Note: Descriptions are shown in the official language in which they were submitted.
1329213
Ei~OC2SS FOR q~E PRODUC~ION OF AZIRI~INES
Field of the Invention
This invention relates to a process for the
production of aziridines. Nore specifically, this
invention relates to a process for converting a
~-hydroxyamine to the corresponding aziridine by
contacting the amina with molecular sieves loaded with
certain metals. The process of the invention is
particularly, though not exclusively, intended for the
conversion of monoethanolamine to ethylenimine.
Backaround 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 ~evere handling
difficulties, which make it highly undesirable to store
or transport the ethylenimine, so that: desirably a
process for the production of ethylenimine should begin
from in~xp~nsive starting materials, and should provide
the ethylenimine in a form which permits its direct feed
to the ethyleneamine production unit without intervening
isolation or storage of the ethylenimine.
Various processes for the production of
ethylenimine are kno~m. For example, ethylenimine may
be produced by the reaction of ethylene dichloride with
anhydrous ammonia. However, this method suffers from
D-14642
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the disadvantages of invoiving halide use and producing
a salt by-product.
one commercially attractive process for the
production of ethylenimine is the catalytic dehydration
of monoethanolamine. Various catalysts capable of
effecting this dehydration are known; most of the Xnown
catalysts are oxides of tungsten, tantalum or niobium,
in some cases pro~oted 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 maXing an alXyleneaziridine (such as
ethylenimine) *rom an alkanolamine (such as
monoethanolamine); the catalyst contains oxides of
either tantalum or niobium together with the oxides of
iron and chromium, in which the ratios of the metals
are:
MloFeo~s-2~gcro~3-l~7
wherein N is tantalum or niobium.
U.S. Pat-nt No. 4,301,036, issued November 17,
1981 to Childress et al., describes a dehydration
c~talyst for the dehydration of alkanolamines to
alkyleneaziridines. This dehyd~ation catalyst is
prepared by applying a solution of a tungsten salt on to
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--3--
a low sur ace area support (usually silicon carbide),
calcining the salt to tungsten oxide, and thereafter
applying silica to the tungs`ten-coated support so as to
form a coating of silica over the tungsten.
U.S. iatent No. 4,337,175, issued June 29,
1982 to Ramirez, describes a dehydration catalyst for
the dehydration of alkanolamines to alkyleneaziridines.
This dehydration catalyst consists essentially of an
oxide of tantalum or niobium with an al~aline 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 con~ersion of monoalXanolamines. For
example, U.S. Patent No. 4,524,143, issued June 18, 1985
- 15 to Vanderpool, describes a process for the production of
linear polyethylenopolyamines from ethylenediamine and
monoethanolamine using thermally activated pelleted
catalyst compositions comprising zirconium silicate
having phosphorus depo~ited thereon.
Also, U.S. Patent No. 4,438,281, issued March
20, 1984 to Johnson, describes the s-lective production
of monoalkanolamin-s from alkylene oxides and a~monia
over acidic inorganic catalysts, such as acidic
silica-aluminas, natural zeolites and acid clays.
It has now be-n discovered that
~-hydroxyalkylamines can be converted to the
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.
~329213
correspondirs aziridines using as catalysts molecular
sieves loaded with certain metals
Summarv of the Invention
This invention provides a process for the
S dehydration of a ~-hydroxyalkylamine to the
corresponding aziridine, which process comprises
contacting the amine with a molecular sieve, the
molecular sieve having incorporated therein at least one
metal selected from the group consisting of the alkali
metals and the alkaline earth metals, the contacting of
the amine with the molecular sieve being effected under
conditions effectiv~ to convert the amine into the
corresponding aziridine
etailed Descri~tiQ~_Qf thç Invention
The molecular SieVQS used in the process of
the present invention can be chosen from any of the
known classos of molecular sieves Thus, for example,
the molecular SieVQ may be a natural or synthetic
zQolite aluminosilicate, or a microporous form of
? silica, such as Silicalite (described in U S Patent No
4,061,724 issu d DecembQr 6, 1977 to R W `Grose et al)
; The molecular SiQVe may also be a non-zeolitic molecular
sievQ of th- aluminophosphate or silicoaluminophosphate
type Such non-zeolitic molecular sieves comprise a
larg- number of aluoinophosphates and
silicoaluminophosphates having a variety of crystal
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structures, ~hich may inciude one or more other elements
in addition to aluminum, phosphorus and silicon. Since
many of the non-zeolitic mol`ecular sieves are not
described in U.S. Patents, and some are not described in
publically-available literature, much material
describing these non-zeolitic molecular sieve has to be
repeated herein. However, for the convenience of the
reader, the manner in which the non-zeolitic and other
molecular sieves are used in the process of the present
invention will ~irst be described, and thereafter the
chemical nature, and methods for the preparation, of the
non-zeolitic molecular sieves will be described.
