Morpholine 15,
together with minor amounts of other alkylamines and
alkanolamines.
Exam~le 3
The first microreactor described above was
charged with 1.0 g. of AlPO4-11 and heated to 350C.
Nitrogen carrier gas was passed through the reactor at a
rate of 40 ml/min. at atmospheric pressure, and liquid
monoethanolamine was fed into the nitrogen stream at a
rate of 0.5 ml/hour. Analysis of the products of the
reaction showed a conversion of approximately 5 percent,
with ethylenimine constituting about 40 percent of the
products, the other products being piperidine,
piperazine, ethylamine, morpholine and other nitrogen
and/or oxygen-containing products.
Examples 4-16
Various molecular sieves were tested for their
activities in the process of the present invention in
the same manner as in Examples 1-3 above, except that in
D-14643
133~717
-23-
some cases the second microreactor described above was
used. Except as specified in Table 1 below, the
experiments were conducted with 1 gram of catalyst in
the microreactor, at a reaction temperature of 375C,
with nitrogen gas flowing at a rate of 40 ml/min. and
monoethanolamine flowing at a rate of 1.6 ml/hr. The
results are shown in Table 1 below, in which the
following abbreviations are used:
Abbreviation Full Term
10 Conv. Conversion
EI Ethylenimine
PIP Piperazine
AEP Aminoethylpiperazine
AEEA Aminoethylethanolamine
15 DEA Diethanolamine
TEA Triethanolamine
DETA Diethylenetriamine
All values for products are percentages based upon the
converted monoethanolamine.
D-14643
- 1336717
--24-- -
TAkr.~ ~
4 ~ 4- 17 .70 0 45 2~ 5 5 10 3 12
AlP~4-31a'~ SO O 40 30 ~ 3 lQ 4 11
6 ~1~4~ 3.0 10 3S 20 ~ 4 4 4 13
C~34 S 3D 10 0 10 ~5 Cl 10 25
& f~ 5 10 ~0 10 l~i 10 0 15 3t:~
9 FeA~UC 3~ 0 4~ 30 4 5 6 ~ g
~11 5 ;~!0 ;113 ~0 5 S 10 0 :L0
lb ~ 5 ~0 10 11:110 15 S 5 15
35 5 2~ ~0 5 Sl~ lC 5
~3 Ç~34 3~ ~ 3S 3t3 3 4 10 4 14
J~ 3~ 5 10 2~ 20 ~ 5 0 10 30
c; ~3~L 5 ~ ~13 10 ~ 10 ~0
lQ~i3t~ ~ 3~ 20 5 ;20 10 5 ~0
~ - ~e~per~tusc 3 5 0 - C
b. Nitr~ te 20 ~lJm~ n .
c. ~~pt~a~re 400~C-
Att~nt~un ~ dl~ected ~0 ~e ~:O-p~
~0 a~plic~ S,r ~cu~ ~ olgon an~ sSe~en ~ ~1$~, O~
*;r~ aat~ ~re~,t;h ~C~di~ri p~tent appl~. Ser. N~. 58~, ~74-0
which ~eEcri~ an~ clal~ ~ 2roce~s fs: r the ~ehyd~tion
a ,~ -hy~roxya~ ne *o the corresponding az ~ ridine,
e~pe~i~lly ~nce~anol~mi~ to ethyleniDl~ne~ ~he
2~ c~t~lys~ u~ is ~ 13o~e~lar S~e~re, ~hich is loaded with
~ra a~ali Qr al~ lne e~a~n~ -
~14 ~i43
- 25 -
NON-ZEOLITIC MOLECULAR SIEVES 13~717
The term "non-zeolitic molecular sieves" or
"NZMS" is defined in the instant invention to
include the "SAPO" molecular sieves of U.S. Patent
No. 4,440,871, "ELAPSO" molecular sieves as
disclosed in U.S. Patent No. 4,793,984 and certain
"AlPO4", "MeAPO", "FeAPO", "TAPO" and "ELAPO"
molecular sieves, as hereinafter described.
Crystalline "AlPO4" aluminophosphates are disclosed
in U.S. Patent No. 4,310,440 issued January 12,
1982; crystalline metal aluminophosphates (MeAPOs
where ~Me~ is at least one of Mg, Mn, Co and Zn) are
disclosed in U.S. Patent No. 4,567,029, issued
January 28, 1986; crystalline ferroaluminophosphates
(FeAPOs) are disclosed in U.S. Patent No. 4,554,143,
issued November 19, 1985; titanium aluminophosphates
(TAPOs) are disclosed in U.S. Patent No. 4,500,651,
issued February 19, 1985; certain non-zeolitic
molecular sieves ("ELAPO") are disclosed in EPC
Patent Application 85104386.9 (Publication No.
0158976, published October 13, 1985) and 85104388.5
(Publication No. 158349, published October 16,
1985); and ELAPSO molecular sieves are disclosed in
U.S. Patent No. 4,793,984 (EPC Publication No.
0159624, published October 30, 1985).
D-14643
- 26 - 133 6717
The nomenclature employed herein to refer to the
members of the aforementioned NZMSs is consistent
with that employed in the aforementioned
applications or patents. A particular member of a
class is generally referred to as a "-n" species
wherein "n" is an integer, e.g., SAPO-ll, MeAPO-ll
and ELAPSO-31. In the following discussion on NZMSs
set forth hereinafter the mole fraction of the NZMSs
are defined as compositional values which are
plotted in phase diagrams in each of the identified
patents, published applications or copending
applications.
ELAPSO MOLECULAR SIEVES
~ 'ELAPSO" molecular sieves are described in
U.S. Patent No. 4,793,984 as crystalline molecular
sieves having three-dimensional microporous
framework structures of ELO2, A102, PO2, SiO2 oxide
units and having an empirical chemical composition
on an anhydrous basis expressed by the formula:
mR : (ELWAlxPysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (ELwAlxPySiz)02 and has a value
of from zero to about 0.3; "EL" represents at least
one element capable of
D-14643
-27- 1336717
forming a three dimensional oxide framework, "EL" being
characterized as an element having a mean "T-O" distance
in tetrahedral oxide structures between about 1.51
Angstroms and about 2.06 Angstroms, "EL" having a cation
electronegativity between about 125 kcal/g-atom to about
310 kcal/gm-atom and "EL" being capable of forming
stable M-O-P, M-O-Al or M-O-M bonds in crystalline three
dimensional oxide structures having a "M-O" bond
dissociation energy greater than about 59 kcal/g-atom at
298-K; and "w", "x", "y" and "z" represent the mole
fractions of "EL", aluminum, phosphorus and silicon,
respectively, present as framework oxides, said mole
fractions being within the limiting compositional
values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.39-(O.Ol)p O.Ol(p + 1)
B 0.39-(O.Olp) 0.60 O.Ol(p + 1)
C 0.01 0.60 0039
D 0.01 0.01 0.98
E 0.60 0.01 0.39
where "p" is an integer corresponding to the number
of elements "El" in the (ElwAlxPySiz)02 constituent.
The "ELAPSO" molecular sieves are also
described as crystalline molecular sieves having
three-dimensional microporous framework structures of
EL02, A102, SiO2 and P02 tetrahedral oxide units and
D-14643
- 28 - 1336717
having an empirical chemical composition on an
anhydrous basis expressed by the formula:
mR : (ELWAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (ELwAlxPySiz)02 and has a value
of from zero to about 0.3; "EL" represents at least
one element capable of forming a framework
tetrahedral oxide and is selected from the group
consisting of arsenic, beryllium, boron, chromium,
cobalt, gallium, germanium, iron, lithium,
magnesium, manganese, titanium and zinc; and ~'w",
"x", "y" and "z" represent the mole fractions of
"EL", aluminum, phosphorus and silicon,
respectively, present as tetrahedral oxides, said
mole fractions being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w)
a 0.60 0.39-(O.Ol)p O.Ol(p + 1)
b 0.39-(O.Olp) 0.60 O.Ol(p + 1)
c 0.10 0.55 0.35
d 0.55 0.10 0.35
where "p" is as above defined.
The "ELAPSO" molecular sieves include
numerous species which are intended herein to be
within the scope of the term "non-zeolitic molecular
sieves" such being disclosed in the following
commonly
D-14643
,., ~ .~-,
- 29 - 1336717
assigned patents or applications, [(A) following a
serial number indicates that the application is
abandoned and (C) indicates that the application is
a continuation of the immediately preceding patent
or application]:
D-14643
13~6717
U.S. Patent/Serial No. Filed NZMS
4,737,353 March 20, 1986 BeAPSO
4,738,837 April 15, 1986 CAPSO
4,735,806 March 31, 1986 GaAPSO
4,992,250 April 15, 1986 GeAPSO
4,684,617 April 13, 1984 TiAPSO
4,801,309(C) May 13, 1987 TiAPSO
4,758,419 April 13, 1984 MgAPSO
4,686,092 April 13, 1984 MnAPSO
4,744,970 April 13, 1984 CoAPSO
Can. Pat. No. 1248079 ZnAPSO
4,683,217 April 13, 1984 FeAPSO
Can. Pat. No. 1248080 QuinAPSO
4,956,164(C) June 22, 1987 QuinAPSO
4,741,892 April 13, 1984 QuinAPSO
D-14643
~ , .
TiAPSO MOLECULAR SIEVES 1 3 3 6 717
The TiAPSO molecular sieves of U.S. Patent
No. 4,684,617 and U.S. Patent No. 4,801,309 have
three-dimensional microporous framework structures
of TiO2, AlO2 ~, PO2+ and SiO2 tetrahedral oxide
units and have an empirical chemical composition on
an anhydrous basis expressed by the formula:
mR : (TiWAlxPysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; ~'m" represents the molar amount of ~R~'
present per mole of (TiwAlxPySiz)O2 and has a value
from zero to about 0.3; and "w", "x", "y" and "z"
represent the mole fractions of titanium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides and each has a value of at least
0.01. The mole fractions "w", "x", "y" and "z" are
generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
D-14643
~'
-32- 1336717
In a subclass of TiAPSo molecular sieves
the values "w", "x", "y" and~"z" in the above formula
are within the tetragonal compositional area defined by
points a, b, c and d, said points a, b, c and d
representing the following values for "w", "x", "y" and
"z":
Mole Fraction
Point x y rz + w)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c o.lO 0.55 0.35
d 0.55 0.10 0.35
TiAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing active sources of titanium, silicon, aluminum
and phosphorus, and preferably an organic templating,
i.e., structure-directing, agent, preferably a compound
of an element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between 50 C and
250 C, and preferably between lOO-C and 200-C until
crystals of the TiAPSo product are obtained, usually a
period of from hours to several weeks. Generally, the
D-14643
- 1~36717
. -33-
crystallization time is from about 2 hours to about 30
days and typically from about 4 hours to about'20 days.
The product is recovered by any convenient method such
- as centrifugation or filtration.
S In synthesizing the TiAPSos, it is preferred
to employ a reaction mixture composition expressed in
terms of the molar ratios as follows:
aR : (TiwAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "w", "x",
"y" and "z" represent the mole fractions of titanium,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y"
and "z" are generally defined as being within the
limiting compositional values or points as follows:
D-14643
- 34 -
1336717
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with
respect to the total of ~w~, "x", "y" and "z" such
that (w + x + y + z) = 1.00 mole. Molecular sieves
containing magnesium, aluminum, phosphorus and
silicon as framework tetrahedral oxides are prepared
as follows:
Preparative Reagents
MgAPSO compositions are prepared using
numerous reagents. Typical reagents which may be
employed to prepare MgAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the trademark
of DuPont for an aqueous solution of
30 weight percent SiO2 and 0.1 weight
percent Na2O;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid in water;
(d) Tiipro: titanium isopropoxide;
D-14643
~ ~,.
-3s- 133 6717
(e) TEAOH: 40 weight percent aqueous ~
solution of tetraethyla~monium
hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3NH: tri-n-propylamine, (C3H7)3N;
(h) Quin: Quinuclidine, (C7H13N);
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H); and
(j) C-hex: cyclohexylamine.
Preparative Procedures
TiAPSOs may be prepared by forming a starting
reaction mixture by adding the H3PO4 and the water.
This mixture is mixed and to this mixture aluminum
isopropoxide is added. This mixture is then blended
until a homogeneous mixture is observed. To this
mixture the LUDOX-LS is added and the resulting mixture
blended (about 2 minutes) until a homogeneous mixture is
observed.
The titanium isopropoxide is added to the
above mixture and the resulting mixture blended until a
homogeneous mixture is observed. The organic templating
agent is then added to the resulting mixture and the
resulting mixture blended until a homogeneous mixture is
observed, i.e., about 2 to 4 minutes. When the organic
templating agent is quinuclidine the procedure is
modified such that the quinuclidine is dissolved in
D-14643
- 36 - 1336717
about one half the water and accordingly the H3PO4
is mixed with about one half the water. (The pH of
the mixture is measured and adjusted for
temperature). The mixture is then placed in a lined
(polytetrafluoroethylene) lined stainless steel
pressure vessel and digested at a temperature (150C
or 200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
The products are removed from the reaction
vessel and cooled.
MqAPSO MOLECULAR SIEVES
The MgAPSO molecular sieves of U.S. Patent
No. 4,758,419 have three-dimensional microporous
framework structures of MgO22-, AlO2-, PO2+ and SiO2
tetrahedral oxide units and have an empirical
chemical composition on an anhydrous basis expressed
by the formula:
mR : (MgwAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (MgwAlxPySiz)O2 and has a value
from zero (0) to about 0.3; and ~w~, "x", "y" and
"z" represent the mole fractions of magnesium,
aluminum, phosphorus and silicon, respectively,
present as tetrahedral oxides and
D-14643
_37_ 1336717
each preferably has a value of at least 0.01. The mole
fractions "w", "x", "y" and "z" are generally defined as
being within the limiting compositional values or points
as follows: .
Mole Fraction
Point x y (z + w~
A 0.60 0.38 0.02
B 0.39 0.59 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the MgAPSO
molecular sieves the values "w", "x", "y" and "z" in the
above formula are within the limiting compositional
values or points as follows:
Mole Fraction
Point x y (z + w)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10 0.35
MgAPSO compositions are generally synthesized
by hydrothermal crystallization for an effective time at
effective pressures and temperatures from a reaction
mixture containing reactive sources of magnesium,
silicon, aluminum and phosphorus, an organic templating,
D-14643
-38- - 1336717
i.e., structure-directing, agent, preferably a compound
of an element of Group VA of~the Periodic Table, and may
be an alkali or other metal. The reaction mixture is
generally placed in a sealed pressure vessel, preferably
lined with an inert plastic material such as polytetra-
fluoroethylene and heated, preferably under autogenous
pressure at a temperature between 50-C and 250-C, and
preferably between lOO-C and 200-C until crystals of the
MgAPSO product are obtained, usually a period of from
several hours to several weeks. Generally, the
crystallization period will be from about 2 hours to
about 30 days with it typically being from about 4 hours
to about 20 days for obtaining MgAPSO crystals. The
product is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the MgAPS0 compositions, it is
preferred to employ reaction mixture compositions
expressed in terms of the molar ratios as follows:
aR : (MgWAlxpySiz)O2 : bH20
wherein "R" is an organic templating agent; "a" is thè
amount of organic templating agent "R" and can have a
value within the range of from zero (0) to about 6 and
is more preferably an effective amount greater than zero
to about 6; "b" has a value of from zero (0) to about
500, preferably between about 2 and about 300; and "w",
"x", "y" and "z" represent the mole fractions of
D-14643
~39~ 133 6717
magnesium, aluminum, phosphorus and silicon,
respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
co~osition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing magnesium, aluminum, phosphorus and silicon
as framework tetrahedral oxides are prepared as follows:
PreDarative Rea~ents
MgAPSO compositions are prepared using
numerous reagents. Typical reagents which may be
employed to prepare MgAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea for
hydrated pseudoboehmite;
D-14643
_40_ 1336717
(c) LUDOX-LS: Trademark of DuPont for
an aqueous solution of 30 weight
percent SiO2 and 0.1 weight
percent Na2O;
(d) Mg(Ac)2: magnesium acetate
tetrahydrate, Mg(C2H3O2).4H2O;
(e) H3PO4: 85 weight percent
aqueous phosphoric acid in water;
(f) TBAOH: tetrabutylammonium hydroxide (40
wt. % in water);
(g) Pr2NH: di-n-propylamine;
(h) Pr3NH: tri-n-propylamine;
(i) Quin: Quinuclidine;
(j) MQuin: Methyl Quinuclidine hydroxide,
(17.9% in water);
(k) C-hex: cyclohexylamine;
(1) TEAOH: tetraethylammonium hydroxide
(40 wt. % in water);
(m) DEEA: Diethylethanolamine;
(n) i-Pr2NH: di-isopropylamine;
(o) TEABr: tetraethylammonium bromide; and
(p) TPAOH: tetrapropylammonium hydroxide
(40 wt. % in water).
D-14643
1336717
Preparative Procedures
The MgAPSO compositions may be prepared by
preparing reaction mixtures having a molar composition
expressed as:
eR fMg hAl23 iP2os gsio2 jH2o
wherein e, f, g, h, i and j represent the moles of
template R, magnesium (expressed as the oxide), SiO2,
Al203, P205 (H3PO4 expressed as P205) and H20,
respectively.
The reaction mixtures may be prepared by the
following representative procedures, designated
hereinafter as Methods A, B and C.
Method A
The reaction mixture is prepared by mixing the
ground aluminum source (Alipro or CATAPAL) with the
H3PO4 and water on a gradual basis with occasional
cooling with an ice bath. The resulting mixture is
blended until a homogeneous mixture is observed. When
the aluminum source is CATAPAL the water and H3PO4 are
first mixed with the CATAPAL added thereto. The
magnesium acetate is dissolved in a portion of the water
and is then added followed by addition of the LUDOX-LS.
The combined mixture is blended until a homogeneous
mixture is observed. The organic templating agent is
added to this mixture and blended until a homogeneous
mixture is observed. The resulting mixture (final
D-14643
1336717
- 42
reaction mixture) is placed in a lined (polytetrafluoro-
ethylene) stainless steel prèssure vessel and digested
at a temperature (150-C or 200-C) for an effective time.
Alternatively, if the digestion temperature is 100-C the
final reaction mixture is placed in a lined
(polytetrafluoroethylene) screw top bottle for a time.
Digestions aré typically carried out under autogenous
pressure. The products are removed from the reaction
vessel, cooled and evaluated as set forth hereinafter.
Method B
When method B is employed the organic
templating agent is di-n-propylamine. The aluminum
source, silicon source and one-half of the water are
first mixed and blended until a homogeneous mixture is
observed. A second solution was prepared by mixing the
remaining water, the H3PO4 and the magnesium acetate.
This solution is then added to the above mixture. The
magnesium acetate and H3PO4 solution is then added to
the above mixture and blended until a homogeneous
mixture is observed. The organic templating agent(s)
is/are then added and the resulting reaction mixture
digested and product recovered as in Method A.
Method C
Method C is carried out by mixing aluminum
isopropoxide, LUDOX LS and water in a blender or by
mixing water and aluminum iso-propoxide in a blender
D-14643
- 43 -
1 3~6717
followed by addition of the LUDOX LS. ~3P~4 and
magnesium acetate are then added to the resulting
mixture. The organic templating agent is then added
to the resulting mixture and digested and product
recovered as in Method A.
MnAPSO MOLECULAR SIEVES
The MnAPSO molecular sieves of U.S. Patent
No. 4,686,092 have a framework structures of
MnO2 -2, AlO2 -, PO2 + and SiO2 tetrahedral units
and have an empirical chemical composition on an
anhydrous basis expressed by the formula:
mR : (MnwAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R~'
present per mole of (MnwAlxPySiz)O2 and has a value
of zero to about 0.3; and "w", "x", "y" and "z"
represent the mole fractions of the elements
manganese, aluminum, phosphorus and silicon,
respectively, present as tetrahedral oxides. The
mole fractions "w", "x", "y" and "z" are generally
defined, as being within the limiting compositional
values or points as follows:
D-14643
~ A
~44~ 1336717
Mole Fraction
Point x ` y ~ ~ (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
s C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
The values of w, x, y and z may be as follows:
Mole Fraction
10 Point x y (z + w)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10 0.35
MnAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of manganese, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50 C and about 250 C, and preferably
D-14643
- 13~6717
-4S- -
between about lOO-C and about 200-C until crystals of
the MnAPSO product are obtai~ed, usually a period of
from several hours to several weeks. Typical effective
times of from 2 hours to about 30 days, generally from
about 4 hours to about 20 days, have been observed. The
product is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the MnA~SO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (MnwAlxpysiz)o2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "w", "x",
"y" and "z" represent the mole fractions of manganese,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
D-14643
- 46 -
Mole Fraction 13~ 6717
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with
respect to the total of ~w~, "x", "y" and "z" such
that (w + x + y + z) = 1.00 mole. Molecular sieves
containing cobalt, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follows:
Preparative Reaqents
MnAPSO compositions may be prepared using
numerous reagents. Reagents which may be employed
to prepare MnAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea
Corporation for pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the trademark
of DuPont for an aqueous solution of
30 weight percent SiO2 and 0.1 weight
percent Na2O;
D-14643
. ~
_47_ 1 3 3 6 71 7
(d) H3PO4: 85-weight percent aqueous
phosphoric acid:
(e) MnAc: Manganese acetate,
Mn(c2H3o2)2.4H2o;
(f) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEEA: 2-diethylaminoethanol.