PROCESS OF T~ yE~TION
As already mentioned, in the process of the
present invention an ~-hydroxyalkylamine is contacted
with a molecular sieve to produce the corresponding
aziridine. The process of the present invention is
especially usoful for the conversion of monoethanolamine
to ethylenimine, but may also be used for other
production of oth~r substituted aziridines, for example
propylenimine ~2-methylaziridine) from propanolamine
(~-hydroxypropylam$ne).
Nhen the molecular sieve used in the process
of the pres~nt invention is a zeolite, it may be any of
the natural Qr synthet~c zeolites known in the art.
Such zeolit-s include, for example, zeolite X, zeolite Y
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(see U S Patent No 3,130,007), steam-stabilized
zeolite Y (ultra-stable Y), zeolite ~ (see U S Patent
No 3 308,069), zeolite KZ-2`0 (see U S Patent No
3,445,~27), faujasite, erionite, mordenite, offretite,
chabazite, LZ-10 (see U X Patent No 2,014,970), LZ-2I0
(see U S Patent No 4,503,023 to Breck), FU-l-type
zeolites, NU-type zeolites, and the ZSM zeolites
denominated by the nomenclature "2SM-n" where "n" is an
integer ZSM zeolites include but are not limited to
ZSM-3 ~seo U S Patent No 3,415,736), ZSM-5 (see U S
Pat~nt No 3,702,886 and RQissu~ No 29,948), ZSM-ll
(SQe U.S. Patent No 3,709,979), ZSM-12 (see U S Patent
No 3,832,449), ZSN-23 ~seQ U S PatQnt No 4,0~6,842),
ZSM-35 tSQQ U S Patent No 4,016,245), ZSM-38 (see U S
lS Patent No 4,046,8S9) and ZSM-48 (see U S Patent No
4,423,021) A particularly preferred zeolite for USQ in
the process of the present invention is LZ-105,
m~nufactured by Union Carbide Corporation; this zeolite
is d~scrib~d and claim~d in U S Patent No 4,257,885
As alroady mentioned, the aluminophosphate or
silicoaluminophosphat~ molecular sieves useful in the
process of tho present invention are described in detail
below Howev~r, at this point it is noted that the
preferr~d ~luminophosphate molecular sieves are the
`25 AlP04's describod and claimed in U S Patent 4,310,440,
issued J~nuary 12, 1982 to Wilson et al }llustrative
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1329213
,
AlP04 species ar~ AlP04-5 and AlP04-11, the latter being
preferred.
The preferred silicoaluminophosphate molecular
sieves for use in the process of the present invention
are the SAP0's described and claimed in U.S. Patent
4,440,871 issued April 23, 1984 to Lo~ et al.
Illustrative SAPo species are SAPO-5, SAPo-ll and
SAP0-34.
In their as-synthesized form, the non-zeolitic
molecular sieves (and some of the other molecular
sieves) contain within their internal pore systems at
least one form of the organic templating agents used in
their synthesis. The organic moiety may be 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,
howev~r, that some or all of the organic moiety is an
occluded molecular species in a particular species of
molecular siev~. Such templating agents within the pore
system may interfere with the catalytic activity and
incorporation of metals into the molecular sieva and
accordingly the templating agents should be removed
before metal is incorporated into the molecular sieve or
the molecular sievQ is used as a catalyst. As a general
rule the templating agent, and hence the occluded
D-14642
1329213
orsanic species, is too large to move freely through the
pore system of the molecular sieve and must be removed
by calcining the molecular sieve at temperatures of 200O
to 700'C, preferably about 350- to about 600'C, to
s 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 solvent extraction, which will be familiar to
those sXilled in the molecular sieve art.
Before being used in the process of the
present invention, the molecular sieve is loaded with
(i.e., has incorporatsd therein) at least one metal
selected from the group consisting of the alkali metals
and the alkaline ear~h metals. Of these metals, the
alkali metals are preferred, with cesium being the
especially pr~ferred motal. Desirably, the amount of
metal incorporated into the molecular sieve is up to
about 20 weight p-rcent Or the weight of the molecular
siove (as measured prior to incorporation of the metal
therein).