Preparative Procedures
MnAPSOs are prepared by forming a starting
reaction mixture by adding the H3PO4 to one half of the
quantity of water. This mixture is mixed and to this
mixture the aluminum isopropoxide or CATAPAL is added.
This mixture is then blended until a homogeneous mixture
is observed. To this mixture the LUDOX LS is added and
the resulting mixture blended (about 2 minutes) until a
homogeneous mixture is observed. A second mixture is
D-14643
- 48 - 1336717
prepared using the manganese acetate and the
remainder (about 50%) Of the water. The two
mixtures are admixed and the resulting mixture
blended until a homogeneous mixture is observed.
The organic templating agent is then added to the
resulting mixture and the resulting mixture blended
until a homogeneous mixture is observed, i.e., about
2 to 4 minutes. (The pH of the mixture is measured
and adjusted for temperature). The mixture is then
placed in a lined (polytetrafluoroethylene)
stainless steel pressure vessel and digested at a
temperature (150C or 200C) for a time or placed in
lined screw top bottles for digestion at 100C.
Digestions are typically carried out at the
autogenous pressure.
CoAPSO MOLECULAR SIEVES
The CoAPSO molecular sieves of U.S. Patent
No. 4,744,970 have three-dimensional microporous
framework structures of CoO2 -2, AlO2 ~, PO2 + and
SiO2 tetrahedral units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (cowAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of ~R~'
present per mole of (CowAlxPySiz)O2 and has a value
of zero to about
D-14643
- -49- 1336717
0.3; and "w", "x", "y" and "z" represent the mole
fractions of cobalt, aluminu~, phosphorus and silicon,
respectively, present as tetrahedral oxides, where the
mole fractions "w", "x", "y" and "z" are each at least
0.01 and are generally defined, as being within the
limiting compositional values or points as follows:
. Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the CoAPSO
molecular sieves the values of "w", "x", "y", and "z" in
the above formula are within the limiting compositional
values or points as follows:
Mole Fraction
Point x y (z + w)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10. 0.35
CoAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of cobalt, silicon, aluminum
D-14643
50- 1336717
~ and phosphorus, an organic templating, i.e., structure-
- directing, agent, preferably~a compound of an element of
Group VA of the Periodic Table, and optionally an alkali
metal. The reaction mixture is generally placed in a
sealed pressure vessel, preferably lined with an inert
plastic material such as polytetrafluoroethylene and
heated, preferably under autogenous pressure at an
effective temperature which is generally between 50-C
and 250-C and preferably between 100~C and 200C until
crystals of the CoAPSO product are obtained, usually for
an effective time of from several hours to several
weeks. Generally the effective crystallization time
will be from about 2 hours to about 30 days and
typically from about 4 hours to about 20 days. The
product is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the CoAPSOs, it is preferred
to employ a reaction mixture composition expressed in
terms of the molar ratios as follows:
aR : (CowAlxPysiz)o2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
preferably between about 2 and 300; and "w", "x", "y"
D-14643
- ~ -51- 1336717
and "z" represent the mole fractions of cobalt,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01. In a preferred embodiment
the reaction mixture is selected such that the mole
fractions "w", "x", "y" and ~Zll are generally defined as
being within the limiting compositional values or points
as follows:
- Mole Fraction
Point x y fz + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing cobalt, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
Preparative Reagents
CoAPSO compositions may be prepared using
numerous reagents. Reagents which may be employed to
prepared CoAPSOs include:
(a) Alipro: aluminum isopropoxide;
D-14643
3367l7
: -52-
(b) CATAPAL: Tradema~rk of Condea Corporation
for pseudoboehmite; t
(c) LUDOX-LS: Trademark of DuPont for an
aqueous solution of 30 weight percent
SiO2 and 0.1 weight percent Na2O;
(d) Co(Ac)2: cobalt acetate,
Co(C2H3O2)2 4H2
(e) CoSO4: cobalt sulfate, (CoSO4.7H2O);
(f) H3PO4: 85 weight percent phosphoric acid
in water;
(g) TBAOH: tetrabutylammonium hydroxide (25
wt % in methanol);
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(l) C-hex: cyclohexylamine;
(m) TEAOH: tetraethylammonium hydroxide
(40 wt. % in water);
(n) DEEA: diethanolamine;
(o) TPAOH: tetrapropylammonium hydroxide
(40 wt. % in water); and
(p) TMAOH: tetramethylammonium hydroxide
(40 wt. % in water).
D-14643
~53~ 133 6717
PreParative-Procedure
CoAPSO compositio~s may be prepared by
preparing reaction mixtures having a molar composition
expressed as:
eR:fCOo:hAl2o3:ip2os gsio2 jH2o
wherein e, f, h, i, g and j represent the moles of
template R, cobalt (expressed as the oxide), Al203, P205
(H3PO4 expressed as P205), sio2 and H2O, respectively.
The reaction mixtures are prepared by forming
a starting reaction mixture comprising the H3P04 and one
half of the water. This mixture is stirred and the
aluminum source (Alipro or CATAPAL) added. The
resulting mixture is blended until a homogeneous mixture
is observed. The LUDOX-LS is then added to the
resulting mixture and the new mixture blended until a
homogeneous mixture is observed. The cobalt source
(e.g., Co(Ac)2, Co(S04) or mixtures thereof) is
dissolved in the remaining water and combined with the
first mixture. The combined mixture is blended until a
homogeneous mixture is observed. The organic templating
agent is added to this mixture and blended for about two
to four minutes until a homogeneous mixture is observed.
The resulting mixture (final reaction mixture) is placed
in a lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150-C,
200-C or 225-C) for a time. Digestions are typically
D-14643
- 54 - 1336717
carried out at the autogenous pressure. The
products are removed from the reaction vessel and
cooled.
ZnAPSO MOLECULAR SIEVES
The ZnAPSO molecular sieves of Canadian
Patent No. 1248079 comprise framework structures of
Zn2 -2, AlO2 -, PO2 + and SiO2 tetrahedral units
having an empirical chemical composition on an
anhydrous basis expressed by the formula:
mR : (ZnwAlxPysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; ~'m" represents the molar amount of "R~'
present per mole of (ZnwAlxPySiz)O2 and has a value
of zero to about 0.3; and "w", "x", "y" and "z"
represent the mole fractions of zinc, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides and each has a value of at least
0.01. The mole fractions "w", "x", "y" and "z" are
generally defined being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
D-14643
-
.
_55_- 1336717
.
In a preferred subcIass of ZnAPSO molecular
sieves the values "w", "x", "y" and "z" in the above
formula are within the limiting compositional values or
points as follows:
Mole Fraction
Point x - y (z + w)
a 0.55 0.43 0.02
b 0.43 0.55 0.02
c 0.10 0.55 0.3S
d O.S5 0.10 0.35
ZnAPSO compositions are generally synthesized
by hydrothermal crystallization at effective process
conditions from a reaction mixture containing active
sources of zinc, silicon, aluminum and phosphorus,
preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element or Group VA of the Periodic Table, and/or
optionally an alkali of other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure, at a temperature between 50C and
250-C, and preferably between lOO-C and 200-C until
crystals of the ZnAPS0 product are obtained, usually a
period of from several hours to several weeks.
Generally the effective crystallization period is from
D-14643
: 56- 1336717
about 2 hours to about 30 days with typical periods of
from about 4 hours to about 20 days being employed to
obtain ZnAPS0 products. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the ZnAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (ZnwAlxPysiz)2 bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
more preferably between about 2 and about 300; and "w",
"x", "y" and "z" represent the mole fractions of zinc,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01. In a preferred embodiment
the reaction mixture is selected such that the mole
fractions "w", "x", "y" and "z" are generally defined as
being within the limiting compositional values or points
as follows:
D-14643
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with
respect to the total of "w", "x", "y" and "z" such
that (w + x + y + z) = 1.00 mole. Molecular sieves
containing zinc, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
Preparative Reaqents
ZnAPSO compositions are typically prepared
using numerous reagents. Reagents which may be
employed to prepare ZnAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the trademark
of DuPont for an aqueous solution of
30 weight percent SiO2 and 0.1 weight
percent Na2O;
(c) CATAPAL: Trademark of Condea
Corporation for hydrated
pseudoboehmite;
D-14643
` 1336717
58-
(d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e) -ZnAc: Zinc Acetate, Zn(C2H3O2)2.4H2O;
(f) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide: -
(g) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(h) TMAOH: Tetramethylammonium hydroxide
pentahydrate, (CH3)4NOH.5H2O;
(i) TPAOH: 40 weight percent aqueous solution
of tetrapropylammonium hydroxide,
(C3H7)4NOH;
(j) Pr2NH: di-n-propylamine, (C3H7)2NH;
(k) Pr3N: Tri-n-propylamine, (C3H7)3N;
(1) Quin: Quinuclidine, (C7H13N);
(m) C-hex: cyclohexylamine; and
(n) DEEA: diethylethanolamine,
( C2H5 ) 2NC2H50H .
Pre~arative Procedure
ZnAPSO compositions are typically prepared by
forming reaction mixtures having a molar composition
expressed as:
eR:fzno:gAl2o3 hp2os isio2 jH2o
wherein e, f, g, h, i and j represent the moles of
template R, zinc (expressed as the oxide), Al2O3, P2O5
(H3PO4 expressed as P2O5), SiO2 and H2O, respectively.
D-14643
133S717
The reaction mixtures are generally
prepared by forming a starting reaction mixture
comprising the H3PO4 and a portion of the water.
This mixture is stirred and the aluminum source
added. The resulting mixture is blended until a
homogeneous mixture is observed. The LUDOX LS is
then added to the resulting mixture and the new
mixture blended until a homogeneous mixture is
observed. The zinc source (zinc acetate) is
dissolved in the remaining water and combined with
the first mixture. The combined mixture is blended
until a homogeneous mixture is observed. The
organic templating agent is added to this mixture
and blended for about two to four minutes until a
homogeneous mixture is observed. The resulting
mixture (final reaction mixture) is placed in a
lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at an effective
temperature for an effective time. Digestions are
typically carried out under autogenous pressure.
The products are removed from the reaction vessel
and cooled.
FeAPSO MOLECULAR SIEVES
The FeAPSO molecular sieves of U.S. Patent
No. 4,683,217 have three-dimensional microporous
crystal framework structures of FeO2-2, (and/or
FeO2~), A102 ~, PO2 + and SiO2 tetrahedral units,
and having a unit empirical formula, on an anhydrous
basis, of:
D-14643
~,
-60- 1336717
w x y iZ)02
~ wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the moles of "R" present per mole of
(FewAlxPySiz)O2 and has a value of from zero (0) to
about 0.3; the maximum value of "m" in each case depends
upon the molecular dimensions of the templating agent
and the available void volume of the pore system of the
particular molecular sieve involved; and "w", "x", "y"
and "z" represent the mole fractions of iron, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides, said mole fractions being such that
they are within the limiting compositional values or
points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
D-14643
`~ -61- 1336717
- The values of w, x, y and z may be as follows:~-
- -Mole Fraction
Point x y (z + w)
a 0.55 0.43 0.02
$ b 0.43 0.55 0.02
c 0.10 0.55 0.35
d 0.55 0.10 0.35
The FeAPSOs of the instant invention are
generally synthesized by hydrothermal crystallization
from a reaction mixture comprising reactive sources of
iron, aluminum, phosphorus and silicon, and preferably
one or more organic templating agents. Optionally,
alkali or other metal(s) may be present in the reaction
mixture and may act as templating agents. The reaction
mixture is generally placed in a pressure vessel,
preferably lined with an inert plastic material, such as
polytetrafluoroethylene, and heated, preferably under
autogenous pressure, at an effective temperature which
is generally between about 50-C and about 2S0-C, and
preferably between about 100-C and 200-C, until crystals
of the FeAPSO product are obtained, usually a period of
from several hours to several weeks. Molecular sieves
containing iron, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are typically prepared
as follows:
D-14643
-62- 1336717
- Preparative Reagents ~- -
- FeAPSO compositions may be prepared using
numerous reagents. Reagents which may employed to
prepare FeAPSOs include: .
(a) Alipro: aluminum isopropoxide,
Al(ocH(cH3)2)3;
(b) LUDOX-LS: LUDOX-LS is the trademark of Du
Pont for an aqueous solution of 30 weight
percent SiO2 and 0.1 weight percent Na2O;
(c) CATAPAL: trademark for hydrated aluminum
oxide containing about 75 wt. percent
A12O3 (pseudoboehmite phase~ and about
25 wt. percent water;
(d) Fe(Ac)2: Iron (II) acetate;
(e) FeSO4: Iron (II) sulfate hexahydrate;
(f) H3PO4: 8S weight percent phosphoric acid
in water;
(g) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(h) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(i) Pr2NH: di-n-propylamine ((C3H7)2NH);
(j) Pr3N: tri-n-propylamine ((C3H7)3N);
(k) Quin: Quinuclidine (C7H13N);
(1) MQuin: Methyl Quinuclidine hydroxide
(C7H13NCH3OH);
D-14643
63- 1336717
(m) TMAOH: tetramethylammonium hydroxide
~pentahydrate; and
(o) C-hex: cyclohexylamine.
Preparative Procedures
a) Reaction mixtures to prepare FeAPSOs are
typically prepared by grinding an aluminum isopropoxide
in a blender followed by slowly adding a H3PO4 solution
with mixing. A solution/dispersion of iron acetate in
water is added and then a silica (e.g., LUDOX-LS) is
added. The organic templating agent is then added to
this mixture, or in some cases one-half of this mixture,
and the mixture blended to form a homogeneous mixture.
For example, in one embodiment, the number of moles of
each component in the reaction mixture is as follows:
15Com~onent Moles
12 3
P205 0 . 9
sio2 0.2
FeO* 0.2
20 TEAOH 1.0
H20 50
* Iron (II) acetate reported as Iron (II) oxide.
The reaction mixture is sealed in a stainless
steel pressure vessel lined with polytetrafluoroethylene
and heated in an oven at a temperature, time and under
autogenous pressure. The solid reaction product is
D-14643
-64- 13~6717
recovered by filtration, washed with water and dried at
room temperature.
b) In another embodiment, reaction mixtures
are prepared by grinding the aluminum isopropoxide in a
blender followed by addition of a solution/dispersion of
iron(II) acetate. H3PO4 is added to this mixture and
the resulting-mixture blended to form a homogeneous
mixture. A silica (e.g., LUDOX-LS) is added to this
mixture except that in some instances the silica may be
added with the H3PO4. The resulting mixtures were
blended until a homogeneous mixture is observed.
Organic templating agent is added to each mixture and
the resulting mixtures placed in a stainless steel
pressure vessel lined with polytetrafluoroethylene and
heated, washed and the product recovered. In this
embodiment the number of moles of each component in the
reaction mixture is as follows:
Com~onent Moles
A123 . 9
20 P2O5
SiO2 0.2
FeO* 0.2
Template 1.0
H2O 50
* Iron(II) acetate reported as Iron(II) oxide.
D-14643
- 65 -
OUINARY MOLECULAR SIEVES 1 3 3 6 717
The QuinAPSO quinary molecular sieves of
Canadian Patent No. 1248080 and U.S. Patent No.
4,741,892 have three-dimensional microporous
framework structures of MO2n, AlO2-, PO2+ and SiO2
tetrahedral units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (MWAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of ~R~
present per mole of (MwAlxPySiz)O2 and has a value
of from zero (0) to about 0.3; M represents at least
two elements selected from the group consisting of
arsenic, beryllium, boron, chromium, cobalt,
gallium, germanium, iron, lithium, magnesium,
manganese, titanium, vanadium and zinc; and "w",
~x", ~y~ and ~'z~ represent the mole fractions of M,
aluminum, phosphorus and silicon, respectively,
present as tetrahedral oxides. Preferably, M
represents the combination of cobalt and manganese.
The mole fractions "w", "x", "y", and "z" are
generally defined as being within the limiting
compositional values or points as follows:
D-14643
. . ,
-66- 13367 17
Mole Fraction
Point x ~ y (z + w)
A - 0.60 - 0.37 0.03
B 0.37 0.60 0.03
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
Preferably the mole fractions w, x, y and z
will fall within the limiting compositional values or
points as follows:
Mole Fraction
Point x y (z + w)
a 0.60 0.37 0.03
b 0.37 0.60 0.03
15 .c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0-.01 0.39
QuinAPSO compositions are generally
synthesized by hydrothermal crystallization from a
reaction mixture containing reactive sources of the
elements M, aluminum, phosphorus and silicon and
preferably an organic templating agent, i.e.,
structure-directing, agent. The structure-directing
agents are preferably a compound of an element of Group
VA of the Periodic Table, and may be an alkali or other
D-14643
-67- 1336717
metal. The reaction mixture is generally placed in a
sealed pressure vessel, preferably lined with an inert
plastic material such as polytetrafluoroethylene and
heated, preferably under autogenous pressure and at
typical effective temperatures between 50-C and 250DC,
preferably between 100C and 200-C, until crystals of
the QuinAPS0 product are obtained, usually over a period
of-from several hours to several weeks. Typical
effective crystallization times are from about 2 hours
to 30 days with from about 4 hours to about 20 days
being generally employed to obtain QuinAPS0 products.
The product is recovered by any convenient method such
as centrifugation or filtration.
In synthesizing the QuinAPS0 compositions, it
is preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (MwAlxpysiz)o2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "w", "x",
"y", and "z" represent the mole fractions of elements M,
2S aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
D-14643
- 68 - 1336717
In one embodiment the reaction mixture is
selected such that the mole fractions'"w", 'ix", "y"
and 'oz" are generally defined as being within tee
limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.37 0.03
G 0.37 0.60 0.03
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with
respect to the total of ~w,~x~ y~ and "z" such
that (w + x + y + z) = 1.00 mole. QuinAPSO
compositions were prepared using numerous regents;
the appropriate sources of the various elements M
are the same as those used in the preparation of the
various APO and APSO molecular sieves containing the
same elementsl as described in detail above and
below.
Reagents which may be employed to prepare
QuinApSOs include:
(a) Alipro: aluminum isopropoxide,
(b) LUDOXLS: LUDOX-LS is the trademark
name of DuPont for an aqeuous solution
of 30
D-14643
t ~ ~
.,~
9 1336717
weight percent SiO2 and 0.1 weight
percent Na20;~
(c) H3PO4: 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate,
Mn(C2H302)2.4H20 (for QuinAPSOs
containing manganese);
(e) CoAc: Cobalt Acetate, Co(C2H302)2.4H20
(for QuinAPSOs containing cobalt);
(f) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide; and
(g) Pr2NH: di-n-propylamine, (C3H7)2NH.
Pre~arative Procedures
QuinAPSOs may be prepared by forming a
starting reaction mixture by adding H3PO4 and one half
of the quantity of water. To this mixture an aluminum
isopropoxide is added. This mixture is then blended
until a homogeneous mixture is observed. To this
mixture a silica (e.g., LUDOX-LS) is added and the
resulting mixture blended (about 2 minutes) until a
homogeneous mixture is observed. A second mixture is
prepared using manganese acetate (or a appropriate
source of another element M) and one half of the
remaining water. A third mixture is prepared using
cobalt acetate (or a appropriate source of another
element M) and one half of the remaining water. The
three mixtures are admixed and the resulting mixture
D-14643
- 70 -
blended until a homogeneous mixture is obsle~v~.717
The organic templating agent is then added to the
resulting mixture and the resulting mixture blended
until a homogeneous mixture is observed, i . e.,
about 2 to 4 minutes. The pH of the mixture is
measured and adjusted for temperature. The mixture
is then placed in a lined (polytetrafluoroethylene)
stainless steel pressure vessel and digested at an
effective temperature for an effective time.
Digestions are typically carried out under
autogenous pressure.
CoMnMqAPSO MOLECULAR SIEVES
The CoMnMgAPSO senary molecular sieves have
three-dimensional microporous framework structures
f C2 2, MnO2~2, Mgo2 2, A102, PO2 and SiO2
tetrahedral oxide units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (CotMnuMgvAlxPysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R~
present per mole of (CotMnuMgvAlxPySiz)02 and has a
value of from zero (0) to about 0.3; "t", "u", and
"v", "x", "y" and "z" represent the mole fractions
of cobalt, manganese, magnesium, aluminum,
phosphorus and silicon,
-71- 1336717
respectively, present as tetrahedral oxides and each has
a value of at least 0.01. The mole fractions "t", "u",
"v", "x", "y" and "z" are generally defined as being
within the limiting compositional values or points as
follows (where w = t + u + v):
Mole Fraction
Point x y (z + w)
A 0.60 0.36 0.04
B 0.36 0.60 0.04
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the CoMnMgAPSO
molecular sieves the values of "w", "x", "y" and "z" in
lS the above formula are within the limiting compositional
values or points as follows:
Mole Fraction
Point x y ~z + w)
a 0.55 0.41 0.04
b 0.41 0.55 0.04
c 0.10 0.55 0.35
d 0.55 0.10 0.35
D-14643
-72- 1336717
~ CoMnMgAPS0 compositions are generally
synthesized by hydrothermal~crystallization from a
reaction mixture containing reactive sources of cobalt,
manganese, magnesium, aluminum, phosphorus and silicon,
and preferably an organic templating agent, i.e.,
structure-directing, agent. The structure-directing
agents are prçferably a compound of an element of Group
VA of the Periodic Table, and/or optionally an alkali or
other metal. The reaction mixture is generally placed
in a sealed pressure vessel, preferably lined with an
inert plastic material such as polytetrafluoroethylene
and heated, preferably under autogenous pressure at a
temperature between 50-C and 250-C, and preferably
between lOO-C and 200-C, until crystals of the
CoMnMgAPSO product are obtained, usually over a period
of from several hours to several weeks. Typical
crystallization times are from about 2 hours to about 30
days with from about 4 hours to about 20 days generally
being employed to obtain CoMnMgAPSO products. The
product is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the CoMnMgAPS0 compositions,
it is preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (COtMnuMgvAlxpysiz)o2 2
D-14643
~73~ 1336717
wherein "R" is an organic templating agent; "a" is the
amount of organic templating~agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
5 about 6 and more preferably from greater than zero to
about 2; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "t", "u",
"v", "x", "y", and n Z 1~ represent the mole fractions of
cobalt, manganese, magnesium, aluminum, phosphorus and
10 silicon, respectively, and each has a value of at least
0.01.
In a preferred embodiment the reaction mixture
is selected such that the mole fractions "w", "x", "y"
and "z", where "w" is the sum of "t" + "u" + "v", are
15 generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.36 0.04
G 0.36 0.60 0.04
H 0.01 0060 0.39
- I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
25 composition, the reactants are normalized with respect
to the total of "t", "u", "v", "x", "y" and "z" such
D-14643
- 74 - 1336717
that (t + u + v + x + y + z) = 1.00 mole. Molecular
sieves containing cobalt, manganese, magnesium,
aluminum, phosphorus and silicon as framework
tetrahedral oxide units are prepared as follows:
Preparative Reaqents
CoMnMgAPSO compositions may be prepared by
using numerous reagents. Reagents which may be
employed to prepare CoMnAPSO include:
(a) Alipro: aluminum isopropoxide;
~b) LUDOX-LS: LUDOX-LS is the trademark of
DuPont for an agueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(c) H3PO4: aqueous solution which is 85
weight percent phosphoric acid;
(d) MnAc: Manganese acetate,
Mn(C2H302)2-4H20;
(e) CoAc: Cobalt Acetate, Co(C2H302)2-4H20;
(f) MgAc: Magnesium Acetate Mg(C2H302)-4H20;
(g) TEAOH: 40 weight percent agueous
solution of tetraethylammonium
hydroxide; and
(h) Pr2NH: di-n-propylamine, (C3H7)2NH.
Preparative Procedures
CoMnMgAPSOs may be prepared by forming a
starting reaction mixture by adding H3PO4 and one
half of the quantity of water. To this mixture
analuminum isopropoxide is added. This mixture is
then blended
D-14643
-75- 1336717
until a homogeneous mixture is observed. To this
mixture a silica (e.g., LUDOX-LS) is added and the
resulting mixture blended (about 2 minutes) until a
homogeneous mixture is observed.
Three additional mixtures are prepared
using cobalt acetate, magnesium acetate and
manganese acetate using one third of the remainder
of the water for each mixture. The four mixtures
are then admixed and the resulting mixture blended
until a homogeneous mixture is observed. An organic
templating agent is then added to the resulting
mixture and the resulting mixture blended until a
homogeneous mixture is observed, i.e., about 2 to 4
minutes. The mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature for a time.
Digestions are typically carried out under
autogenous pressure.
SenAPSO MOLECULAR SIEVES
The SenAPSO molecular sieves have
three-dimensional microporous framework structures
of Mo2n, A102-, PO2+ and SiO2 tetrahedral oxide
units, where "n" is -3, -2, -1, 0 or +1, and have an
empirical chemical composition on an anhydrous basis
expressed by the formula:
mR : (MWAlxpysiz)o2
D-14643
~'
.~
1336717
.76-
wherein "R" represents at least one organic templating
agent present in the intracrystalline~pore system; "m"
represents the molar amount of "R" present per mole of
(MwAlxPySiz)02r and has a value of from zero to about
0.3; "M" represents three elements selected from the
group consisting of arsenic, beryllium, boron, chromium,
cobalt, gallium, germanium, iron, lithium, magnesium,
manganese, titanium, vanadium and zinc; "n" may have the
aforementioned values depending upon the oxidation state
of "M"; and "w", "x", "y" and "z" represent the mole
fractions of elements "M", aluminum, phosphorus and
silicon, respectively, present as tetrahedral oxides.
The mole fractions "w", "x", "y" and "z" are generally
defined as being within the limiting compositional
values or points as follows, wherein "w" denotes the
combined mole fractions of the three elements "M" such
that "w" = "wl" + "w2" + "w3'l and each element "M" has a
mole fraction of at least 0.01:
Mole Fraction
20 Point x y (z + w)
A 0.60 0.36 0,04
B 0.36 0.60 0.04
C 0.01 0.60 0.39
D 0.01 0.01 0c98
E 0.60 OoOl 0u39
D-14643
_-77_ 1336717
In a preferred subclass of the SenAPSO
molecular sieves the values of "w", "x", "y" and "z" in
the above formula are within the limiting compositional
values or points as follows:
Mole Fraction
Point ` x y (z + w)
a 0.60 0.36 0.04
-b 0.36 0.60 0.04
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
SenAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
lS containing reactive sources of elements "M", aluminum,
phosphorus and silicon, and preferably an organic
templating, i.e., structure-directing, agent. The
structure-directing agents are preferably a compound of
an element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between 50 C and
250-C, and preferably between lOO-C and 200-C, until
crystals of the SenAPSO product are obtained, usually
D-14643
1336717
~ 78-
over a period of from several hours to several weeks.
Typical crystallization time~s are from about 2 hours to
about 30 days with from about 4 hours to about 20 days
generally being employed to obtain SenAPS0 products.
The product is recovered by any convenient method such
as centrifugation or filtration.
In synthesizing the SenAPSO compositions, it
is preferred to~employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (MwAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6 and more preferably from greater than zero to
about 2; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "w", "x",
"y", and "z" represent the mole fractions of elements
"M", aluminum, phosphorus and silicon, respectively, and
each has a value of at least 0.01, with the proviso that
each "M" is present in a mole fraction of at least 0.01.
In a preferred embodiment the reaction mixture
is selected such that the mole fractions "w", "x", "y"
and "z" are generally defined as being within the
limiting compositional values or points as follows:
D-14643
_79 1336717
Mole Fraction
Point x ` y (z + w~
F 0.60 0.36 0.04
G 0.36 0.60 0.04
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that (w + x +
y + z) = 1.00 mole. The SenAPSO molecular sieves are
prepared by preparative techniques, and using sources of
the elements "M" similar to those described for the
other APSO molecular sieves described above and below.
. AsAPSO MOLECULAR SIEVES
The AsAPSO molecular sieves of U.S. Serial No.
599,808, filed April 13, 1984, and U.S. Serial No.
845,484 filed March 31, 1986 have a framework structure
of AsO2n, AlO2 , PO2+ and SiO2 tetrahedral units having
an empirical chemical composition on an anhydrous basis
expressed by the formula:
mR : (AswAlxPySiz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(AswAlxPySiz)O2 and has a value of zero to about 0.3,
D-14643
1336717
-80- -
but is preferably not greater than o.i5; and "w", "x",
"y" and "z" represent the mole fractions of the elements
arsenic, aluminum, phosphorus and silicon, respectively,
present as tetrahedral oxides. The mole fractions "w",
"x", "y" and "z" are generally defined as being within
the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the AsAPS0
molecular sieves, the values of w, x, y and z are as
follows:
Mole Fraction
Point x y (z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
D-14643
- -81~ 67 17
In an especially preferred su~class of the
AsAPSO molecular sieves, the~values of w, x, y and z are
as follows:
- Mole Fraction
5 Point x ~ (z + w)
g 0.50 0.40 0.10
h 0.42 0.48 0.10
i 0.38 0.48 0.14
j 0.38 0.37 0.25
k 0.45 0.30 0.25
1 0.50 0.30 0.20
AsAPS0 compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of arsenic, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50-C and about 250-C, and preferably
between about lOO-C and about 200-C until crystals of
the AsAPSO product are obtained, usually a period of
from several hours to several weeks. Typical effective
D-14643
1336717
.-82
~ times of from 2 hours to about 30 days, generally from
~ about 12 hours to about 10 d~ays, have been observed.
The product is recovered by any convenient method such
as centrifugation or filtration.
In synthesizing the AsAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (AswAlxPySiz)o2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 1.0;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 60; and "w", "x", "y"
and "z" represent the mole fractions of arsenic,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
D-14643
1336717
83
Mole Fraction
Point x ~ y ~ (z + w)
F 0.60 0.38 . 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especialiy preferred reaction mixtures are
those containing from about 1 to about 2 total moles of
silicon and arsenic, and from about 1 to about 2 moles
of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of-"w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing arsenic, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
Preparative Reaqents
AsAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare AsAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation
for hydrated pseudoboehmite;
D-14643
-84- 1336717
(c) LUDOX-LS: LUDOX-LS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3PO4 : 85 weight percent aqueous
phosphoric acid;
(e) As205, arsenic(V) oxide;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
Preparative Procedures
AsAPSOs may be prepared by forming a
starting reaction mixture by dissolving the
arsenic(V) oxide and the H3PO4 in at least part of
the water. To this
D-14643
~,
",, ~,
-8S- 1~36717
solution the aluminum isopropoxide or CATAPAL is
added. This mixture is then blended until a
homogeneous mixture is Observed. To this mixture
the templating agent and then the silica is added
and the resulting mixture blended until a
homogeneous mixture is observed. The mixture is
then placed in a lined (polytetrafluoro-ethylene)
stainless steel pressure vessel and digested at a
temperature (150C or 200C) for a time or placed in
lined screw top bottles for digestion at 100C.
Digestions are typically carried out under
autogenous pressure.
BAPSO MOLECULAR SIEVES
The BAPSO molecular sieves have a framework
structure of BO2-, AlO2-, PO2+ and SiO2 tetrahedral
units having an empirical chemical composition on an
anhydrous basis expressed by the formula:
Mr : (BWAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of ~'R"
present per mole of (BwAlxPySiz)O2 and has a value
of zero to about 0.3, but is preferably not greater
than 0.15; and "w", "x", "y" and "z" represent the
mole fractions of the elements boron, aluminum,
phosphorus and silicon, respectively,
D-14643
~ -86- 1336717
present as tetrahedral oxides. The mole fractions "w",
"x", "y" and "z" are generally defined as being within
the limiting compositional values or points as follows:
Mole Fraction
5 Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the BAPS0 molecular
sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e - 0.39 0.01 0.60
f 0.60 0.01 0.39
In an especially preferred subclass of the
BAPSO molecular sieves, the values of w, x, y and z are
as follows:
D-14643
1336717
-87-
- - - Mole Fraction
Point x ~ y (z +-w)
g 0.51 0.42 0.07
h 0.45 0.48 0.07
i 0.33 0.48 0.19
j 0.33 0.38 0.29
k 0.36 0.35 0.29
1 0.51 0.35 0.14
BAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of boron, silicon, aluminum
and phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50C
20 and about 250-C, and preferably between about 100C and
about 200-C until crystals of the BAPSO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 4 hours to about
20 days, have been observed. The product is recovered
D-14643
1336717
-88- -
by any convenient method such as centrifugation or
filtration. ~ -
In synthesizing the BAPS0 compositions, it ispreferred to employ a reaction mixture composition
S expressed in terms of the molar ratios as follows:
w x y z) 2 2
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20; and "w", "x", "y"
and "zf' represent the mole fractions of boron, aluminum,
phosphorus and silicon, respectively, and each has a
value of at least 0.01.
In one embo~ nt the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
D-14643
1336717
-89-
~ Mole Fraction
Point x ~ y (z + w)
- F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especialiy preferred reaction mixtures are
those containing from about 1.0 to about 2 total moles
of silicon and boron, and from about 0.75 to about 1.25
moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing boron, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
Preparative Reagents
BAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare BAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation
Z5 for hydrated pseudoboehmite;
D-14643
-90- 1336717
(c) LUDOX-LS: LUDOX-LS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3PO4 : 85 weight percent aqueous
phosphoric acid;
(e) H3BO3, boric acid, and trialkyl borates;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
Preparative Procedures
BAPSOs may be prepared by forming a
starting reaction mixture by dissolving aluminum
isopropoxide in an alcohol such as isopropanol,
adding the H3PO4 and
D-14643
9l 1336717
recovering the solid which precipitates. This solid
is then added to water, and trialkylborate (for
example trimethyi borate added, followed by silica
and the templating agent. This mixture is then
blended until a homogeneous mixture is observed.
The mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
BeAPSO MOLECULAR SIEVES
The BeAPSO molecular sieves of U.S. Patent
No. 4,737,353 have a framework structure of BeO2~2,
AlO2-,AlO2-, PO2+ and SiO2 tetrahedral units having
an empirical chemical composition on an anhydrous
basis expressed by the formula:
mR : (BewAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (BewAlxPySiz)O2 and has a value
of zero to about 0.3, but is preferably not greater
than 0.15; and "w", "x", "y" and "z" represent the
mole fractions of the elements beryllium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides. The mole
D-14643
1336717
-92-
fractions "w", "x", "y" and "z" are generally defined
as being within the limiting~compos~itional values or
points as~follows:
Mole Fraction
5 Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the BeAPS0
molecular sieves, the values of w, x, y and z are as
follows:
Mole Fraction
15 Point x y (z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
BeAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of beryllium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
D-14643
-93_ 1336717
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vesse}, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50C and about 250-C, and preferably
between about lOO-C and about 200-C, until crystals of
the BeAPSO product are obtained, usually a period of
from several hours to several weeks. Typical effective
times of from 2 hours to about 30 days, generally from
about 4 hours to about 20 days, have been observed, with
from 1 to 10 days being preferred. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the BeAPSO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (BewAlxpysiz)o2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
D-14643
-94~ 133 6~17
preferably not greater than about 20; and "w", "x", "y"
and "z" represent the mole fractions of ~eryllium,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
10 Point x y ~z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing beryllium, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follows:
Preparative Reagents
BeAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare BeAPSOs include:
D-14643
-95-
(a) Alipro: aluminum isopropoxi~;3 6 71 7
(b) CATAPAL: Trademark of Condea
Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3PO4 : 85 weight percent aqueous
phosphoric acid;
(e) beryllium sulfate, BeSO4;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) Mquin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEBA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
D-14643
- 96 -
Preparative Procedures ¦ 3 3 6 717
BeAPsos may be prepared by forming a
starting solution by mixing H3PO4 in at least part
of-the water. To this solution is added beryllium
sulfate (or another beryllium salt) and the
resultant mixture stirred until a homogeneous
solution is obtained. To this solution may be added
successively the aluminum oxidel the silica and the
templatingagent, with the mixture being stirred
between each addition until it is homogeneous. The
mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
CAPSO MOLECULAR SIEVES
The CAPSO molecular sieves of and U.S.
Patent No. 4,738,837 have a framework structure of
CrO2n, A102-, PO2-, PO2+ and SiO2 tetrahedral units
(where "n" is -1, 0 or +1) having an empirical
chemical composition on an anhydrous basis expressed
by the formula:
mR : (crwAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m"
D-14643
. .
-9-7- 1336717
~ represents the molar amount of "R" present per-mole of
~ (CrwAlxPySiz)02 and has a value of zero to ab~ut 0.3,
but is preferably not greater than 0.15; and "w", "x",
"y" and "z" represent the mole fractions of the elements
S chromium, aluminum, phosphorus and silicon,
respectively, present as tetrahedral oxides. The mole
fractions "w", "x", "y" and "z" are generally defined as
being within the limiting compositional values or points
as follows:
Mole Fraction
Point x y rz + w~
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the CAPS0 molecular
sieves, the values of w, x, y and z are as follows:
Mole Fraction
20 Point x y (z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
D-14643
98- 1336717
In an especially preferred subclass of the
CAPS0 molecular sieves, the values of x and y in the
above formula are each within the range of about 0.4 to
0.5 and (z + w) is in the range of about 0.02 to 0.15.
Since the exact nature of the CAPSO molecular
sieves is not clearly understood at present, although
all are believed to contain CrO2 tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the CAPS0
molec~lar sieves by means of their chemical composition.
This is due to the low level of chromium present in
certain of the CAPSO molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction between chromium, aluminum,
phosphorus and silicon. As a result, although it is
believed that CrO2 tetrahedra are substituted
isomorphously for A102, PO2 or SiO2 tetrahedra, it is
appropriate to characterize certain CAPSO compositions
by reference to their chemical composition in terms of
the mole ratios of oxides.
CAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of chromium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
D-14643
` _99_ 1 3 3 6717
Table, and/or optionally an alkali or other metal. The
reaction mixture is generalLy placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50-C and about 250-C, and preferably
between about lOO-C and about 200-C, until crystals of
the CAPS0 product are obtained, usually a period of from
several hours to several weeks. Typical effective times
of from 2 hours to about 30 days, generally from about 4
hours to about 20 days, and preferably about 1 to about
10 days, have been observed. The product is recovered
by any convenient method such as centrifugation or
filtration.
In synthesizing the CAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (CrwAlxPysiz )2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20; and "w", "x", "y"
D-14643
-loo- 1336717
and "z" represent the mole fractions of chromium,
aluminum, phosphorus and silïcon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y (z + w~
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especially preferred reaction mixtures are
those containing from about 0.3 to about 0.5 total moles
of silicon and chromium, and from about 0.75 to about
1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", -y" and "z" such that
(w + x + y + z) = l.00 mole. Molecular sieves
containing chromium, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
D-14643
- 101 -
PreParative Reagents 13 3 6 717
CAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed
to prepare MnAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea
Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e) chromium acetate, and chromium acetate
hydroxide;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
D-14643
,, ~
-102- 1336717
(n) TPAOH: tetrapropylammonium hydroxide; and
~ (o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
Preparative Procedures
CAPSOs may be prepared by forming a starting
solution by dissolving H3PO4 in at least part of the
water. To this solution the aluminum isopropoxide is
added. This mixture is then blended until a homogeneous
mixture is observed. To this mixture the silica, the
chromium acetate or chromium acetate hydroxide and the
templating agent are successively added and at each step
the resulting mixture is blended until a homogeneous
mixture is observed.
Alternatively, the water and aluminum
isopropoxide may first be mixed, and then the silica,
the chromium acetate or chromium acetate hydroxide, the
phosphoric acid and the templating agent added, and
again at each step the resulting mixture is blended
until a homogeneous mixture is observed.
In either case, the mixture is then placed in
a lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150-C or
200-C) for a time or placed in lined screw top bottles
for digestion at 100-C. Digestions are typically
carried out under autogenous pressure.
D-14643
-103- 1 3~6717
GaAPSO MOLECULAR SIEVES
The GaAPSO molecular sieves of U.S. Patent
No. 4,735,806 have a framework structure of GaO2-,
AlO2-, PO2+ and SiO2 tetrahedral units having an
empirical chemical composition on an anhydrous basis
expressed by the formula:
mR : (GaWAlxpysiz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (GawAlxPySiz)O2 and has a value
of zero to about 0.3, but is preferably not greater
than 0.2; and "w", "x", "y" and "z" represent the
mole fractions of the elements gallium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides. The mole fractions "w", "x",
"y" and "z" are generally defined as being within
the limiting compositional values or points as
follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
D-14643
..~. -,
1336717
-104-
- In-a preferred subclass of the GaAPS0
molecular sieves, the values of w, x, y and z are a~
follows:
Mole Fraction
`5 Point x y (z.+ w~
a 0.60 0.38 0.02
b 0.38 0.60 0.02
-c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
In an especially preferred subclass of the
GaAPSO molecular sieves, the values of w, x, y and z are
as follows:
Mole Fraction
Point x y (z + w)
g 0.45 0.40 0.15
h 0.33 0.52 0.15
i 0.20 0.52 0.28
j 0.20 0.45 0.35
k 0.36 0 29 0.35
1 0.45 0.29 0.26
GaAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of gallium, silicon,
aluminum and phosphorus, preferably an organic
D-14643
-105- 1336717
templating, i~.e., structure-directing, agent, preferably
a compound of an element of 6roup VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50-C and about 250-C, and preferably
between about lOO-C and about 200-C, until crystals of
the GaAPS0 product are obtained, usually a period of
from several hours to several weeks. Typical effective
times of from 2 hours to about 30 days, generally from
about 4 hours to about 20 days, and preferably about 2
to about 15 days, have been observed. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the GaAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (GaWAlxPysiz)o2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 1.0;
"b" has a value of from zero (0) to about 500,
~-14643
-106- 1336717
preferably between about 2 and about 300, most
preferably not greater than ~about 20; and "w", "x"-, "y"
and "z" represent the mole fractions of gallium,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y ~z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especially preferred reaction mixtures are
those containing from about 0.5 to about 1.0 total moles
of silicon and gallium, and from about 0.75 about 1.25
moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing gallium, aluminum, phosphorus and silicon as
D-14643
-107- 1336717
framework tetrahedral oxide units are prepared as
follows:
Preparative Reaqents
GaAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare GaAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea
Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUOOX-lS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3P04 : 85 weight percent aqueous
phosphoric acid;
(e) gallium hydroxide, or gallium sulfate;
(f) TFAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
D-14643
. ~3 .