ThQ incorporation of the metal into the
molecul~r sieve may be effected by any of the techniques
well-known to thosQ skilled in the molecular sieve art
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1329213
g
for loading metals into the pores of molecular sieves;
the preferred technique for metal incorporation depends
upon the type of molecular sieve used. In the case of
those molecular sieves having a significant ion-change
capacity, such as zeolites, silicoaluminophosphates and
aluminophosphates containing at least one framework
element in àddition to aluminum and phosphorus, the
metal is desirably incorporated by ion-exchange;
appropriate techniques for such ion-exchange are well-
known to thosa sXilled in the molecular sieve art.Following the ion-exchange, the catalyst may be washed,
but such washing is not recommended since in some cases
it has been found to lower the selectivity of the
catalyst to the desired aziridine.
In the case of those molecular sieves not
having a significant ion-change capacity, such as the
AlP04 aluminophosphates and silica molecular sieves, the
metal is desirably incorporatQd into the molecular sieve
by contacting the mol~cular sieve with a solution of a
salt of the metal under conditions allowing the solution
to p n~trate the pore~ of the molecular sieve, and
ther~after drying the molecular sieve to drive off the
solvent from the catalyst. To ~acilitate the entry of
the solution into the pore~ of the molecular sieve, the
molecular sieve i-~ prefQrably degassed prior to being
contacted with the solution of the metal salt. The
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--10--
solution is conveniently introduced into the molecular
sieve by the so-called "incipient wetness" technique; in
this technique, the pore voiume of the molecular sieve
is determined and the volume of the solution of the
metal added to the molecular sieve (preferably after
degassing of the molecular sieve) is adjusted to
substantially equal this pore volume; this technique
enables the amount of metal added to the molecular sieve
to be controlled accurately Following the addition of
the metal, the molecular sieva is normally dried and
then calcined to convert the metals to their oxides
When loading the metal into the molecular
sieve by ion-exchange, incipient wetness or other
tec~nique, the nature of the metal compound used is not
critical; in general àny sufficiently soluble compound
of the relevant m tal may be employed, provided of
course th~t the compound does not leavQ in the molecular
sieve residu-Q which interfere with the desired
cat~lytic activity It has been found that acetates and
nitrateQ are often useful for introducing the metal into
the molecular sieve
The process of the present invention may be
conducted with the amine in the liquid phase However,
in view of the temperatures which are needed in practice
to carry out the process of the present invention at an
economical rate, it is preferred that the process o~ the
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present imlention be operated as a hetero~eneous, gas
phase reaction with the amine in the gaseous phase,
since a gas phase process càn be run at higher
temperatures under relatively moderate pressures
s (typically of the order of a few atmospheres) using
comparatively inexpensive equipment.
In such a gas phase process, the amine may be
mixed with an inert (i.e., such that it does not
interfere with the course of ~he amine-aziridine
reaction~ carrier gas, (such as nitrogen or ammonia)
while being contacted with the molecular sieve, although
the use of such an inert carrier gas is not essential in
the process of the present invention, which can ~e
operated using pure amine as the gaseous feed. The
degree of dilution of the amine with such an inart
carrier gas may vary considerably depending upon any
process constraints restricting the use of inert
dilu~nts. (For examplQ, in co~mercial production, the
use of very large quantities of inert carrier gas is
disadvantageous due to the co~t of pumping large volumes
o~ gas and increased difficulty in i~olating the
product, which increase the energy costs of the
process.) If the procesQ of the present invention is to
be carried out using an inert gas, in general it is
recommended that the amine constitute ~rom about 1 to
about 90, and preferably about 9 to about 30, mole
D-14642
1329~3
-12-
percent of the amine/inert ~as feed. Increasing the
dilution of the amine tends to increase the selectivity
of the reaction to the desirèd aziridine, but at the
cost of reduced conversion.
Selection of the temperature at which the
process of the present invention i5 to be conducted
involves a compromise between selectivity to the desired
aziridine product and conversion of the amine used as
starting material. It is recommended that the process
of th~ present invention be conducted 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 aziridine product decreases dramatically.
At least ~or ethylenimine production, the preferred
temperature range is from about 350'C to about 425'C.