- -108- 1336717
~ (m~~ TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrap~ropyl~ammonium hydroxide-; and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
~ Preparative Procedures
GaAPSOs may be prepared by forming a starting
solution by dissolving the H3PO4 in at least part of the
water. To this solution the aluminum hydroxide or
isopropoxide is added. This mixture is then blended
until a homogeneous mixture is observed. -To this
mixture is added a second solution prepared by adding
silica to a solution containing the gallium hydroxide
and the templating agent and then the combined mixture
is blended until a homogeneous mixture is observed.
Alternatively, the templating agent may be
added to the solution containing the phosphoric acid and
water, and a solution of gallium sulfate in water added,
followed by successive additions of silica and aluminum
oxide and then the combined mixture is blended until a
homogeneous mixture is observed.
In either case, the mixture is then placed in
a lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150C or
200-C) for a time or placed in lined screw top bottles
D-14643
lOg- 1336717
for digestion at 100C. Digestions are typically
carried out under autogenous pressure.
GeAPSO MOLECULAR SIEVES
The GeAPSO molecular sieves have a
framework structure of GeO2, AlO2-, PO2+ and SiO2
tetrahedral units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (GewAlxpysiz)o2
wherein ~R~ represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R~
present per mole of (GewAlxPySiz)O2 and has a value
of zero to about 0.3, but is preferably not greater
than 0.15; and "w", "x", "y" and "z" represent the
mole fractions of the elements germanium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral oxides. The mole fractions "w", "x",
"y" and "z" are generally defined as being within
the limiting compositional values or points as
follows:
D-14643
- ` 1336717
--110-- -
- - ~ -- - Mole Fraction
Point _ ~ y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 - 0.01 0.98
E 0.60 0.01 0.39
. In.a preferred subclass of the GeAPSO
molecular sieves, the values of w, x, y and z are as
follows:
Mole Fraction
Point x y ~z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
. In an especially preferred subclass of the
GeAPSO molecular sieves, the values of w, x, y~and z are
as follows:
D-14643
3 6 7 1 7
- -- - Mole Fraction
Point x ~ y (z + w)
g 0.60 0.35 0.05
h 0.47 0.48 0.05
i 0.40 0.48 0.12
j 0.40 0.36 0.24
k 0.46 0.30 0.24
1 0.60 0.30 0.10
GeAPS0 compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of germanium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50-C and about 250C, and preferably
between about lOO-C and about 200-C until crystals of
the GeAPS0 product are obtained, usually a period of
from several hours to several weeks. Typical effective
times of from 2 hours to about 30 days, generally from
2s about 4 hours to about 20 days, and preferably about 12
hours to about 7 days have been observed. The product
D-14643
112- 1336717
is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the GeAPSO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (GewAlxPysiz)o2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20, and desirably not
greater than about 10; and "w", "x", "y" and "z"
represent the mole fractions of germanium, aluminum,
phosphorus and silicon, respectively, and each has a
value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
D-14643
-113- 1336717
- Mole Fraction
Point _ y (z + w)
. F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especially preferred reaction mixtures are
those containing from about 0.2 to about 0.3 total moles
of silicon and germanium, and from about 0.75 to about
1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = 1.00 mole. Molecular sieves
containing germanium, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follows:
Preparative Reaqents
GeAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare GeAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation
for hydrated pseudoboehmite;
D-14643
-114- 1336717
(c) LUDOX-LS: LUDOX-LS is the-trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na20;
(d) H3PO4 : 85 weight percent aqueous
phosphoric acid;
(e) germanium tetrachloride or germanium
ethoxide;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQquin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEBA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate;
(q) aluminum chlorhydrol.
D-14643
'?
..~ ~, .
-11S- 1336717
Preparative Procedures
In some cases, it may ba advantageous, when
syntheslzing the GeAPSO compositions, to flrst combine
sources of germanium and aluminum, or of germanium,
aluminum and silicon, to form a mixed germanium/aluminum
or germanium/aluminum/silicon compound (this compound
being typically a mixed oxide) and thereafter to combine
this mixed compound with a source of phosphorus to form
the final GeAPSO composition. Such mixed oxides may be
prepared for example by hydrolyzing aqueous solutions
containing germanium tetrachloride and aluminum
chlorhydrol, or germanium ethoxide,
tetraethylorthosilicate, and aluminum tri-sec-butoxide.
GeAPSOs may be prepared by forming a starting
solution by dissolving the H3PO4 in at least part of the
water. To this solution the aluminum isopropoxide or
CATAPAL is added. This mixture is then blended until a
- homogeneous mixture is observed. To this mixture the
templating agent and then a solution containing
tetraethylorthosilicate and germanium ethoxide, and the
resulting mixture blended until a homogeneous mixture is
observed.
Alternatively, the phosphoric acid may first
be mixed with the templating agent, and then a solution
containing tetraethylorthosilicate and germanium
ethoxide combined with the phosphoric acid/templating
D-14643
-116- 1336717
agent solution. Then the aluminum' oxide is added
and the resultant mixture blended until homogeneous.
In a third procedure, the phosphorlc acid
may first be mixed with the templating agent and
water, and to the resultant solution is added the
solid aluminum/silicon/germanium mixed oxide
prepared as described above. The resultant mixture
is then blended until homogeneous.
Whichever procedure is adopted, the final
mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
LiAPSO MOLECULAR SIEVES
The LiAPSO molecular sieves have a
framework structure of Lio2-3, AlO2-, PO2+ and SiO2
tetrahedral units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (LiWAlxpysiz)o2
wherein ~'R" represents at least one organic
templating agent present in the intracrystalline
pore system; ~'m" represents the molar amount of ~R~'
present per mole of
D-14643
.~, .
:-117-- 133~717
(LiwAlxPySiz)02 and has a value of-zero to about 0.3,
but is preferably not greater than O.15; and "w", "x",
''y" and "z" represent the mole fractions of the elements
lithium, aluminum, phosphorus and silicon, respectively,
present as tetrahedral oxides. The mole fractions "w",
"x", "y" and "z" are generally defined as being within
the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0098
E 0.60 0.01 0.39
In a preferred subclass of the LiAPSo
molecular sieves, the values of w, x, y and z are as
follows:
Mole Fraction
Point x y (z + w)
a 0.60 0~38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f . 0.60 0.01 0.39
D-14643
118- 1336717
- In an especially preferred subclass of the
LiAPSo molecular sieves, the value of WTZ is not greater
than about 0.20.
Since the exact nature of the LiAPSo molecular
S sieves is not clearly understood at present, although -
all are believed to contain Lio2 tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the LiAPSo
molecular sieves by means of their chemical composition.
This is due to the low level of lithium present in
certain of the LiAPo molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction between lithium, aluminum, phosphorus
and silicon. As a result, although it is believed that
Lio2 tetrahedra are substituted isomorphously for AlO2,
PO2 or SiO2 tetrahedra, it is appropriate to
characterize certain LiAPS0 compositions by reference to
their chemical composition in terms of the mole ratios
of oxides.
LiAPSO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of lithium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
D-14643
- 1336717
~119-- -
reaction mixture is generally placed in-a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between about 50-C and about 250C, and preferably
between about lOO-C and about 200-C until crystals of
the LiAPS0 product are obtained, usually a period of
from several hours to several weeks. Typical effective
times of from 2 hours to about 30 days, generally from
about 4 hours to about 20 days, and preferably about 1
to about 10 days, have been observed. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the LiAPSo compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (LiwAlxPySiz)O2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20, and most desirably
not greater than about 10; and "w", "x", "y" and "z"
D-14643
~-120- 1336717
represent the mole fractions of lithium,-aluminum,
phosphorus and silicon, respectively, and each has a
value of at-least 0.01.
In one embodiment the reaction mixture is
S selected such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
- Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w + x + y + z) = l.00 mole. Molecular sieves
containing lithium, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
Preparative Rea~ents
LiAPSo compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare LiAPSos include:
(a) Alipro: aluminum isopropoxide;
D-14643
-121- 1336717
(b) CATAPAL: Trademark of Condea Corporation for hydrated
pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the trademark of DuPont for an
aqueous solution of 30 weight percent SiO2 and 0.1
weight percent Na20;
(d) H3PO4: 85 weight percent aqueous phosphoric acidi
(e) lithium orthophosphate;
(f) TEAOH: 40 weight percent aqueous solution of
tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of
tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide, (C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.'
Preparative Procedures
LiAPSOs may be prepared by forming a starting
D-14643
~, ,
-122- 1336717
reaction mixture mixing lithium phosphate and
aluminum oxide, then adding the resultant mixture to
the H3P04. To the resultant mixture is added silica
and the templating agent and the resulting mixture
is blended until a homogeneous mixture is
observed. The mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
AlPO4 ALUMINOPHOSPHATE MOLECULAR SIEVES
The AlPO4 aluminophosphate molecular sieves
of U.S. Patent No. 4,310,440 are disclosed as
microporous crystalline aluminophosphates having an
essential crystal line framework structure whose
chemical composition, expressed in terms of molar
ratios of oxides, is:
A12O3: 0-8-1-2 P205-
The pores of the framework structure are uniform and in
each species have nominal diameters of from 3 to 10
Angstroms; the aluminophosphates have an
intracrystalline adsorption capacity for water at 4.6
Torr and 24C of at least 3.5 weight percent, the
adsorption of water being completely reversible while
D-14643
-123- 13~ 6717
retaining the same essential framework topology in both
the hydrated and dehydrated~state. By the ter~
"essential framework topology" is meant the spatial
arrangement of the primary Al-O and P-O bond linkages.
S No change in the framework topology indicates that there
is no disruption of these primary bond linkages.
The aluminophosphates are prepared by
hydrothermal crystallization of a reaction mixture
prepared by combining a reactive source of phosphate,
alumina and water and at least one structure-directing
or templating agent which can include an organic amine
and a quaternary ammonium salt. In the as-synthesized
form, the structure-directing agent is contained within
the framework structure of the aluminophosphate in
amounts which vary from species to species but usually
do not exceed one mole per mole of A1203 thereof. This
structure-directing agent is readily removed by water
washing or calcination and does not appear to be an
essential constituent of the aluminophosphate, as
evidenced by essentially complete absence of ion-
exchangeability of the as-synthesized compositions and
also the complete absence of any internally-contained
organic molecules in the as-synthesized form of at least
one species of the generic class. Evidence that
structure-directing agent is a critical constituent is
contained in certain of the Examples of the Patent
D-14643
- . ~
1336717
-124- ~
- 4,310,440, wherein reaction mixtures,~-otherwise
identical to those which yield the AlPO4 products except
for the presence of templating agents, yield instead the
previously known aluminophosphate phases AlPO4.I.I-1.3
H2O, AlPO4-tridymite, AlPO4-quartz and
AlPO4-cristobalite.
The AlPO4 aluminophosphates are prepared by
forming a reaction mixture which contains, in terms of
molar ratios of oxides:
A12O3 : 0.5-1.5 P2O5 :7-100 H2O
and contains from about 0.2 to 2.0 moles of templating
agent per mole of A12O3. The reaction mixture is placed
in a reaction vessel inert toward the reaction system
and heated at a-temperature of at least about 100-C,
preferably between 100-C and 300-C, until crystallized,
usually a period from 2 hours to 2 weeks. The-solid
crystalline reaction product is then recovered by any
convenient method, such as filtration or centrifugation,
washed with water and dried at a temperature between
ambient and llO-C, preferably in air.
MeAPO MOLECULAR SIEVES
MeAPO molecular sieves are crystalline
microporous aluminophosphates in which the substituent
metal is one of a mixture of two or more divalent metals
of the group magnesium, manganese, zinc and cobalt and
are disclosed in U.S. Patent No. 4,567,029. ~embers of
D-14643
-125- - 133671~
- this novel class of compositions have-a thre-e-
dimensional microporous crystal framewor~ st.~cture of
M02 2, A10 2 and PO 2 tetrahedral units and have an
essential empirical chemical composition, on an
anhydrous basis, of:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the moles of "R" present per mole of
(MXAlyPz)02 and has a value of from zero to 0.3, the
maximum value in each case depending upon the molecular
dimensions of the templating agent and the available
void volume of the pore system of the particular metal
aluminophosphate involved; "x", "y", and "z" represent
the mole fractions of the metal "M", (i.e., magnesium,
manganese, zinc and cobalt), aluminum and phosphorus,
respectively, present as tetrahedral oxides, said mole
fractions being such that they are representing the
following values for "x", "y", and "z":
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.35 0.05 0.60
D 0O35 0060 0.05
D-14643
-126- 13367 1~
When synthesized the minimum value of "m" in-the formula
above is 0.02. In a preferrèd subclass of the metal
aluminophosphates of this invention, the values of "x",
"y" and "z" in the formula above are representing the
following values for "x", "y" and -z":
Mole Fraction
Point x Y z
a 0.01 0.52 0.47
b 0.01 0.39 0.60
c 0.25 0.15 0.60
d 0.25 0.40 0.35
The as-synthesized compositions are capable of
withstanding 350-C calcination in air for extended
periods, i.e., at least 2 hours, without becoming
amorphous. While it is believed that the M, Al and P
framework constituents are present in tetrahedral
coordination with oxyqen, it is theoretically possible
that some minor fraction of these framework constituents
are present in coordination with five or six oxygen
atoms. It is not, moreover, necessarily the case that
all of the M, Al and/or P content of any given
synthesized product is a part of the framework in the
aforesaid types of coordination with oxygen. Some of
each constituent may be merely occluded or in some as
yet undetermined form and may or may not be structurally
significant.
D-14643
1336717
-127-
~ Since the term "metal aluminophosphate" is
somewhat cumbersome, particularly in view of the need
for numerous repetitions thereof in describing such
compositions, the "short-hand" reference "MeAPO" is
S employed hereinafter. Also in those cases where the
metal "Me" in the composition is magnesium, the acronym
MAPO is applied to the composition. Similarly, ZAPO,
MnAPO, and CoAPO are applied to the compositions which
contain zinc, manganese and cobalt, respectively. To
identify the various structural species which make up
each of the subgeneric classes MAPO, ZAPO, CoAPO and
MnAPO, each species is assigned a number and is
identified, for example, as ZAPO-5, MAPO-ll, CoAPO-ll
and so forth.
The term "essential empirical chemical
composition" is meant to include the crystal framework
and can include any organic templating agent present in
the pore system, but does not include al~ali metal or
other ions which can be present by virtue of being
contained in the reaction mixture or as a result of
post-synthesis ion-exchange. Such ionic species, when
present, function primarily as charge-balancing ions for
A102 and/or M02 2 tetrahedra not associated with P02+
tetrahedra or an organic ion derived from the organic
templating agent.
D-14643
~-128- 1336717
- The metal aluminophosphates ("MeAPOs"~ are
- synthesized by hydrothermal crystallization from a
reaction mixture containing reactive sources of the
metal "M", alumina and phosphate, an organic templating,
i.e., structure-directing, agent, preferably a compound
of an element of Group VA of the Periodic Table, and
optionally an alkali metal. The reaction mixture is
placed in a sealed pressure vessel, preferably lined
with an inert plastic material such as polytetra-
fluoroethylene and heated, preferably under autogenouspressure at a temperature between 100C and 225C, and
preferably between 100C and 200-C, until crystals of
the metal aluminophosphate product are obtained, usually
a period of from 4 hours to 2 weeks. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the MeAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of molar ratios as follows:
aR : (MXAlyPz)O2 : b~2O
wherein "R" is an organic templating agent; "a" has a
value great enough to constitute an effective
concentration of "R" and is within the rànge of >0 to 6;
"b" has a value of from zero to 500, preferably 2 to 30
"M" represents a metal of the group zinc, magnesium,
manganese and cobalt, "x", "y" and "z" represent the
D-14643
`129- 133-6717
~ mole fractions, respectively, of "M", aluminum and
- phosphorus in the (MXAlyPz)02 constituent, and each has
a value of at least 0.01, the said points E, F, G, H, I,
and J representing the following values for "x", "y" and
nzn
Mole Fraction
Point x y z
E 0.01 0.70 0.29
F 0.01 0.29 0.70
G 0.29 0.01 0.70
H 0.40 0.01 0.59
I 0.40 0.59 0.01
J 0.29 0.70 0.01
In the foregoing expression of the reaction composition,
the reactants are normalized with respect to a total of
(M + Al + P) = (x + y + z) = 1.00 mole.
In forming the reaction mixture from which the
metal aluminophosphates are crystallized the organic
templating agent can be any of those heretofore proposed
for use in the synthesis of conventional zeolite
aluminosilicates and microporous aluminophosphates. In
general these compounds contain elements of Group VA of
the Periodic Table of Elements, particularly nitrogen,
phosphorus, arsenic and antimony, preferably N or P and
most preferably N, which compounds also contain at least
one alkyl or aryl group having from 1 to 8 carbon atoms.
D-14643
1336717
-130-
Particularly preferred nitrogen-containing compounds for
use as templating agents are the amines and quaternary
ammonium compounds, the latter being represènted
generally by the formula R4N wherein each R is an alkyl
or aryl group containing from 1 to 8 carbon atoms.
Polymeric quaternary ammonium salts such as
~(C14H32N2)(0H)2]x wherein "x" has a value of at least 2
are also suitably employed. Both mono-, di- and
triamines are advantageously utilized, either alone or
in combination with a quaternary ammonium compound or
other templating compound. Mixtures of two or more
templating agents can either produce mixtures of the
desired metal aluminophosphates or the more strongly
directing templating species may control the course of
the reaction with the other templating species serving
primarily to establish the pH conditions of the reaction
gel. Representative templating agents include
tetramethylammonium, tetraethylammonium,
tetrapropylammonium or tetrabutylammonium ions:
di-n-propylamine; tripropylamine; triethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N,N-dimethylbenzylamine;
N-N-dimethylethanolamine; choline;
N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2)
octane; N-methyldiethanolamine; N-methylethanolamine;
N-methylpiperidine; 3-methylpiperidine;
D-14643
.
131- 1336717
- N-methylcyclohexylamine; 3-methylpyridine: - ~
~ 4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating
agent will direct the formation of every species of
metal aluminophosphate (MeAPO), i.e., a single
templating agent can, with proper manipulation of the
reaction conditions, direct the formation of several
MeAPO compositions, and a given MeAPO composition can be
produced using several different templating agents.
The preferred phosphorus source is phosphoric
acid, but organic phosphates such as triethylphosphate
have been found satisfactory, and so also have
crystalline or amorphous aluminophosphates such as the
AlPO4 composition of U.S. Patent No. 4,310,440.
Organo-phosphorus compounds, such as tetrabutyl-
phosphonium bromide do not, apparently serve as reactive
sources of phosphorus, but these compounds do function
as templating agents. Conventional phosphorus salts
such as sodium metaphosphate, may be used, at least in
part, as the phosphorus source, but are not preferred.
The aluminum source is preferably either an
aluminum al~oxide, such as aluminum isopropoxide, or
pseudoboehmite. The crystalline or amorphous
D-14643
I336717
-132-
aluminophosphates which are a suitable source of ~ --
- phosphorus are, of course, a~lso suitable sources of
aluminum. Other sources of aluminum used in zeolite
synthesis, such as gibbsite, sodium aluminate and
aluminum trichloride, can be employed but are not
preferred.
The metals zinc, cobalt, magnesium and
manganese can be introduced into the reaction system in
any form which permits the formation in situ of reactive
divalent ions of the respective metals. Advantageously
salts, oxides or hydroxides of the metals are employed
such as cobalt chloride hexahydrate, alpha cobaltous
iodide, cobaltous sulfate, cobalt acetate, cobaltous
bromide, cobaltous chloride, zinc acetate, zinc bromide,
zinc formate, zinc iodide, zinc sulfate heptahydrate,
magnesium acetate, magnesium bromide, magnesium
chloride, magnesium iodide, magnesium nitrate, magnesium
sulfate, manganous acetate, manganous bromide, manganous
sulfate, and the like.
While not essential to the synthesis of MeAPO
compositions, it has been found that in general,
stirring or other moderate agitation of the reaction
mixture and/or seeding the reaction mixture with seed
crystals of either the MeAPO species to be produced or a
topologically similar aluminophosphate or
D-14643
1336717
-133-
aluminosilicate composition, facilitates the ~- - -
- crystallization procedure.
After crystallization the MeAP0 product is
isolated and advantageously washed with water and dried
in air. The as-synthesized MeAP0 contains within its
internal pore system at least one form of the templating
agent employed in its formation. Most commonly the
organic moiety is present, at least in part, as a
charge-balancing cation as is generally the case with
as-synthesized aluminosilicate zeolites prepared from
organic-containing reaction systems. It is possible,
however, that some or all of the organic moiety is an
occluded molecular species in a particular MeAP0
species. As a general rule, the templating agent, and
hence the occluded organic species, is too large to move
freely through the pore system of the MeAP0 product and
must be removed by calcining the MeAP0 at temperatures
of 200-C to 700-C to thermally degrade the organic
species. In a few instances the pores of the MeAP0
product are sufficiently large to permit transport of
the templating agent, particularly if the latter is a
small molecule, and accordingly complete or partial
removal thereof can be accomplished by conventional
desorption procedures such as carried out in the case of
zeolites. It will be understood that the term
"as-synthesized" as used herein does not include the
D-14643
1336717
-134-
condition of the MeAPO phase wherein the organic moiety
occupying the intracrystalline pore system as a result
of the hydrothermal crystallization process has been
reduced by post-synthesis treatment such that the value
of "m" in the composition formula:
mR : (MxAlyPz)O2
has a value of less than 0.02. The other symbols of the
formula are as defined hereinabove. In those
preparations in which an aluminum alkoxide is employed
as the source of aluminum, the corresponding alcohol is
necec-~Arily present in the reaction mixture since it is
a hydrolysis product of the alkoxide. It has not been
determined whether this alcohol participates in the
synthesis process as a templating agent. For the
lS purposes of this application, however, this alcohol is
arbitrarily omitted from the class of templating agents,
even if it is present in the as-synthesized MeAPO
material.
Since the MeAPO compositions are formed from
AlO2, PO2, and MO2 tetrahedral units which,
respectively, have a net charge of -1, +1, and -2, the
matter of cation exchangeability is considerably more
complicated than in the case of zeolitic molecular
sieves in which, ideally, there is a stoichiometric
relationship between AlO2 tetrahedra and
charge-balancing cations. In the MeAPO compositions, an
D-14643
- 135 -
A102- tetrahedron can be balanced electrica~ e7r
by association with a P02+ tetrahedron or a simple
cation, such as an alkali metal cation, a cation of the
metal ~M~ present in the reaction mixture, or an
organic cation derived from the templating agent.
Similarly an M02-2 tetrahedron can be balanced
electrically by association with PO2+ tetrahedra, a
cation of the metal "M", organic cations derived from
the templating agent, or other divalent or polyvalent
metal cations introduced from an extraneous source. It
has also been postulated that non-adjacent A102- and
PO2+ tetrahedral pairs can be balanced by Na+ and OH-,
respectively [Flanigen and Grose, Molecular Sieve
Zeolites-I, ACS, Washington, D.C. (1971)].
FAPO MOLECULAR SIEVES
Ferroaluminophosphates are disclosed in U.S.
Patent No. 4,554,143, and have a three-dimensional
microporous crystal framework structure of FeO2n, A102-
and P02+ tetrahedral units and have an essential
empirical chemical composition, on an anhydrous basis,
of:
mR : (Fe~Alypz)o2
wherein "R" represents at least one organic templating
agent present in the intracrystal line pore system; "m"
represents the moles of "R" present per mole of
(Fe~AlyPz)02 and has a value of from zero to 0.3, the
D-i4643
i
-I36- - 1336717
maximum value in each case depending upon the molecular
dimensions of the templating agent and the available
void volume of the pore system of the particular
ferroaluminophosphate involved; "x", "y", and "z"
represent the mole fractions of iron, aluminum and
phosphorus, respectively, present as tetrahedral oxides,
representing the following values for "x", "y", and "z":
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.35 0.05 0.60
D 0.35 0.60 0.05
When synthesized the minimum value of "m" in the formula
above is 0.02. In.a preferred subclass of the
ferroaluminophosphates the values of "x", "y" and "z" in
the formula above are representing the following values
for "x", nyn and "z":
Mole Fraction
20 Point x y Z
a 0.01 - 0.52 0.47
b 0.01 0.39 0.60
c 0.25 0.15 0.60
d 0.25 0.40 0.35
The iron of the FeO2 structural units can be
in either the ferric or ferrous valence state, depending
D-14643
-137- 1336717
largely upon the source of the iron in the synthesis
gel. Thus, an FeO2 tetrahedron in the structure can
have a net charge of either -1 or -2. While it is
believed that the Fe, Al and P framework constituents
are present in tetrahedral coordination with oxygen (and
are referred to herein as such), it is theoretically
possible that some minor fraction of these framework
constituents are present in coordination with five or
six oxygen atoms. It is not, moreover, necessarily the
case that all of the Fe, Al and/or P content of any
given synthesized product is a part of the framework in
the aforesaid types of coordination with oxygen. Some
of each constituent may be merely occluded or in some as
yet undetermined form, and may or may not be
structurally significant.
For convenience in describing the
ferroaluminophosphates, the "short-hand" acronym "FAPO"
is sometimes employed hereinafter. To identify the
various structural species which make up the generic
class FAPO, each species is assigned a number and is
identified, for example, as FAPO-11, FAPO-31 and so
forth.
The term "essential empirical chemical
composition" is meant to include the crystal framework
and can include any organic templating agent present in
the pore system, but does not include alkali metal or
D-14643
-138- 1336717
other ions which can be present by virtue of being
contained in the~reaction ~ixture or as a result of
post-synthesis ion-exchange. Such ionic species, when
present, function primarily as charge-balancing ions for
FeO2 and/or AlO2 2 tetrahedra, FeO2 2 tetrahedra
associated with PO2+ tetrahedra or not associated with
PO2 tetrahedra or an organic ion derived from the
organic templating agent.
The af oresaid ferroaluminophosphates are
synthesized by hydrothermal crystallization from a
reaction mixture containing reactive sources of iron
oxide, alumina and phosphate, an organic templating,
i.e., structure-directing, agent, preferably a compound
of an element of Group VA of the Periodic Table, and
optionally an alkali metal. The reaction mixture is
placed in a sealed pressure vessel, preferably lined
with an inert plastic material such as polytetra-
fluoroethylene and heated, preferably under autogenous
pressure at a temperature of at least lOO-C, and
preferably between lOO-C and 250-C, until crystals of
the ~etal aluminophosphate product are obtained, usually
a period of from 2 hours to 2 weeks. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the FAP0 compositions, it is
D-14643
_139_ 1 3 3 6 7 17
preferred to employ a reaction mixture composition
expressed in terms of molar ratios as follows:
aR : (FexAlyPz)02 : bH2O
wherein "R" is an organic templating agent; "a" has a
value great enough to constitute an effective
concentration of "R" and is within the range of >0 to 6;
"b" has a value of from zero to 500, preferably 2 to 80;
"x", "y" and "z" represent the mole fractions,
respectively, of iron, aluminum and phosphorus in the
(FexAlyPz)O2 constituent, and each has a value of at
least 0.01, and representing the following values for
"x", "y" and -z":
Mole Fraction
Point x y z
E 0.01 0.70 0.29
F 0.01 0.29 0.70
G 0.29 0.01 0.70
H 0.40 0.01 0.59
I 0.40 0.59 0.01
J 0.29 0.70 0.01
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to a total of (Fe + Al + P) = (x + y + z) - 1.00 mole.
In forming the reaction mixture from which the
ferroaluminophosphates are crystallized, the organic
templating agent can be any of those heretofore proposed
D-14643
1336717
140-
for use in the synthesis of conventional zeolite
aluminosilicates and microporous aluminophosphates. In
general these compounds contain elements of Group VA of
the Periodic Table of Elements, particularly nitrogen,
phosphorus, arsenic and antimony, preferably N or P and
most preferably N, which compounds also contain at least
one alkyl or aryl group having from 1 to 8 carbon atoms.
Particularly preferred nitrogen-containing compounds for
use as templating agents are the amines and quaternary
ammonium compounds, the latter being represented
generally by the formula R4N wherein each R is an alkyl
or aryl group containing from 1 to 8 carbon atoms.
Polymeric quaternary ammonium salts such as
[(C14H32N2)(OH)2]X wherein "x" has a value of at least 2
are also suitably employed. Mono-, di- and triamines
are advantageously utilized, either alone or in
combination with a quaternary ammonium compound or other
templating compound. Mixtures of two or more templating
agents can either produce mixtures of the desired metal
aluminophosphates or the more strongly directing
templating species may control the course of the
reaction with the other templating species serving
primarily to establish the pH conditions of the reaction
gel. Representative templating agents include
tetramethylammonium, tetraethylammonium,
tetrapropylammonium or tetrabutylammonium ions;
D-14643
1336717
-141-
di-n-propylamine; tri-n-propylamine; triethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N,N-dimethylbenzylamine;
N-N-dimethylethanolamine; choline;
N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2)
octane; N-methyldiethanolamine; N-methylethanolamine;
N-methylpiperidine; 3-methylpiperidine;
N-methylcyclohexylamine; 3-methylpyridine;
4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
di-n-butylamine; neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating
agent will direct the formation of every species of
ferroaluminophosphate (FAPO), i.e., a single templating
agent can, with proper manipulation of the reaction
conditions, direct the formation of several FAPO
compositions, and a given FAPO composition can be
produced using several different templating agents.
The phosphorus source is preferably phosphoric
acid, but organic phosphates such as triethylphosphate
have been found satisfactory, and so also have
crystalline or amorphous aluminophosphates such as the
AlP04 composition of U.S. Patent No. 4,310,440.
Organo-phosphorus compounds, such as tetrabutyl-
phosphonium bromide do not, apparently serve as reactive
D-14643
- - ` 1336717
-142-
sources of phosphorus, but these compounds do function
as templating agents. Conventional phosphorus salts
such as sodium metaphosphate, may be used, at least in
part, as the phosphorus source, but are not preferred.
The aluminum source is preferably either an
aluminum alkoxide, such as aluminum isopropoxide, or
pseudoboehmite. The crystalline or amorphous
aluminophosphates which are a suitable source of
phosphorus are, of course, also suitable sources of
aluminum. Other sources of aluminum used in zeolite
synthesis, such as gibbsite, sodium aluminate and
aluminum trichloride, can be employed but are not
preferred.
Iron can be introduced into the reaction
system in any form which permits the formation in situ
of reactive ferrous or ferric ions. Advantageously
iron salts, oxides or hydroxides are employed such as
iron sulfate, iron acetate, iron nitrate, or the like.
Other sources such as a freshly precipitated iron oxide
r-Fe~OH, are also suitable.
While not essential to the synthesis of FAPO
compositions, it has been found that in general,
stirring or other moderate agitation of the reaction
mixture and/or seeding the reaction mixture with seed
crystals of either the FAPO species to be produced or a
topologically similar aluminophosphate or
D-14643
-
- -143- 133 67 17
aluminosllicate composition, facilitates the
crystallization procedure.
After crystallization the FAPO product is
isolated and advantageously washed with water and dried
in air. The as-synthesized FAPO contains within its
internal pore system at least one form of the templating
agent employed in its formation. Most commonly the
organic moiety is present, at least in part, as a
charge-balancing cation as is generally the case with
as-synthesized aluminosilicate zeolites prepared from
organic-containing reaction systems. It is possible,
however, that some or all of the organic moiety is an
occluded molecular species in a particular FAPO species.
As a general rule, the templating agent, and hence the
occluded organic species, is too large to move freely
through the pore system of the FAPO product and must be
removed by calcining the FAPO at temperatures of 200C
to 700 C to thermally degrade the organic species. In a
few instances the pores of the FAPO product are
sufficiently large to permit transport of the templating
agent, particularly if the latter is a small molecule,
and accordingly complete or partial removal thereof can
be accomplished by conventional desorption procedures
such as carried out in the case of zeolites. It will be
understood that the term "as-synthesized" as used herein
and in the claims does not include the condition of the
D-14643
-144- 1336717
FAP0 phase wherein the organic moiety occupying the
intracrystalline pore system`as a result of the
hydrothermal crystallization process has been reduced by
post-synthesis treatment such that the value of "m" in
the composition formula:
mR : (FexAlyPz)O2
has a value of less than 0.02. The other symbols of the
formula are as defined hereinabove. In those
preparations in which an aluminum alkoxide is employed
as the source of aluminum, the corresponding alcohol is
necessarily present in the reaction mixture since it is
a hydrolysis product of the alkoxide. It has not been
determined whether this alcohol participates in the
syntheses process as a templating agent. For the
purposes of this application, however, this alcohol is
arbitrarily omitted from the class of templating agents,
even if it is present in the as-synthesized FAPO
material.
Since the FAPO compositions are formed from
AlO2 , PO2 , FeO2 and/or FeO2 2 units the matter of
cation exchangeability is considerably more complicated
than in the case of zeolitic molecular sieves in which,
ideally, there is a stoichiometric relationship between
A102 tetrahedra and charge-balancing cations. In the
FAPO compositions, an A102 tetrahedron can be balanced
electrically either by association with a PO2
D-14643
- 145 - 113 3 6717
tetrahedron or a Simple cation such as an kali metal
cation, a Fe+2 or Fe+3 cation present in the reaction
mixture, or an organic cation derived from the
templating agent. Similarly an Fe02~ or FeO2~2
tetrahedron can be balanced electrically by association
with PO2+ tetrahedron, a Fe+2 or Fe+3 cation, organic
cations derived from the templating agent, or other
metal cat ion introduced from an extraneous source. It
has also been postulated that non-adjacent A102- and
P02+ tetrahedral pairs can be balanced by Na+ and OH-,
respectively [Flanigen and Grose, Molecular 5ieve
Zeolites-I, ACS, Washington, D.C. (1971)).
TAPO MOLECULAR SIEVES
TAPO molecular sieves are disclosed in U.S. IS
Patent No. 4,500,561, and comprise a three-dimensional
microporous crystal framework structure of TiO2, A102-
and P02+ tetrahedral units which has a unit empirical
formula on an anhydrous basis of:
mR: (TixAlypz)o2
wherein ~R~ represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the moles of "R" present per mole of
(TiXAlyPz)02 and has a value of between zero and about
5.0, the maximum value in each case depending upon the
molecular dimensions of the templating agent and the
D-14643
B~
- 1336717
-146-
available void volume of~pore system of the particular
titanium molecular sieve; 'ix", "y" and "z" represent the
mole fractions of titanium, aluminum and phosphorus,
respectively, present as tetrahedral oxides,
representing the following values for "x", "y" and "z":
. Mole Fraction
Point x y z
A 0.001 0.45 0.549
B 0.88 0.01 0.11
C 0.98 0.01 0.01
D 0.29 0.70 0.01
E 0.001 0.70 0.299
The parameters "x", "y" and "z" are preferably within
the following values for "x", "y" and "z":
. Mole Fraction
Point x y z
a 0.002 0.499 0.499
b 0.20 0.40 0.40
c 0.20 0.50 0.30
d 0.10 0.60 0.30
e 0.002 0.60 0.398
The titanium-containing molecular sieves are
referred to hereinafter, solely for point of reference
herein as "TAPO" molecular sieves, or as "TAPOs" if the
reference is to the class as a whole. This designation
is simply made for the sake of convenient reference
D-14643
-147- 1336717
herein and is not meant to designate a particular
structure for any given TAPO molecular sieve. The
members of the class of TAPO's employed hereinafter in
the examples will be characterized simply by referring
S to such members as TAPO-5, TAPO-ll, etc, i.e., a
particular species will be referred to as TAPO-n where
"n" is a number specific to a given class member as its
preparation is reported herein. This designation is an
arbitrary one and is not intended to denote structural
relationship to another material(s) which may also be
characterized by a numbering system.
The term "unit empirical formula" is used
herein according to its common meaning to designate the
simplest formula which gives the relative number of
lS moles of titanium, aluminum and phosphorus which form
the ~Tio2], tPO2] and ~AlO2] tetrahedral unit within a
titanium-containing molecular sieve and which forms the
molecular framework of the TAPO composition(s). The
unit empirical formula is given in terms of titanium,
- 20 aluminum and phosphorus as shown in Formula (1), above,
and does not include other compounds, cations or anions
which may be present as a result of the preparation or
the existence of other impurities or materials in the
bulk composition not containing the aforementioned
tetrahedral unit. The amount of template R is reported
as part of the composition when the as-synthesized unit
D-14643
- 1336717
- -148- -
empirical formula is given, and water may also be
reported unless such is defined as the anhydrous form.
For convenience, coefficient "m" for template "R" is
reported as a value that is normalized by dividing the
number of moles of organic templating agent ~y the total
moles of titanium, aluminum and phosphorus.
The unit empirical formula for a TAPO may be
given on an "as-synthesized" basis or may be given after
an "as-synthesized" TAPO composition has been subjected
to some post treatment process, e.g., calcination. The
term "as-synthesized" herein shall be used to refer to
the TAPO composition(s) formed as a result of the
hydrothermal crystallization but before the TAPO
composition has been subjected to post treatment to
remove any volatile components present therein. The
actual value of "m" for a post-treated TAPO will depend
on several factors (including: the particular TAPO,
template, severity of the post-treatment in terms of its
ability to remove the template from the TAPO, the
proposed application of the TAPO composition, and etc.)
and the value for "m" can be within the range of values
as defined for the as-synthesized TAP0 compositions
although such is generally less than the as-synthesized
TAPO unless such post-treatment process adds template to
the TAPO so treated. A TAP0 composition which is in the
calcined or other post-treatment form generally has an
D-14643
-149- ~ 1336717
~ empirical formula represented by Formula~(l), except
that the value of "m" is genèrally less than about 0.02t.
Under sufficiently severe post-treatment conditions,
e.g., roasting in air at high temperature for long
periods (over 1 hr.), the value of "m" may be zero (0)
or, in any event, the template, R, is undetectable by
normal analytical procedures.
The TAPO molecular sieves are generally
further characterized by an intracrystalline adsorption
capacity for water at 4.6 torr and about 24C of about
3.0 weight percent. The adsorption of water has been
- observed to be completely reversible while retaining the
same essential framework topology in both the hydrated
and dehydrated state. The term "essential framework
topology" is meant to designate the spatial arrangement
of the primary bond linkages. A lack of change in the
framework topology indicates that there is no disruption
of these primary bond linkages.
The TAPO molecular sieves are generally
synthesized by hydrothermal crystallization from a
reaction mixture comprising reactive sources of
titanium, aluminum and phosphorus, and one or more
organic templating agents. Optionally, alkali metal(s)
may be present in the reaction mixture. The reaction
mixture is placed in a pressure vessel, preferably lined
with an inert plastic material, such as polytetra-
D-14643
` 1336717
-150-
fluoroethylene, and heated, preferably under autogenous
~ pressure, at a temperature of at least about 1007C, and
preferably between lOO'C and 250C, until crystals of
the molecular sieve product are obtained, usually for a
period of from 2 hours to 2 weeks. While not essential
to the synthesis of the TAPO molecular sieves, it has
been found that in general stirring or other moderate
agitation of the reaction mixture and/or seeding the
reaction mixture with seed crystals of either the TAPO
to be produced, or a topologically similar composition,
facilitates the crystallization procedure. The product
is recovered by any convenient method such as
centrifugation or filtration.
After crystallization the TAPO(s) may be
isolated and washed with water and dried in airO As a
result of the hydrothermal crystallization, the
as-synthesized TAPO contains within its intracrystalline
pore system at least one form of the template employed
in its formation. Generally, the template is a
molecular species, but it is possible, steric
considerations permitting, that at least some of the
template is present as a charge-balancing cation.
Generally the template is too large to move freely
through the intracrystalline pore system of the formed
TAP0 and may be removed by a post-treatment process,
such as by calcining the TAPO at temperatures of between
D-14643
` 1336717
-151-
about 200~C and to about 700C so as to thermally
degrade the template or by employing some other
post-treatment process for removal of at least part of
the template from the TAPO. In some instances the pores
of the TAPO are sufficiently large to permit transport
of the template, and, accordingly, complete or partial
removal thereof can be accomplished by conventional
desorption procedures such as carried out in the case of
zeolites.
The TAPOs are preferably formed from a
reaction mixture having a mole fraction of alkali metal
cation which is sufficiently low that it does not
interfere with the formation of the TAPO composition.
The TAPO compositions are generally formed from a
reaction mixture containing reactive sources of TiO2,
A12O3, and P2O5 and an organic templating agent, said
reaction mixture comprising a composition expressed in
terms of molar oxide ratios of:
fR2O : (TixAlyPz)O2 : g H2O
wherein "R" is an organic templating agent; "f" has a
value large enough to constitute an effective amount of
"R", said effective amount being that amount which form
said TAPO compositions; "g" has a value of from zero to
500; "x", "y" and "z" represent the mole fractions,
respectively of titanium, aluminum and phosphorus in the
(TiXAlyPz)02 constituent, and each has a value of at
D-14643
1336717
-152-
least 0.001 and being within the following values for
"x", "y" and "z":
Mole Fraction
Point x y z
h 0.001 0.989 0.01
i 0.001 0.01 0.989
j 0.32 0.24 0.44
k 0.98 0.01 0.01
Although the TAP0 compositions will form if
higher concentrations of alkali metal cation are
present, such reaction mixtures are not generally
preferred. A reaction mixture, expressed in terms of
molar oxide ratios, comprising the following bulk
composition is preferred:
oR2 WM2 (TixAlyPz)2 nH2
wherein "R" is an organic template; "o" has a value
great enough to constitute an effective concentration of
"R" and is preferably within the range of from greater
than zero (0) to about S.0; "M" is an alkali metal
cation; "w" has a value of from zero to 2.5; "n" has a
value between about zero (0) and about 500; "x", "y" and
"z" represent the mole fractions, respectively, of
titanium, aluminum and phosphorus in the (TiXAlyPz)02
constituent, and each has a value of at least 0.001 and
being within the following values for "x", '~y" and "z":
D-14643
-153- 1336717
Mole Fraction
Point x y z
h 0.001 0.989 0.01
i 0.001 0.01 0.989
S j 0.32 0.24 0.44
k - 0.98 0.01 0.01
When the TAPOs are synthesized by this method
the value of "m" in Formula (1) is generally above about
0.02.