The process of the present invention can be
run ovQr a wide ran~e of pressurQs ranging from
sub-atmospheric pressure~ to 1000 psig. (6.9 MPa.) or
more. However, since the use of very high pressures
does not confer any significant advantages but increases
oquipment costs, it is recommended that the process of
the present invention be carried out at a pressure of
from about atmospheric pressure to about 100 psig.
(about 0.7 MPa.).
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The process of the present invention can also
be carried out over a wide range of weight hourly space
velocities of the amine. Fo`r example, weight hourly
space ~elocities 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 amine.
The molecular sieve catalysts used in the
process of the present invention enable the
amine-aziridine reaction to be carried out at high
selectivities. ~s illustrated in the Examples below,
the process of the present invention can be carried out
with a selectivity to the aziridine of at least about
50%.
As with some reactions catalyzed by molecular
sieves, the conversion achieved in the process of the
present invQntion may fall as the time for which the
molecular sieve catalyst has been used in the process
increases. If the molecular sieve catalysts become
deactivatQd, then the deactivated catalyst can readily
be r generatQd by heating in air at an appropriate
temperature (typically about 500'C) and for an
appropriate period (typically one hour).
ThQ molecular sieve may be modified by
depositing or impregnating the molecular sieve with
cations, anions or salts (other than the alkali metal or
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1329213
- alkaline ea~~ met 1 used to rende. the molecular sieve
.
efficacious in the process of the present invention) so
-- as to improve its efficacy as a catalyst in ~he 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
procedures may involve suc~ procedures as (1)
i=pregnating 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, or by the
exchangQ of cationQ present in the molecular sieve with
cations that provide for the desired properties
(provided of course that the molecular sieve is one
having a sisnificant 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
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~5
I~pr2s~.a~ion o. e~^ha..~e procedu.es
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 general:Ly
susceptible to the loss of the modifying materials by
abrasion.
Suitable modifying mate-ials include
transition metals and the salts thereof including
inorganic and organic salts such as nitrates, halides,
hydroxides, sulfatas and carboxylates. Other modifying
materials generally employed in the art are also
belie~Qd to bQ employablQ in the molecular`sieves.
In carrying out the process of the present
invention, the molecular sieves may be admixed (blended)
or provid~d seguentially to other materials which may
provide some prop~rty which is beneficial under process
condition~, such as improved temperature resistance or
impro~ed catalyst life by minimization o~ 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
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and mixtures thereof. In addition, the molecular sieves
may be formed with materials such as silica, alumina,
silica-alumina, silica-magne`sia, silica-zirconia,
siIica-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 sieve content ranging between about 1 and
about 99 percent by weight of the composite.
The following Exa~ples 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 Exa~ples illustrate the use of
cesium-loaded AlPO4-11 and LZ-105 in the process of the
present invention. The characteristic X-ray table for
AlPO4-11 is given in U.S. Patent No. 4,310,440 at Table
8 in column 15, but is repeatad below for convenience.
Q4-11
Relative
2~ dfALIntensity 100 x I/Io
9.4 - 9.5 9.41 - 9.31 31-49
2520.5 - 20.6 4.33 - 4.31 34-53
21.0 - 21.25 4.23 - 4.19 100
22.15- 22.25 4.01 - 4.00 12-58
22.5 - 22.7 3.95 - 3.92 47-75
23.15- 23.5 3.84 - 3.79 10-68
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1329213
~ Ex~erimental Conditions
The various molecular 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 500 C
in air for 1 to 12 hours.
The experiments were conducted using a micro
reactor 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
disposad vertically with a downward flow of reactants
and products. Connected to the inlet of the reactor
werQ a ~ource of nitrogen carrier gas and a liquid feed
line containing monoethanolamine connected to a high
. .
pressure liguid chromatography (HPLC) type solvent pump.
Immediately below the reactor was disposed a cold trap
kept at O'C. Gas chromatographic analysis of the outlet
gas indicated that all of the ethylenimine produced was
retained in the cold trap and only very small amounts of
ammonia and a material with a retention time similar to
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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 Chromosorb~ 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.
Exam~le 1
A sample of AlPO4-11 was loaded with 20
percent of its own weight of cesium acetate by the
incipient wetness technique described above; thus,
the concentration of cesium in the metal-loaded
catalyst was approximately 0~104 moles per 100 grams
of AlPO~-ll prior to metal loading. The reactor was
charged with 1.0 9~ of the cesium-loaded catalyst and
heated to 375C. Nitrogen carrier gas was passed
through the reactor at a rate of 20 ml/min. at
atmospheric pressure, and liquid monoethanolamine was
fed into the nitrogen stream at a rate of 8 ml/hour.