Though the presence of alkali metal cations is
not preferred, when they are present in the reaction
mixture it is preferred to first admix at least a
portion (e.g., at least about 10 weight percent) of each
of the aluminum and phosphorus sources in the
substantial absence (e.g., preferably less than about 20
percent of the total weight of the aluminum source and
phosphorus source) of the titanium source. This
procedure avoids adding the phosphorus source to a basic
reaction mixture containing the titanium source and
aluminum source, (as was done in most of the published
attempts to substitute isomorphously [PO2] tetrahedra
for ~SiO2] tetrahedra in zeolitic structures). Although
the reaction mechanism is by no means clear at this
time, the function of the template may be to favor the
incorporation of [PO2] and ~Al02] tetrahedra in the
framework structures of the crystalline products with
D-14643
- - 1336717
.
~Tio2] tetrahedra isomorphously replacing ~PO2]
tetrahedra.
The reaction mixture from which these TAPOs
are formed contains one or more organic templating
agents (templates) which can be most any of those
heretofore proposed for use in the synthesis of
aluminosilicates and aluminophosphates. The template
preferably contains at least one element of Group VA of
the Periodic Table, particularly nitrogen, phosphorus,
arsenic and/or antimony, more preferably nitrogen or
phosphorus and most preferably nitrogen and is desirably
of the formula R4X wherein X is selected from the group
consisting of nitrogen, phosphorus, arsenic and/or
antimony and R may be hydrogen, alkyl, aryl, aralkyl, or
alkylaryl group and is preferably aryl or alkyl
containing between 1 and 8 carbon atoms, although more
than eight carbon atoms may be present in the group "R"
of the template. Nitrogen-containing templates are
preferred, including amines and quaternary ammonium
compounds, the latter being represented generally by the
formula R'4N wherein each R' is an alkyl, aryl,
alkylaryl, or aralkyl group; wherein R' preferably
contains from l to 8 carbon atoms or higher when R' is
alkyl and greater than 6 carbon atoms when R' is
otherwise, as hereinbefore discussed. Polymeric
quaternary ammonium salts such as ~(Cl4H32N2)(0H)2]X
D-14643
1336717
155-
wherein "x" has a value of at least 2 may also be
employed. The mono-, di- and triamines, including mixed
amines, may also be employed as templates either alone
or in combination with a quaternary ammonium compound or
another template. The exact relationship of various
templates when concurrently employed is not clearly
understood. Mixtures of two or more templating agents
can produce either mixtures of TAPOs or in the instance
where one template is more strongly directing than
another template the more strongly directing template
may control the course of the hydrothermal
crystallization wherein with the other template serving
primarily to establish the pH conditions of the reaction
mixture.
Representative templates include
tetramethylammonium, tetraethylammonium,
tetrapropylammonium or tetrabutylammonium ions;
di-n-propylamine; tripropylamine; triethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N,N-dimethylbenzylamine;
N,N-diethylethanolamine; dicyclohexylamine;
N,N-dimethylethanolamine; 1,4-diazabicyclo (2,2,2)
octane; N-methyldiethanolamine, N-methyl-ethanolamine;
N-methylcy~lohexylamine; 3-methyl-pyridine;
4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
D-14643
-156- 1336717
di-n-butylamine; neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every template
will produce every TAPO composition although a single
S template can, with proper selection of the reaction
conditions, cause the formation of different TAPO
compositions, and a given TAPO composition can be
produced using different templates.
In those instances where an aluminum alkoxide
is the reactive aluminum source, the corresponding
alcohol is necessarily present in the reaction mixture
since it is a hydrolysis product of the alkoxide. It
has not as yet been determined whether this alcohol
participates in the synthesis process as a templating
agent, or in some other function and, accordingly, is
not reported as a template in the unit formula of the
TAPOs, although such may be acting as templates.
Alkali metal cations, if present in the
reaction mixture, may facilitate the crystallization of
certain TAPO phases, although the exact function of such
cations, when present, in crystallization, if any, is
not presently known. Alkali cations present in the
reaction mixture generally appear in the formed TAPO
composition, either as occluded (extraneous) cations
and/or as structural cations balancing net negative
charges at various sites in the crystal lattice. It
D-14643
-1-7 1336717
should be understood that alShough the unit formula for
the TAPOs does not specifically recite the presence of
alkali cations they are not excluded in the same sense
that hydrogen cations and/or hydroxyl groups are not
S specifically provided for in the traditional formulae
for zeolitic aluminosilicates.
Almost any reactive titanium source may be
employed herein. The preferred reactive titanium
sources include titanium alkoxides, water-soluble
titanates and titanium chelates.
Almost any reactive phosphorus source may be
employed. Phosphoric acid is the most suitable
phosphorus source employed to date. Accordingly, other
acids of phosphorus are generally believed to be
lS suitable phosphorus sources for use herein. Organic
phosphates such as triethyl phosphate have been found
satisfactory, and so also have crystalline or amorphous
aluminophosphates such as the AlPO4 compositions of U.S.
Patent 4,310,440. Organo-phosphorus compounds, such as
tetrabutyl-phosphonium bromide have not, apparently,
served as reactive sources of phosphorus, but these
compounds do function as templating agents and may also
be capable of being suitable phosphorus sources under
proper process conditions (yet to be ascertained).
Organic phosphorus compounds, e.g., esters, are believed
to be generally suitable since they can generate acids
D-14643
-158- 1336717
of phosphorus in situ. Conventional phosphorus salts,
such as sodium metaphosphate, may be used, at least in
part as the phosphorus source, but they are not
preferred.
Almost any reactive aluminum source may be
employed herein. The preferred reactive aluminum
sources include aluminum alkoxides, such as aluminum
isopropoxide, and pseudoboehmite. Crystalline or
amorphous aluminophosphates which are a suitable source
of phosphorus are, of course, also suitable sources of
aluminum. Other sources of aluminum used in zeolite
synthesis, such as gibbsite, sodium aluminate and
aluminum trichloride, can be employed but as generally
not preferred.
Since the exact nature of the TAPO molecular
sieves are not clearly understood at present, although
all are believed to contain ~TiO2] tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the TAPO
molecular sieves by means of their chemical composition.
This is due to the low level of titanium present in
certain of the TAPO molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction between titanium, aluminum and
phosphorus. As a result, although it is believed that
titanium, [Tio2], has substituted isomorphously for
D-14643
- - 1336717
_159_
[Al02] or [P02] tetrahedra, it is appropriate to
characterize certain TAPO compositions by reference to
their chemical composition in terms of the mole ratios
of oxides in the as-synthesized and anhydrous form as:
vR : pTio2 : qA12O3 : rP2O5
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "v"
represents an effective amount of the organic templating
agent to form said TAP0 compositions and preferably has
a value between and including zero and about 3.0; "p",
"q" and "r" represent moles, respectively, of titanium,
alumina and phosphorus pentoxide, based on said moles
being such that they are within the following values for
"p", "q" and "r":
Mole Fraction
Point ~ g
A 0.004 1.0 1.22
B 176 1.0 11.0
C 196 1.0 1.0
D 0O828 1.0 0.0143
E - 0.003 1.0 0.427
The parameters "p", "q" and "r" are preferably within
the following values for "p", "q" and "r":
D-14643
`~ 1336717
160
Mole Fraction
Polnt ~ ~ E
a 0.008 1.0 1.0
b 1.0 1.0 1.0
c 0.80 1.0 0.60
d - 0.333 1.0 0.50
e 0.067 1.0 0.663
ELAPO MOLECULAR SIEVES
"ELAPO" molecular sieves are a class of
crystalline molecular sieves in which at least one
element capable of forming a three-dimensional
microporous framework forms crystal framework structures
of AlO2 , PO2 and MO2n tetrahedral oxide units wherein
"MO2n" represents at least one different element (other
1~ than Al or P) present as tetrahedral oxide units "MO2n"
with charge "n" where "n" may be -3, -2, -1, 0 or +1.
The members of this novel class of molecular sieve
compositions have crystal framework structures of AlO2 ,
PO2 and MO2n tetrahedral units and have an empirical
chemical composition on an anhydrous basis expressed by
the formula:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(MXAlyPz)O2; "M" represents at least one element capable
D-14643
- 161 - 1~6717
of forming framework tetrahedral oxides; and "x", "y"
and "z" represent the mole fractions of "M", aluminum
and phosphorus, respectively, present as tetrahedral
oxides. "M" is at least one different (i.e., not
aluminum, phosphorus or oxygen) element such that the
molecular sieves contain at least one framework
tetrahedral unit in addition to AlO2- and PO2+. "M" is
at least one element selected from the group consisting
of arsenic, beryllium, boron, cobalt, chromium,
gallium, germanium, iron, lithium, magnesium,
manganese, titanium and zinc, subject to certain
restrictions on the combinations of elements as will
appear from the discussions of individual groups of
ELAPOs below. ELAPOs and their preparation are
disclosed in European Patent Application Serial No.
85104386.9, filed April 11, 1985 (EPC Publication No.
0158976, published October 13, 1985) and 85104388.5,
filed April 11, 1985 (EPC Publication No. 158349,
published October 16, 1985.
The "ELAPO" molecular sieves further include
numerous species which are intended herein to be within
the scope of the term "non-zeolitic molecular sieves"
such being disclosed in the following commonly assigned
patents or applications [(A) following a serial number
D-14643
-162- 1336717
indicates that the application is abandoned and (C)
indicates that the application is a continuation of the
immediately preceding patent or application):
D-14643
~,.j
- 163 - 1 33 6717
U.S. Patent Serial No. Filed
4,913,888 Feb. 19, 1986 AsAPo
4,952,383 March 24, 1987 BAPO
4,940,570 March 3, 1986 BeAPO
4,759,919 Feb. 19, 1986 CAPO
4,888,167 March 20, 1986 GeAPO
4,789,535 Feb. 28, 1986 LiAPo
4,686,093 April 13, 1984 FCAPO
The ELAPO molecular sieves are generally
referred to herein by the acronym "ELAPO" to
designate
D-14643
- 1~36717
164
element(s) "M" in a framework of Al02 , P02 and M02n
tetrahedral oxide units. Actual class members will be
identified by replacing the "EL" of the acronym with the
elements present as M02n tetrahedral units. For
example, "MgBeAPO" designates a molecular sieve
comprised of Al02 , P02 , Mgo2 2 and BeO2 2 tetrahedral
units. To identify various structural species which
make up each of the subgeneric classes, each species is
assigned a number and is identified as "ELAPO-i" wherein
"i" is an integer. The given species designation is not
intended to denote a similarity in structure to any
other species denominated by a similar identification
system.
The ELAPO molecular sieves comprise at least
one additional element capable of forming framework
tetrahedral oxide units (M02n) to form crystal framework
structures with Al02 and P02 tetrahedral oxide units
wherein "M" represents at least one element capable of
forming tetrahedral units "M02n" where "n" is -3, -2,
-1, 0 or +1 and is at least one element selected from
the group consisting of arsenic, beryllium, boron,
cobalt, chromium, gallium, germanium, iron, lithium,
magnesium, manganese, titanium and zinc.
The ELAPO molecular sieves have crystalline
three-dimensional microporous framework structures of
Al02 , P02 and M02n tetrahedral units and have an
D-14643
~ - -165- 133 67 17
empirical chemical composition on an anhydrous basis
expressed by the formula:
mR : (MXAlyPz)O2;
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(MXAlyPz)02 and has a value of zero to about 0.3; "M"
represents at least one element capable of forming
framewor~ tetrahedral oxides where "M" is at least one
element selected from the group consisting of arsenic,
beryllium, boron, cobalt, chromium, gallium, germanium,
iron, lithium, magnesium, manganese, titanium and zinc.
The relative amounts of element(s) "M",
aluminum and phosphorus are expressed by the empirical
5 chemical formula (anhydrous):
mR : (MxAlyPz)02
where "x", "y" and "z" represent the mole fractions of
said "M", aluminum and phosphorus. The individual mole
fractions of each "M" (or when M denotes two or more
elements, Ml, M2, M3, etc.) may be represented by "x1",
"x ", "x3", etc. wherein "x1", "x2", and X3 etc.
represent the individual mole fractions of elements Ml,
M2, M3, and etc. for "M" as above defined. The values
of "xl", "x2", "x3ll, etc. are as defined for "x",
hereinafter, where "xl" + "x2" + I'x3" . . . = "x" and
where xl, x2, X3, etc. are each at least 0.01.
D-14643
1336717
-166- -
The ELAP0 mo-lecular sieves have crystalline
three-dimensiona~l microporo~s framework structures of
M02n, Al02 and P02 tetrahedral units having an -
empirical chemical composition on an anhydrous basis
5 expressed by the formula:
mR : (MxAlyPz)2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents a molar amount of "R" present per mole of
(MXAlyPz)02 and has a value of zero to about 0.3; "M"
represents at least one different element (other than Al
or P) capable of forming framework tetrahedral oxides,
as hereinbefore defined, and "x", "y" and "z" represent
the mole fractions of "M", aluminum and phosphorus,
respectively, present as tetrahedral oxides; in general,
said mole fractions "x", "y" and "z" are within the
following values for "x", "y" and "z", although as will
appear hereinbelow, the limits for "x", "y" and "z" may
vary slightly with the nature of the element "M":
Mole Fraction
Point x y Z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
D-14643
-167- 133 67 1~
Also, in general, in a preferred sub-class of
the ELAPOs of this invention, the values of 1'x"; "y" and
"z" in the formula above are within the following values
for "x", "y" and "z", although again the relevant limits
may vary somewhat with the nature of the element "M", as
set forth hereinbelow:
Mole Fraction
Point x y z
a 0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 0.01
f 0.39 0.60 0.01
EL~PO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of the elements "M",
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
reaction mixture is generally placed in a sealed
pressure vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
preferably under autogenous pressure at a temperature
between 50-C and 250-C, and preferably between 100C and
D-14643
-168- 13~6717
200C, until crystals of the ELAPO product are obtained,
usually a period of from several hours to several weeks.
Typical crystallization times are from about 2 hours to
about 30 days with from about 2 hours to about 20 days
S being generally employed to obtain crystals of the ELAP0
products. The product is recovered by any convenient
method such as centrifugation or filtration.
In synthesizing the ELAPO compositions of the
instant invention, it is in general preferred to employ
a reaction mixture composition expressed in terms of the
molar ratios as follows:
aR : (MXAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "~" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about 500,
preferably between about 2 and 300; "M" represents at
least one element, as above described, capable of
forming tetrahedral oxide framework units, MO2n, with
AlO2 and PO2+ tetrahedral units; "n" has a value of -3,
-2, -1, 0 or +1; and "x", "y" and "z" represent the mole
fractions of "M", aluminum and phosphorus, respectively;
"y" and "z" each have a value of at least 0.01 and "x"
has a value of at least 0.01 with each element "M"
having a mole fraction of at least 0.01. In general,
D-14643
1336717
169
the mole fractions "x", "y" and "z" are preferably
within the following values for "x", "y" and "z": -
Mole Fraction
Point x y z
F 0.01 0.60 0.39
G 0.01 0.39 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
Further guidance concerning the preferred reaction
mixtures for forming ELAPOs with various elements "M"
will be given below.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to a total of (M + Al + P) = (x + y + z) = 1.00 mole,
whereas in other cases the reaction mixtures are
expressed in terms of molar oxide ratios and may be
normalized to 1.00 mole of P205 and/or A1203. This
latter form is readily converted to the former form by
routine calculations by dividing the total number of
moles of "M", aluminum and phospho NS into the moles of
each of "M", aluminum and phosphorus. The moles of
template and water are similarly normalized by dividing
by the total moles of "M", aluminum and phosphorus.
In forming the reaction mixture from which the
instant molecular sieves are formed the organic
D-146~3
- i336717
-170-
templating agent can be any of those heretofore proposed
for use in the synthesis of conventional zeolite
aluminosilicates. In general these compounds contain
elements of Group VA of the Periodic Table of Elements,
particularly nitrogen, phosphorus, arsenic and antimony,
preferably nitrogen or phosphorus and most preferably
nitrogen, which compounds also contain at least one
alkyl or aryl group having from 1 to 8 carbon atoms.
Particularly preferred compounds for use as templating
agents are the amines, quaternary phosphonium compounds
and quaternary ammonium compounds, the latter two being
represented generally by the formula R4X+ wherein "X" is
nitrogen or phosphorus and each R is an alkyl or aryl
group containing from 1 to 8 carbon atoms. Polymeric
quaternary ammonium salts such as ~(C14H32N2)(OH)2]X
wherein "x" has a value of at least 2 are also suitably
employed. The mono-, di- and tri-amines are
advantageously utilized, either alone or in combination
with a quaternary ammonium compound or other templating
compound. Mixtures of two or more templating agents can
either produce mixtures of the desired ELAPOs or the
more strongly directing templating species may control
the course of the reaction with the other templating
species serving primarily to establish the pH conditions
of the reaction gel. Representative templating agents
include tetramethylammonium, tetraethylammonium,
D-14643
`. 1336717
171
tetrapropylammonium or tetrabutylammonium ions;
tetrapentylammonium ion; di-n-propylamine;
tripropylamine; triethylamine; triethanolamine;
piperidine; cyclohexylamine; 2-methylpyridine;
N,N-dimethylbenzylamine; N,N-dimethylethanolamine;
choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo
(2,2,2,) octane; N-methyldiethanolamine;
N-methylethanolamine; N-methylpiperidine;
3-methylpiperidine; N-methylcyclohexylamine;
3-methylpyridine; 4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
isopropylamine: t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating
agent will direct the formation of every spécies of
ELAPO, i.e., a single templating agent can, with proper
manipulation of the reaction conditions, direct the
formation of several ELAPO compositions, and a given
ELAPO composition can be produced using several
different templating agents. The phosphorus source is
preferably phosphoric acid, but organic phosphates such
as triethyl phosphate may be satisfactory, and so also
may crystalline or amorphous aluminophosphates such as
the AlPO4 composition of U.S.P. 4,310,440. Organo-
2S phosphorus compounds, such as tetrabutylphosphoniumbromide, do not apparently serve as reactive sources of
D-14643
~ -`172- 1336717
phosphorus, but these compounds may function as
templating agents. Conventional phosphorus salts such
as sodium metaphosphate, may be used, at least in part,
as the phosphorus source, but are not preferred.
The aluminum source is preferably either an
aluminum alkoxide, such as aluminum isopropoxide, or
pseudoboehmite. The crystalline or amorphous
aluminophosphates which are a suitable source of
phosphorus are, of course, also suitable sources of
aluminum. Other sources of aluminum used in zeolite
synthesis, such as gibbsite, sodium aluminate and
aluminum trichloride, can be employed but are not
preferred.
The element(s) "M" can be introduced into the
reaction system in any form which permits the formation
in situ of reactive form of the element, i.e., reactive
to form the framework tetrahedral oxide unit of the
element. The organic and inorganic salts, of "M" such
as oxides, alkoxides, hydroxides, halides and
carboxylates, may be employed including the chlorides,
bromides, iodides, nitrates, sulfates, phosphates,
acetates, formates, and alkoxides, including ethoxides,
propoxides and the like. Specific preferred reagents for
introducing various elements "M" are discussed
hereinbelow.
D-14643
- -173- 1336717
While not essential to the synthesis of ELAP0
compositions, stirring or other moderate agitation of
the reaction mixture and/or seeding the reaction mixture
with seed crystals of either the ELAPO species to be
produced or a topologically similar species, such as
aluminophosphate, alumino-silicate or molecular sieve
compositions, facilitates the crystallization procedure.
After crystallization the ELAPO product may be
isolated and advantageously washed with water and dried
in air. The as-synthesized ELAPO generally contains
within its internal pore system at least one form of the
templating agent employed in its formation. Most
commonly the organic moiety is present, at least in
part, as a charge-balancing cation as is generally the
case with as-synthesized aluminosilicate zeolites
prepared from organic-containing reaction systems. It
is possible, however, that some or all of the organic
moiety is an occluded molecular species in a particular
ELAPO species. As a general rule the templating agent,
and hence the occluded organic species, is too large to
move freely through the pore system of the ELAPO product
and must be removed by calcining the ELAPO at
temperatures of 200-C to 700C to thermally degrade the
organic species. In a few instances the pores of the
ELAPO product are sufficiently large to permit transport
of the templating agent, particularly if the latter is a
D-14643
- -174- 1336717
small molecule, and accordingly complete or partial
removal thereof can be accomplished by conventional
desorption procedures such as carried out in the case of
zeolites. It will be understood that the term
"as-synthesized" as used herein does not include the
condition of the ELAP0 phase wherein the organic moiety
occupying the intracrystalline pore system as a result
of the hydrothermal crystallization process has been
reduced by post-synthesis treatment such that the value
of "m" in the composition formula:
mR : (MXAlyPz)02
has a value of less than 0.02. The other symbols of the
formula are as defined hereinabove. In those
preparations in which an alkoxide is employed as the
source of element "M", aluminum or phosphorus, the
corresponding alcohol is necesc~rily present in the
reaction mixture since it is a hydrolysis product of the
alkoxide. It has not been determined whether this
alcohol participates in the synthesis process as a
templating agent. For the purposes of this application,
however, this alcohol is arbitrarily omitted from the
class of templating agents, even if it is present in the
as-synthesized ELAPO material.