Analysis of the products of the reaction showed that
more than 70 percent of the products were
ethylenimine, and that this aziridine was formed at a
rate of appro~imately 3 lb/hour/ft3 of catalysts
(approximately 48 kg/hour/m3 of catalyst).
*Registered Trademarks
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Exam~le 2
LZ-105 zeolite was ion-exchanged with a
solution of cesium acetate until the ion-exchange was
- total. The ion-exchanged zeolite was not washed. The
reactor was charged with 1.0 g. of the cesium-loaded
catalyst and heated to 375'C. Nitrogen carrier gas was
passed through the reactor at a rate of 2 0 ml/min. at
atmospheric pressure, and liquid monoethanolamine was
fed into the nitrogen stream at a rate of 0. 6 ml/hour.
Analysis of the products of the reaction during the
first hour of operation of the catalyst showed that
about 50-60 percent of the products were ethylenimine,
and that t~is aziridine was formed at a rate of
approximately 10 lbfhour/ft3. of catalyst (approximately
160 kg/hour/m3. of catalyst). As the operating time of
the catalyst increaQed, the -~electivity to ethylenimine
decreased and evQntually morpholine became the major
product.
ExamDle 3
Samples of AlP04-11 was loaded with 20 percent
of their own weight of ceaium acetate or cesium nitrate
by the incipient wetness techni~ue described above: the
samples were refluxed for 3 hours with 0.5M solutions of
the cesium salt, then filtered, the salt
2S solution treatmQnt was repeated, the product re-filtered
and the solids dried in an oven overnight at llO-C.
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Runs were conducted at varying temperatures and
monoethanolamine and nitrogen flow rates, as set
forth in Table 1 below. The conversions and
selectivities to ethylenimine achieved are shown in
Table 1.
Table 1
N2 flo~ rate MEA flow rate Conversion Selectivity
Tem~. (C) (ml/min.)(ml/hr.) (%) (%)
375 20 0.5 1.0 60
375 20 2.0 1.0 65
400 20 2.0 1.5 60
425 20 8.0 2.0 40
425 20 2.0 10.0 20
425 40 2.0 5.0 30
420 66 2.0 5.0 35
420 66 1.0 5.0 35
350 20 2.0 0
Attention is directed to the application of
Xurt D. Olson and Steven W. Kaiser (Canadian
Application No. 586724), which describes and claims a
process for the catalytic dehydration and/or
deamination of alkanolamines, including
monoethanolamine to give mixtures of alkanolamines,
alkylamines and ~in come cases) aziridines, including
ethylenimine. The catalyst used is a non-zeolitic
molecular sieve, which is not metal-loaded.
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NON-ZEOLITIC MOLECULAR SIEVES
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 4,793,984 and certain ~AlPO4n, "MeAPO",
"FeAPO", ~TAPO" and "ELAPO" molecular sieves, as
hereinafter described. Crystalline AlPO4~
aluminopho~phates are disclosed in U.S. Patent No.
4,310,440; crystalline me~al aluminophosphates
(MeAPOs where "Me" is at least one of Mg, Mn, Co and
Zn) are disclosed in U.S. Patent No. 4,567,029;
crystalline ferroaluminophosphates (FeAPOs) are
disclosed in U.S. Patent No. 4,554,143; titanium
aluminophosphates ~TAPOs) are disclosed in U.S.
Patent No. 4,500,651; 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.
:`
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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
copending U~S. Patent No. 4,793,9R4 as crystalline
molecular sieves having three-dimensional microporous
framework structures of ELO2, AlPO2, PO2, SiO2 oxide
units and having an empirical chemical composition on
an anhydrous basis expressed by the formula:
mR : (ELwAl~PySiz)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
D-14642-C
.
,~ ~
1329~
-23-
0.3; "EL" represents at least one element capable of
forming a three dimensional oxide framework, "EL" being
characterized as an element having a mean "T-o" dictance
in tetrahedral oxide structures between about 1.51
Angstroms and about 2.06 Angstroms, "EL" having a cation
electronegativity between about 12S 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 ~wn, nxn, nyn and "z" represent the mole
~ractions of "E~n, aluminum, phosphorus and silicon,
respectively, present as framework oxides, said mole
fractions being within the limiting compositional
values or points as follows:
Mole E~S~ion
Poin~ ~ y t2 + W)
A 0.60 0.39-(O.Ol)p O.Ol(p + l)
B 0.39-(O.Olp) 0.60 O.Ol(p + l)
C 0.01 0~60 0.39
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 (ElwAlxPy~iz)02 constituent.