Since the present ELAPO compositions are
formed from MO2n, A102 and PO2+ tetrahedral oxide units
which, respectively, havé a net charge of "n", (where
D-14643
-175-
"m" may be -3, -2, -1, 0 or +1), -1 and +1~ ~ ~ 717
matter of cation exchangeability is considerably
more complicated than in the case of zeolitic
molecular sieves in which, ideally, there is a
stoichiometric relationship between A102- tetrahedra
and charge-balancing cations. In the instant
compositions, an A102- tetrahedron can be balanced
electrically either by association with a PO2+
tetrahedron or a simple cation such as an alkali
metal cation, a proton (H+), a cation of "M" present
in the reaction mixture, or an organic cation
derived from the templating agent. Similarly an
MO2n tetrahedron, where "n" is negative, can be
balanced electrically by association with PO2+
tetrahedra, a cation of "M" present in the reaction
mixture, organic cations derived from the templating
agent, a simple cation such as an alkali metal
cation, or other divalent or polyvalent metal
cation, a proton (H+), or anions or cations
introduced from an extraneous source. It has also
been postulated that non-adjacent A102- and PO2+
tetrahedral pairs can be balanced by Na+ and OH-
respectively (Flanigen and Grose, Molecular Sieve
Zeolites-I, ACS, Washington, DC (1971).
AsAPO MOLECULAR SIEVES
The AsAPO molecular sieves have a framework
D-14643
~,i'
,.., .~
- ` 1336717
-176-
structure of AsO2n, A102 and PO2 tetrahedral units
- (where "n" is -1 or +1) and have an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (AsxAlyPz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(AsxAlyPz~O2 and has a value of zero to about 0.3, but
is preferably not greater than 0.15; and "x", -y" and
"z" represent the mole fractions of the elements
arsenic, aluminum and phosphorus, respectively, present
as tetrahedral oxides. The mole fractions "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
20 C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
There are two preferred subclasses of the
25 AsAPO molecular sieves, depending upon whether the value
of "n" is -1 or +1 (i.e. whether the arsenic is
D-14643
- 1336717
177
trivalent or pentavalent), it being understood that
mixtures of such are permitted in a given AsAPO. When
"n" is -1, the preferred values of x, y and z are within
the limiting compositional values or points as follows:
Mole Fraction
Point x y z
a 0.01 0.59 0.40
b 0.01 0.39 0.60
c 0.39 0.01 0.60
d 0.59 0.01 0.40
When "n" is +1, the preferred values of x, y and z are
within the limiting compositional values or points as
follows:
Mole Fraction
15 Point x y z
e 0.01 0.60 0.39
f 0.01 0.40 0.59
g 0-59 0.40 0.01
h 0.39 0.60 0.01
In an especially preferred subclass of the
AsAPO molecular sieves in which "n" = +1, the values of
x, y and z are as follows:
D-14643
`- 1336717
-178- -
Mole Fraction
Point x - y z
i 0.03 0.52 0.45
j 0.03 0.45 0.52
k 0.08 0.40 0.52
1 0.33 0.40 0.27
m 0.33 0.41 0.26
n 0.22 0.52 0.26
AsAPO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of arsenic, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50C
and about 250-C, and preferably between about lOO-C and
about 200-C until crystals of the AsAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 2 hours to about
20 days, and preferably about 12 hours to about 7 days,
D-14643
179- - 1336717
have been observed. The product is recovered by any
convenient method such as ce`ntrifugation or filtration.
In synthesizing the AsAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (ASxAlyPz)2 bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20; and "x", "y" and
"z" represent the mole fractions of arsenic, aluminum
and phosphorus, respectively, and each has a value of
at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
D-14643
-1~0- 1336717
Mole Fraction
Point x ~ y z
G 0.01 0.60 0.39
H ~ 0.01 0.39 0.60
I 0.39 0.01 0.60
0.98 0.01 0.01
K 0.39 0.60 0.01
- Especially preferred reaction mixtures are
those wherein the mole fractions "x", "y" and "z" are
within the limiting compositional values or points as
follows:
Mole Fraction
Point x y z
a 0.20 0.55 0.25
b 0.20 0.50 .0~30
c 0.30 0.40 0.30
d 0.40 0.40 0.20
e 0.40 0.50 0.10
f 0.35 0.55 0.10
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
tx + y + z) = 1.00 mole. Molecular sieves containing
arsenic, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
D-14643
-181- 1336717
Pre~arative Reaqents
AsAPO compositions`may be prepared by using
numerous reagents. Reagents which may be employed to
prepare AsAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) As2O5, arsenic(V) oxide;
(e) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Pre~arative Procedures
AsAPOs may be prepared by forming a starting
2S reaction mixture by dissolving the arsenic(V) oxide and
the H3PO4 in at least part of the water. To this
D-14643
-182- 1336717
solution the aluminum oxide or isopropoxide is
added. This mixture is then blended until a
homogeneous mixture is observed. To this mixture
the templating agent and the resulting mixture
blended until a homogeneous mixture is observed.
The mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
BAPO MOLECULAR SIEVES
The BAPO molecular sieves have a framework
structure of B02-, AlO2- and P02+ tetrahedral units
and have an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (BXAlypz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (BXAlyPz)O2 and has a value of
zero to about 0.3, "x", "y" and "z" represent the
mole fractions of the elements boron, aluminum and
phosphorus, respectively, present as tetrahedral
oxides. The mole fractions "x", "y" and "z"
D-14643
-183- 1336717
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B - 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In a preferred subclass of the BAPO molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
15 Point x y Z
a 0.01 0O59 0.40
b 0.01 0.39 0060
c 0.39 0.01 0.60
d 0.59 OoOl 0.40
An especially preferred subclass of the BAPO
molecular sieves are those in which the mole fraction,
"x", of boron is not greater than about 0.3.
BAPO compositions are generally synthesized by
hydrothermal crystallization from a reaction mixture
containing reactive sources of boron, aluminum and
phosphorus, preferably an organic templating, i.e.,
D-14643
1336717
-184-
structure-directing, agent, preferably a compound of an
element of Group VA of the Pèriodic Table, and~or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
- 5 preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous préssure at a temperature between about 50~C
and about 250-C, and preferably between about lOO-C and
about 200-C until crystals of the BAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 4 hours to about
14 days, and preferably about 1 to about 7 days, have
been observed. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the BAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (BXAlyPz)02 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and is an
effective amount preferably within the range of greater
than zero (0) to about 6, and most preferably not more
than about 1.0; "b" has a value of from zero (0) to
about 500, preferably between about 2 and about 300,
desirably not greater than about 20, and most desirably
D-14643
` 1336717
185
not greater than about 10; and "x", "y" and "z"
represent the mole fractions` of boron, aluminum and
phosphorus, respectively, and each has a value of at
least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
lO Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are
those containing from 0.5 to 2.0 moles of B2O3 and from
0.75 to 1.25 moles of Al2O3 for each mole of P205.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = l.00 mole.
The exact nature of the BAP0 molecular sieves
is not entirely understood at present, although all are
believed to contain BO2, Al02 and PO2 tetrahedra in the
three-dimensional microporous framework structure. The
D-14643
1336717
-186-
low level of boron present in some of the instant
molecular sieves makes it di~fficult to ascertain the
exact nature of the interactions among boron, aluminum
and phospho~us. As a result, although it is believed
that BO2 tetrahedra are present in the three-dimensional
microporous framework structure, it is appropriate to
characterize certain BAPO compositions in terms of the
molar ratios of oxides.
Molecular sieves containing boron, aluminum
and phosphorus as framework tetrahedral oxide units are
prepared as follows:
Preparative Reagents
BAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare BAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) boric acid or trimethylborate;
(e) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
D-14643
~ 1336717
187
(i) Quin: Quinuclidine, (C7~13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Pre~arative Procedures
In the preferred method of synthesizing the
BAPO compositions, one first combines sources of boron,
aluminum and phosphorus to form an amorphous material
containing all three elements, and thereafter heats the
amorphous material to produce a crystalline BAPO
molecular sieve. It is not necessary that the total
quantities of the reactive sources of boron, aluminum
and phosphorus to be used in the final reaction mixture
be present in the amorphous material, since additional
quantities of the elements can be added during the later
heat treatment; i`n particular, it has been found
convenient to add additional quantities of phosphorus to
the amorphous material before the heat treatment. The
preliminary formation of the amorphous material assists
in the incorporation of the boron into the final
molecular sieve.
For example, BAPOs may be prepared by forming
a solution of boric acid in a methanolic solution of the
D-14643
-188- 1336717
templating agent, then adding a hydrated
aluminophosphate and water and stirring to form a
homogeneous reaction slurry. This slurry is then
placed in a lined (polytetrafluoroethylene)
"stainless steel pressure vessel and digested at a
temperature (150C or 200C) for a time or placed in
lined screw top bottles for digestion at 100C.
Digestions are typically carried out under
autogenous pressure.
BeAPO MOLECULAR SIEVES
The BeAPO molecular sieves have a framework
structure of BeO2-2, AlO2- and P02+ tetrahedral
units and have an empirical chemical composition on
an anhydrous basis expressed by the formula:
mA : (BxAlypz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (BXAlyPz)O2 and has a value of
zero to about 0.3, but is preferably not greater
than 0.15; and "x", "y" and "z" represent the mole
fractions of the elements beryllium, aluminum and
phosphorus, respectively, present as tetrahedral
oxides. The mole fractions "x", "y" and "z" are
generally defined as being within the limiting
compositional values or points as follows:
D-14643
. .
~'~
~ 189- 1 336717
Mole Fraction
Point _ y z
A O.Ol 0.60 0.39
B O.Ol 0.39 0.60
C 0.39 O.Ol 0.60
D . 0.60 O.Ol 0.39
E 0.60 0.39 O.Ol
F 0.39 0.60 O.Ol
In a preferred subclass of the BeAP0 molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
a O.Ol 0.60 0.39
b O.Ol 0.39 0.60
c 0.35 0.05 0.60
d 0.35 0.60 0.05
In an especially preferred subclass of the
BeAPO molecular sieves the values of x, y and z are as
follows:
Mole Fraction
Point x y z
e 0.02 0.46 0.52
f OolO 0.38 0052
g OolO 0O46 0.44
D-14643
` . 1~3671~
19 0--
BeAPO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of beryllium, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50C
and about 250C, and preferably between about 100C and
about 200-C until crystals of the BeAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of f~om 2 hours
to about 30 days, generally from about 4 hours to about
14 days, and preferably about 1 to about 7 days, have
been observed. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the BeAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (BexAlyPz)O2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
D-14643
- 1336717
amount within the range of greater than zero (0) to
about 6, and most preferably`not more than about 1.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 50; and "x", "y" and
"z" represent the mole fractions of beryllium, aluminum
and phosphorus, respectively, and each has a value of
at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are
those wherein the mole fractions "x", "y" and "z" are
within the limiting compositional values or points as
follows:
D-14643
-192- 1 3 3 6717 - -
Mole Fraction
Point x y z
g 0.04 0.46 0.50
h 0.16 0.34 0.50
i 0.17 0.34 0.49
j 0.17 0.43 0.40
k 0.14 0.46 0.40
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = 1.00 mole. Molecular sieves containing
beryllium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
Preparative Reaqents
BeAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare BeAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) beryllium sulfate:
(e) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
D-14643
-193-
(g) Pr2NH: di-n-propylamine, (C3H7~2NH7
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(1) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide;
and
(n) DEEA: 2-diethylaminoethanol.
Preparative Procedures
BeAPOs may be prepared by forming a
starting reaction mixture by dissolving the
beryllium sulfate and the H3PO4 in at least part of
the water. To this solution the aluminum oxide or
isopropoxide is added. This mixture is then blended
until a homogeneous mixture is observed. To this
mixture the templating agent and the resulting
mixture blended until a homogeneous mixture is
observed. The mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
CAPO MOLECULAR SIEVES
The CAPO molecular sieves
D-14643
-194- 1336717
have a framework structure of CrO2n, AlO2- and PO2+
tetrahedral units (where "n" is -1, 0 or +1) and
have an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (CrxAlypz)o2
wherein "R" represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (CrxAlyPz)O2 and has a value of
zero to about 0.3, but is preferably not greater
than 0.15; and "x", "y" and "z" represent the mole
fractions of the elements chromium, aluminum and
phosphorus, respectively, present as tetrahedral
oxides. When "n" is -1 or +1, the mole fractions
"x", "y" and "z" are generally defined as being
within the limiting compositional values or points
as follows:
Mole Fraction
Point x y z
A 0.010.60 0.39
B 0.010.39 0.60
C 0.390.01 0.60
D 0.600.01 0.39
E 0.600.39 0.01
F 0.390.60 0.01
D-14643
A~
l95- 13367I7
When "n" is 0, the mole fractions "x", "y" and "z" are
-generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
5 Point x v z
G 0.01 0.60 0.39
H 0.01 0.47 0.52
I 0.94 0.01 0.05
J 0.98 0.01 0.01
K 0.39 0.60 0.01
There are three preferred subclasses of the
CAPO molecular sieves, depending upon whether the value
of "n" is -l, 0 or +1 (i.e. whether the chromium has an
oxidation number of 3, 4 or 5), it being understood that
mixtures of such are permitted in a given CAPO. When
"n" is -1, the preferred values of x, y and z are within
the limiting compositional values or points as follows:
Mole Fraction
Point x y z
a 0.01 0.59 0O40
b 0.01 0.39 0.60
c 0.39 0.01 0.60
d 0.59 0.01 0.40
In an especially preferred subclass of these
CAPSO molecular sieves in which "n" = -1, the values of
x, y and z are as follows:
D-14643
- . -196- 1336717
Mole Fraction
Point x y z
n 0.01 0.52 0.47
o 0.01 0.42 0.57
p 0.03 0.40 0.57
q - 0.07 0.40 0.53
r 0.07 0.47 0.46
s 0.02 0.52 0.46
When "n" is 0, the preferred values of x, y and z are
within the limiting compositional values or points as
follows:
Mole Fraction
Point x y z
e 0.01 0.60 0O39
lS f 0.01 0.47 0.52
g 0.50 0.225 0.275
h 0.50 0.40 0.10
i 0.30 0.60 0.10
When "n" is +1, the preferred values of x, y and z are
within the limiting compositional values or points as
follows:
D-14643
1336717
197-
Mole Fraction
Point x y z
j 0.01 0.60 0.39
k 0.01 0.40 0.59
1 0.59 0.40 0.01
m - 0.39 0.60 0.10
Since the exact nature of the CAPO molecular
sieves is not clearly understood at present, although
all are believed to contain CrO2 tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the CAP0
molecular sieves by means of their chemical composition.
This is due to the low level of chromium present in
certain of the CAPO molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction between chromium, aluminum and
phosphorus. As a result, although it is believed that
CrO2 tetrahedra are substituted isomorphously for A102
or PO2 tetrahedra, it is appropriate to characterize
certain CAPO compositions by reference to their chemical
composition in terms of the mole ratios of oxides.
CAPO compositions are generally synthesized by
hydrothermal crystallization from a reaction mixture
containing reactive sources of chromium, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
D-14643
-198- 1336717
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50~C
and about 250-C, and preferably between about 100C and
about 200-C until crystals of the CAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 2 hours to about
20 days, and preferably about 1 to about 10 days, have
been observed. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the CAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (CrxAlyPz)o2 : bH2O
wherein UR" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.6;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably not greater than about 20; and "x", "y" and
D-14643
-199- 1336717
"z" represent the mole fractions of chromium, aluminum
and phosphorus, respectively, and each has a value of
at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
L 0.01 0.60 0.39
M 0.01 0.39 0.60
N 0.39 0.01 0.60
O 0.98 0.01 0.01
P 0.39 0.60 0.01
lS Especially preferred reaction mixtures are
those containing from about 0.1 to about 0.4 moles of
chromium, and from about 0.75 to about 1.25 moles of
aluminum, per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = 1.00 mole. Molecular sieves containing
chromium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
D-14643
-200- 1336717
Pre~arative Reaqents
CAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare CAPOs include:
(a) aluminum isopropoxide, or aluminum
chlorhydrol;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) chromium(III) orthophosphate,
chromium(III) acetate and chromium
acetate hydroxide,
(Cr3(OH)2(CH3COO)7);
(e) TEAOH: 40 weight percent aqueous solution
. of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
2S (m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
D-14643
1336717
-201-
- Preparative Procedures
CAPOs may be prepared by forming a starting
reaction mixture by adding aluminum chlorhydrol or
aluminum oxide to a solution of chromium acetate
hydroxide in water, then adding successively phosphoric
acid and the templating agent. Between each addition,
and after formation of the final mixture, the mixture is
blended until a homogeneous mixture is observed.
Alternatively, the phosphoric acid may be
mixed with at least part of the water, and aluminum
oxide or isopropoxide mixed in. A solution of chromium
acetate hydroxide is then added, followed by the
templating agent, and the resultant mixture mixed until
homogeneous.
In a third procedure, amorphous chromium
phosphate is ground dry with aluminum oxide and the
resultant dry mixture added to an aqueous solution of
phosphoric acid in an ice bath. The templating agent is
then added, and the final mixture mixed until
homogeneous.
Whichever technique is employed to produce the
reaction mixture, this mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150-C or 200C)
for a time or placed in lined screw top bottles for
D-14643
-202- 1336717
digestion at 100C. Digestions are typically
carried out under autogenous pressure.
GaAPO MOLECULAR SIEVES
The GaAPO molecular sieves have a framework
structure of GaO2~, AlO2- and PO2+ tetrahedral units
and have an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (GaxAlypz)o2
wherein ~R~ represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of (GaxAlyPz)O2 and has a value of
zero to about 0.3, but is preferably not greater
than 0.15; and "x", "y" and "z" represent the mole
fractions of the elements gallium, aluminum and
phosphorus, respectively, present as tetrahedral
oxides. The mole fractions "x", "y" and "z" are
generally defined as being within the limiting
compositional values or points as follows:
D-14643
-
~203- 1336717
- ~ Mole Fraction
Point x ~ y z ~
- A 0.01 0.60 0.39
B - 0.01 0.34 0.65
C 0.34 0.01 0.65
D 0.60 - 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In general, the value of "z" in the GaAP0
molecular sieves is not greater than about 0.60.
In a preferred subclass of the GaAPO molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
15 Point x y z
a 0.01 0.59 0.40
b 0.01 0.34 0.65
c 0.34 0.01 0.65
d O.S9 0.01 0.40
In an especially preferred subclass of the
GaAPO molecular sieves the values of x, y and z are as
follows:
D-14643
- - 1336717
-204-
- Mole Fraction
Po-nt x ~ y z
e 0.03 0.52 0.45
f 0.03 0.33 0.64
g 0.16 0.20 0.64
h 0.25 0.20 0.5S
i 0.25 0.33 0.42
j 0.06 0.52 0.42
GaAPO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of gallium, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50C
and about 250-C, and preferably between about lOO-C and
about 200-C, until crystals of the GaAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 4 hours to about
20 days, and preferably about 1 to about 7 days, have
D-14643
. ~ 205- 1336717
been observed. The product is recovered by any
convenient method such as c~ntrifus2tion or filtration.~
In synthesizing the GaAP0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (GaxAlyPz)o2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "~" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 1.0;
"b" has a value of from zero (0) to about S00,
preferably between about 2 and about 300, most
preferably between about 2 and about 20; and "x", "y"
and "zi' represent the mole fractions of gall,ium,
aluminum and phosphorus, respectively, and each has a
value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
D-14643
- 13367i7
-206-
Mole Fraction
Point x- ~ y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
- Especially preferred reaction mixtures are
those containing from 0.2 to 0.5 mole of Ga203 and from
0.3 to 1 mole of A1203 for each mole of P205.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = 1.00 mole. Molecular sieves containing
gallium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
Preparative Reagents
Ga~PO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare GaAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) gallium sulfate or gallium(III)
hydroxide;
D-14643
_ 07_ 1 33 6 71 7
(e) TEAOH: 40 weight percent aqueous solution
of tetraethyl~ammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
S (g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7Hl3N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Preparative Procedures
GaAPOs may be prepared by forming a starting
reaction mixture by mixing the phosphoric acid with at
least part of the water. To this solution the aluminum
oxide or isopropoxide is added. This mixture is then
blended until a homogeneous mixture is observed. To
this mixture the gallium sulfate or gallium hydroxide
and the templating agent are successively added and the
resulting mixture blended until a homogeneous mixture is
observed.
Alternatively, the aluminum oxide may be mixed
with a solution of the gallium sulfate or hydroxide, and
then the phosphoric acid and the templating agent
D-14643
-Z08- 1336717
successively added. The resulting mixture is then
blended until a homogeneous mixture is observed.
In a third process, the templating agent
may be dissolved in water, the gallium hydroxide or
sulfate added with stirring, a solution of the
phosphoric acid added, and finally the aluminum
oxide mixed in. The resulting mixture is then
blended until a homogeneous mixture is observed.
Whichever technique is employed to form the
reaction mixture, the mixture is then placed in a
lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150C
or 200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
GeAPO MOLECULAR SIEVES
The GeAPO molecular sieves have a framework
structure of GeO2, AlO2- and P02+ tetrahedral units
and have an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (GexAlypz)o2
wherein "R' represents at least one organic
templating agent present in the intracrystalline
pore system; "m" represents the molar amount of "R"
present per mole of
D-14643
~;~.~
. . .,~
-209- 1336717
(GexAlyPz)02 and has a value of zero to about 0.~3, but
is preferably not greater than 0.2: and "x", "y" and "z"
represent the mole fractions of the elements germanium,
- aluminum and phosphorus, respectively, present as
`5 tetrahedral oxides. The mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.47 O.S2
C 0.94 0.01 0.05
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the GeAP0 molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
Point _ y z
a 0.01 0.60 0.39
b 0.01 0.47 0.52
c 0.50 0.225 0.275
d 0.50 0.40 0.10
e 0.30 0.60 0.10
D-14643
-210- 1336717
An especially preferred subclass of the GeAP0
molecular sieves are those i~n which the value of "x" is
not greater than about 0.13.
GeAPO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of germanium, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50~C
and about 250~C, and preferably between about 100C and
about 200C, until crystals of the GeAP0 product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally from about 2 hours to about
20 days, and preferably about 1 to about 10 days, have
been observed. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the GeAPO compositions, it is
preferred to employ a reaction mixture composition
5 expressed in terms of the molar ratios as follows:
aR : (GexAlyPz)02 : bH20
D-14643
- 1~36717
:-211-
wherein "R" is an organic templating agent; "a" is the ~
~ amount of organic templating~agent "R" and has a value
. of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.6;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
preferably between about 10 and about 60; and "x", "y"
and "z" represent the mole fractions of germanium,
aluminum and phosphorus, respectively, and each has a
value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
F 0.01 0.60 0.39
G 0.01 0.39 0.60
H 0.39 0.01 0060
I 0.98 0.01 OoO1
J 0.39 0.60 0.01
Especially preferred reaction mixtures are
those containing from 0.2 to 0.4 mole of GeO2 and from
0.75 to 1.25 mole of Al203 for each mole of P205.
D-14643
.
1336717
-212-
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z)`= 1.00 mole. Molecular sieves containing
S germanium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
Pre~arative Reaqents
GeAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare GeAPOs include:
(a) aluminum isopropoxide:
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) germanium tetrachloride, germanium
ethoxide and germanium dioxide;
(e) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(~7H13NCH3OH);
(k) C-hex: cyclohexylamine;
D-14643
- 213- 1336717
- (l) TMAOH: tetramethylammonium hydroxide; ~ -
- (m) TPAOH: tetrapropylammonium hydrorxide; and
(n) DEEA: 2-diethylaminoethanol.
Preparative Procedures
In some cases, it may be advantageous, when
synthesizing the GeA-PO compositions, to first combine
sources of germanium and aluminum, to form a mixed
germanium/aluminum compound ~this compound being
typically a mixed oxide) and thereafter to combine this
mixed compound with a source of phosphorus to form the
final GeAPO composition. Such mixed oxides may be
prepared for example by hydrolyzing aqueous solutions
containing germanium tetrachloride and aluminum
chlorhydrol, or aluminum tri-sec-butoxide.
GeAPOs may be prepared by forming a starting
reaction mixture by mixing the phosphoric acid with at
least part of the water. To this solution is added the
mixed germanium/aluminum oxide prepared as described
above. This mixture is then blended until a homogeneous
mixture is observed. To this mixture the templating
agent is added and the resulting mixture blended until a
homogeneous mixture is observed.
Alternatively, to a solution of aluminum
isopropoxide may be added germanium ethoxide. The
resultant solution may optionally be dried to produce a
mixed oxide. To the mixed solution or dried oxide are
D-14643
-214- 1336717
added successively the phosphoric acid and the
templating agent. The resulting mixture is then
blended until a homogeneous mixture is observed.
In a third process, a solution is formed by
dissolving the phosphoric acid in water, adding
aluminum oxide or isopropoxide and mixing
thoroughly. To the resultant mixture is added a
solution containing the templating agent and
germanium dioxide. The resulting mixture is then
blended until a homogeneous mixture is observed.
Whichever technique is employed to form the
reaction mixture, the mixture is then placed in a
lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150C
or 200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
LiAPO MOLECULAR SIEVES
The LiAPO molecular sieves of U.S. Patent
No. 4,789,535 have a framework structure of Lio2-3,
AlO2+ and PO2+ tetrahedral units and have an
empirical chemical composition on an anhydrous basis
expressed by the formula:
mA : (LiXAlypz)o2
D-14643
:-215- 1336717
- - wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(LiXAlyPz)O2 and has a value of zero to about 0.3, but
is preferably not greater than 0.15; and "x", "y" and
"z" represent the mole fractions of the elements
lithium, aluminum and phosphorus, respectively, present
as tetrahedral oxides. The mole fractions "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0O39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In a preferred subclass of the LiAPo molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
D-14643
216- 1336717
- ~- Mole Fraction
Point x -y z
a 0.01 0.60 0.39
b 0.01 0.39 0.60
c 0.35 0.05 0.60
d 0.35 0.60 O.OS
In an especially preferred subclass of the
LiAP0 molecular sieves the values of x, y and z are
within the following limits:
Mole Fraction
Point x y z
e 0.01 O.S2 0.47
f 0.01 0.47 0.52
g 0.03 0.45 0.52
h 0.10 0.45 0.45
i 0.10 0.49 0.41
j 0.07 O.S2 0.41
LiAPo compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
cont~;n;ng reactive sources of lithium, aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
D-14643
:,217- 1336717
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50 C
and about 250-C, and preferably between about 100C and
about 200-C until crystals of the LiAPo product are
obtained, usually a period of from several hours to
several wee~s. Typical effective times of from 2 hours
to about 30 days, generally from about 12 hours to about
5 days, have been observed. The product is recovered by
any convenient method such as centrifugation or
filtration.
In synthesizing the LiAPo compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (LiXAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 2; "b"
has a value of from zero (0) to about 500, preferably
between about 2 and about 300, most preferably not
greater than about 40; and "x", "y" and "z" represent
the mole fractions of lithium, aluminum and phosphorus,
respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
D-14643
1336717
-218-
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
In an especially preferred subclass of the
reaction mixtures, the values of "x", "y" and "z" are
within the limiting compositional values or points as
follows:
Mole Fraction
15 Point x Y z
l 0.03 O.5o 0.47
m 0.03 0.45 0.52
n 0.08 0.40 0.52
o 0.10 0.40 0.50
q 0.04 0.50 0.46
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = 1.00 mole.
Since the exact nature of the LiAPO molecular
sieves is not clearly understood at present, although
D-14643
F2l9- 1336717
all are believed to contain Lio2 tetrahedra in the
three-dimensional microporo~s crystal framework
structure, it is advantageous to characterize the LiAPo
molecular sieves by means of their chemical composition.
This is due to the low level of lithium present in
certain of the LiAPo molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction between lithium, aluminum and
phosphorus. As a result, although it is believed that
Lio2 tetrahedra are substituted isomorphously for Al02
or P02 tetrahedra, it is appropriate to characterize
certain LiAPO compositions by reference to their
chemical composition in terms of the mole ratios of
oxides.
.Molecular sieves containing lithium, aluminum
and phosphorus as framework tetrahedral oxide units are
prepared as follows:
Preparative Rea~ents
LiAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare LiAPos include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3P04: 85 weight percent aqueous
phosphoric acid;
D-14643
-220- 1336717
(d) lithium suifate or lithium
orthophosphate;
(e) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
- (h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(l) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Pre~arative Procedures
LiAPos may be prepared by forming a starting
reaction mixture by suspending aluminum oxide in at
least part of the water. To this mixture the templating
agent is added. The resultant mixture is then blended
until a homogeneous mixture is observed. To this
mixture the lithium phosphate or sulfate is added and
the resulting mixture blended until a homogeneous
mixture is observed. Alternatively, an initial mixture
may be formed by mixing aluminum oxide and lithium
phosphate or sulfate. To the resultant mixture are
D-14643
-221- I 33 6717
added successively phosphoric acid and an aqueous
solution of the templating agent, and the resulting
mixture blended until a homogeneous mixture is
observed.
In a third procedure, the phosphoric acid
is mixed with at least part of the water, and the
aluminum oxide is mixed in. To the resultant
mixture are added lithium sulfate and the templating
agent, and the resulting mixture blended until a
homogeneous mixture is observed.
Whichever procedure is adopted to form the
reaction mixture, the mixture is then placed in a
lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature (150C
or 200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
FeTiAPO MOLECULAR SIEVES
The FeTiAPO molecular sieves have
three-dimensional microporous framework structures
of FeO2n, TiO2, AlO2- and P02+ tetrahedral oxide
units having an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (MXAlyPz)o2
D-14643
~..
- - 22- 1336717
wherein "R" represents at least one o~rganic templating
agent present in the intr~c~ystalline pore system; "M"
represents iron and titanium; "m" represents the molar
amount of "R" present per mole of (MXAlyPz)02 and has a
value of zero (0) to about 0.3; and "x", "y" and "z"
represent the mole fractions of "M", aluminum and
phosphorus, respectively, present as tetrahedral oxides.
The mole fractions "x", "y" and "z" are generally
defined as being within the limiting compositional
values or points as follows:
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39. 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the FeTiAP0
molecular sieves the values of x, y and z are within the
limiting compositional values or points as follows:
D-14643
~23 1336717
.
Mole Fraction
Point x ~ y z
a ~0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 0.01
-f 0.39 0.60 0.01
FeTiAPO compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of iron, titanium, aluminum
and phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50C
and about 250C, and preferably between about 100C and
about 200C until crystals of the FeTiAPO product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
to about 30 days, generally-from about 12 hours to about
2S S days, have been observed. The product is recovered by
D-14643
-
~ 1336717
-224-
any convenient method such as centrifugation or
filtration.
In synthesizing the FeTiAPO compositions, it
is preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (MXAlyPz)O2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "b" has a value of from zero (0) to about S00,
preferably between about 2 and about 300; and "x", "y"
and "z" represent the mole fractions of "M" (iron and
titanium, aluminum and phosphorus, respectively, and
each has a value of at least 0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x v z
F 0.02 0.60 0038
G 0.02 0c38 0.60
H 0O39 0.01 0.60
2S I 0.98 0.01 0.01
J 0.39 0.60 0.01
D-14643
1~36717
225
In the foregoing expression of the reaction
composition, the reactants àre normalized with respect
to the total of "x", "y" and "z" such that
(x + y + zj = 1.00 mole.
Molecular sieves containing iron, titanium,
aluminum and phosphorus as framewor~ tetrahedral oxide
units are prépared as follows:
Preparative Reaqents
FeTiAPO compositions may be prepared by using
numerous reagents. The preferred sources of iron and
titanium for preparing FeTiAPOs are the same as those
for preparing the FeAPOs and TiAPOs already described
above. Other reagents which may be employed to prepare
FeTiAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(e) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3N: tri-n-propylamine, (C3H7)3N;
(h) Quin: Quinuclidine, (C7H13N):
D-14643
-226- 1336717
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(j) C-hex: cycloherylamine;
(k) TMAOH: tetramethylammonium hydroxide;
(1) TPAOH: tetrapropylammonium hydroxide;
and
(m) DEEA: 2 -diethylaminoethanol.
Preparative Procedures
FeTiAPOs may be prepared by forming a
homogeneous reaction mixture containing reactive
sources of iron, titanium, aluminum and phosphorus.
The reaction mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or
200C) for a time or placed in lined screw top
bottles for digestion at 100C. Digestions are
typically carried out under autogenous pressure.
XAPO MOLECULAR SIEVES
The XAPO molecular sieves have a
three-dimensional microporous framework structures
of MO2n, AlO2- and P02+ tetrahedral oxide units
having an empirical chemical composition on an
anhydrous basis expressed by the formula:
mA : (MXAlypz)o2
D-14643
~,,'
1336717
--2 ? 7--
wherein "R" represents at least one organic templating
agent present in the intracr~stalline pore system; "M"
represents at least one element from each of the classes
of: 1) iron and titanium; and 2) cobalt, magnesium,
manganese and zinc; "n" is 0, -1 or -2; "m" represents a
molar amount of "R" present per mole of (MXAlyPz)O2 and
has a value of zero (0) to about 0.3; and "x", "y" and
"z" represent the mole fractions of "M", aluminum and
phosphorus, respectively, present as tetrahedral oxides.
The mole fractions "x", "y" and "z" are generally
defined as being within the limiting compositional
values or points as follows:
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0 r 60
D 0.98 0.01 0.01
~ E 0.39 0.60 0.01
In a preferred subclass of the XAPO molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
D-14643
-228- 1336717
Mole Fraction
Point ~ x ~ y z
a 0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 0.01
-f 0.39 0.60 0.01
XA~O compositions are generally synthesized by
hydrothermal crystallization from a reaction mixture
containing reactive sources of "M", aluminum and
phosphorus, preferably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the Periodic Table, and/or
lS optionally an alkali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50 C
and about 250-C, and preferably between about lOO~C and
about 200-C until crystals of the XAP0 product are
obtained, usually a period of from several hours to
several wee~s. Typical effective times of from 2 hours
to about 30 days, generally from about 2 hours to about
2S 20 days, have been observed. The product is recovered
D-14643
~ -229- 1336717
by any convenient method such as centrifugation or
filtration. ~ ~ f
In synthesizing the XAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (MxAlyPz)2 bH2
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6; "M" represents at least one element from each
of the classes of: l) iron and titanium; and 2) cobalt,
magnesium, manganese and zinc; "b" has a value of from
zero (03 to about S00, preferably between about 2 and
about 300; and NX~ y~ and "z" represent the mole
fractions of "M" (iron and/or titanium, and at least one
of cobalt, magnesium, manganese and zinc), aluminum and
phosphorus, respectively, and éach has a value of at
least 0.01, with the proviso that "x" has a value of at
least 0.02.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
D-14643
1336717
-230- -
~ ~ Mole Fraction
Point ~ y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z-- such that
(x + y + z) = 1.00 mole.
XAPO molecular sieves are prepared as follows:
Prezarative Reagents
XAPO compositions may be prepared by using
numerous reagents. The preferred sources of elements
"M" for preparing XAPOs are the same as those for
preparing other APOs containing the same elements, as
described above and below. Other reagents which may be
employed to prepare XAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
D-14643
-231-
(e) TBAOH: 40 weight percent aql ~ 717
solution of tetrabutylammonium hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3N: tri-n-propylamine, (C3H7)3N;
(h) Quin: Quinuclidine, (C7H13N);
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(j) C-hex: cyclohexylamine;
(k) TMAOH: tetramethylammonium hydroxide;
(1) TPAOH: tetrapropylammonium hydroxide; and
(m) DEEA: 2-diethylaminoethanol.
Preparative Procedures
XAPOs may be prepared by forming a
homogeneous reaction mixture containing reactive
sources of elements "M", aluminum and phosphorus. The
reaction mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or 200C)
for a time or placed in lined screw top bottles for
digestion at 100C.
Digestions are typically carried out under
autogenous pressure.
MIXED-ELEMENT APO MOLECULAR SIEVES
The mixed element APO molecular sieves have a
framework structure of MO2n, A102 and P02+
tetrahedral units,
D-14643
~: `
. -; .~
~-232- 1336717
wherein M02n represents at least two different eiements
present as t~trahedral units "M02n" with charge~"n",
where "n" may be -3, -2, -1, 0 or +1. One of the
elements "M" is selected from the group consisting of
arsenic, beryllium, boron, chromium, gallium, germanium,
lithium and vanadium, while a second one of the elements
"M" is selected from the group consisting of cobalt,
iron, magnesium, manganese, titanium and zinc.
Preferably, "M" is a mixture of lithium and magnesium.
The mixed-element molecular sieves have an empirical
chemical composition on an anhydrous basis expressed by
the formula:
mR : (MxAlyPz)02
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(LiXAlyPz)02 and has a value of zero to about 0.3, but
is preferably not greater than 0.15; and "x", "y" and
"z" represent the mole fractions of the elements "M"
(i.e. "x" is the total of the mole fractions of the two
or more elements "M"), aluminum and phosphorus,
respectively, present as tetrahedral oxides. The mole
fractions "x", "y" and "z" are generally defined as
being within the limiting compositional values or points
as follows:
D-14643
Mole Fraction 1 3 3 6 717
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the
mixed-element APO molecular sieves the values of x,
y and z are within the limiting compositional values
or points as follows:
Mole Fraction
Point x y z
a 0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 0.01
f 0.39 0.60 0.01
An especially preferred subclass of the mixed
element APO molecular sieves are those in which the
value of x is not greater than about 0.10.
A second group (FCAPO's) of mixed element APO
molecular sieves described in U. S. Patent No.
4,686,093 issued August 11, 1987, have a framework
structure of M02n, A102- and P02+ tetrahedral units,
wherein MO2n
D-14643
1336717
-234-
represents at least two different elements which are
present as tetrahedral units "M02n" with charge "nU,
where "n" may be -3, -2, -1, 0 or +1 and which are
selected from the group consisting of arsenic,
beryllium, boron, chromium, gallium, germanium, lithium
and vanadium. These mixed-element molecular sieves have
an empirical chemical composition on an anhydrous basis
expressed by the formula:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(MXAlyPz)02 and has a value of zero to about 0.3; and
"x", "y" and "z" represent the mole fractions of the
elements "M" (i.e. "x" is the total of the mole
fractions of the two or more elements "M"), aluminum and
phosphorus, respectively, present as tetrahedral oxides.
The mole fractions "x", "y" and "z" are generally
defined as being within the limiting compositional
values or points as follows:
D-14643
1336717
.
235-
- - Mole-Fraction
Point x - y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of these mixed-element
APO molecular sieves the values of x, y and z are within
the limiting compositional values or points as follows:
Mole Fraction
Point x y z
a 0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 0.01 0.39
e 0.60 0.39 OoOl
f 0.39 0.60 0.01
The mixed-element APO compositions are
generally synthesized by hydrothermal crystallization
from a reaction mixture containing reactive sources of
the elements "M", aluminum and phosphorus, preferably an
organic templating, i.e., structure-directing, agent,
preferably a compound of an element of Group VA of the
Periodic Table, and/or optionally an alkali or other
metal. The reaction mixture is generally placed in a
D-14643
` - 36- 1336717
- sealed pressure vessel, preferably lined with an inert
plastic material such as polytetrafluoroethylene and
heated, preferably under autogenous pressure at a
temperature between about 50-C and about 250-C, and
preferably between about lOO C and about 200-C until
crystals of the AP0 product are obtained, usually a
period of from several hours to several weeks. Typical
effective times of from 2 hours to about 30 days,
generally from about 2 hours to about 20 days, and
preferably about 12 hours to about 5 days, have been
observed. The product is recovered by any convenient
method such as centrifugation or filtration.
In synthesizing the mixed-element APO
compositions, it is preferred to employ a reaction
mixture composition expressed in terms of the molar
ratios as follows:
aR : (MXAlyPz)O2 : bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6, and most preferably not more than about 0.5;
"b" has a value of from zero (0) to about S00,
preferably between about 2 and about 300, most
2S preferably not greater than about 20, and most desirably
not more than about 10; and "x", "y" and "z" represent
D-14643
- 1336717
~-237-
- the mole fractions of "M", aluminum and phosphorus,
respectively, "y" and "z" each having a value of at
least 0.01 and "x" having a value of at least 0.02,
with each element "M" having a mole fraction of at least
0.01.
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point x y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
Preferred reaction mixtures are those
cont~;ning not more than about 0.2 moles of the metals
"M" per mole of phosphorus.
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "x", "y" and "z" such that
(x + y + z) = 1.00 mole.
Since the exact nature of the mixed-element
APO molecular sieves is not clearly understood at
present, although all are believed to contain M02
D-14643
- 23~- 1336717
tetrahedra in the three-dimensional microporous crystal
framework structure, it is -advantaseous to characterize
the mixed-element APO molecular sieves by means of their
chemical composition. This is due to the low level of
the elements "M" present in certain of the mixed-element
APO molecular sieves prepared to date which makes it
difficult to ascertain the exact nature of the
interaction between the metals "M", aluminum and
phosphorus. As a result, although it is believed that
MO2 tetrahedra are substituted isomorphously for A102 or
PO2 tetrahedra, it is appropriate to characterize
certain mixed-element APO compositions by reference to
their chemical composition in terms of the mole ratios
of oxides.
Molecular sieves containing the metals "M",
aluminum and phosphorus as framework tetrahedral oxide
units are prepared as follows:
Preparative Reaqents
Mixed-element APO compositions may be prepared
by using numerous reagents. Reagents which may be
employed to prepare mixed-element APOs include:
(a) aluminum isopropcxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
~d) lithium phosphate or magnesium hydroxide
D-14643
- 1~36717
-239-
or appropriate salts of the other
elements "M",~as described akove;
(e) TEAOH: 40 weight percent aqueous solution
- of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution
. of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
PreDarative Procedures
Mixed element APOs may be prepared by forming
a starting reaction mixture by mixing aluminum oxide,
magnesium hydroxide, lithium phosphate (or the
corresponding salts of the other elements "M"). To this
mixture the phosphoric acid is added. The resultant
mixture is then blended until a homogeneous mixture is
observed. To this mixture the templating agent is added
and the resulting mixture blended until a homogeneous
mixture is observed.
D-14643
-240- 1336717
- The reaction mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vessel and digested at a temperature (150C or 200C)
for a time or placed in lined screw top bottles for
digestion at 100C. Digestions are typically carried
out under autogenous pressure.
D-14643