The "E~APSO" molecular sieves are also
described as crystalline molecular sieves having
D-14642
.
1329213
-24-
three-dimensional microporous framework structures of
EL02, ~12, sio2 and P02 tetrahedral oxide units and
having an empirical chemical composition on an anhydrous
basis expressed by the formula:
mR : (ELwAlxPySiz)2
wherein "R" represents at least one organic templating
agent presènt in the intracrystalline pore system; "m"
represents the molar amount of ~ present per mole of
(E ~ AlxPySiz)02 and has a value of from zero to about
0~3: "EL" represents at least one element capable of
forming a framework tRtrahedral oxide and is selected
from the group consisting of arsQnic, beryllium, boron,
chromium, cobalt, gallium, germanium, iron, lithium,
magnesium, manganese, titanium and zinc; and "w", "x",
"y" and "z" repre-Qent the mole fractions of "EL",
aluminum, phoQphorus and silicon, respectively, present
as tetrahedral oxid~s, said mole fractions being within
the limiting compositional values or points as follows:
Mole Fraction
20 Point ~ ~ 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.
D-14642
' ' . .: '
- 25 - 1329213
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 assigned patents and applications [(A)
following a serial number indicates that the
application is abandoned and (C) indicates that the
application is a continuation o~ the immediately
preceding patent or application]:
D-14642-C
~.~
1329213
- 26 -
U.S. Patent/S~rial No. Filed NZMS
599,808(A) April 13, 1984 AsAPSO
4,701,281 Mar~h 31, 1986 AsAPSO
600,177(A) April 13, 1984 BAPSO
845,255(A) March 28, 1986 BAPSO
600,176(A) April 13, 1984 BeAPSO
841,752(A) March 20, 1986 BeAPSO
599,830(A) April 13, 1984 CAPSO
4,738,837 April 15, 1986 CAPSO
599,925(A) April 13~ 1984 GaAPSO
4,735,806 March 31, 1986 GaAPSO
599,971(A) April 13, 1984 GeAPSO
4,992,250 April 15, 1986 GeAPSO
599,952(A) April 13, 1984 LiAPSO
847,227(A) April 2, 1986 LiAPSO
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
4,935,216 April 13, 1984 ZnAPSO
4,683,217 April 13, 1984 FeAPSO
CAN. 1 248 080 April 13, 1984 QuinAPSO
4,956,164(C) June 22, 1987 QuinAPSO
4,741,892 April 13, 1984 QuinAPSO
600,182(A) April 13, 1984 CoMnMgAPSO
57,648(A) June 9, 1987 CoMnMgAPSO
600,183(A) April 13, 1984 SenAPSO
D-14642-C
- 27 - ~329213
TiAPSO MOLECULAR SIEVES
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 : (TiWAl~pysiz)o2
wherein "R" represents at least one organic
templating a~ent present in the intracrystalline pore
system; ~mN represents the molar amount of `'R"
present per mole of tTiwAlxPySiz)02 and has a value
from zero to about 0.3; and "wn, "xn, "y" and "z"
represent the mole fractions of titanium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral o~ides and each has a value of at least
0.01. The mole ~ractions nwn, nxn, -yn and nZ~ are
generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point ~ y (z I 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-14642-C
1329213
-28-
In a subclass of TiAPSo molecular sieves
the values "w", "xn, "y" and "z~ in the above formula
are within the tetragonal compositional area defined by
points a, b, c and d, said points a, ~, c and d
representing the following values for "w", "x", "y" and
nzn
Nole Fraction
Point ~ y (z + w)
a 0 55 0 43 0 02
b 0 43 0 55 0 02
c 0 1~ 0 55 0 35
d 0 5S 0 10 0 35
TiAPS0 compositions are generally synthesized
by hydroth-r~al crystallization from a reaction mixture
containing active sources of titaniumj silicon, aluminum
and phosphorus, ~nd preferably an organic templating,
i - , structura-direct~ng, agent, preferably a compound
an el~m~nt of Group VA of the Periodic Table, and/or
optionally ~n alkali or oth-r ~etal The reaction
mixture is generally placed in a sealed pressure vessel,
pr f~rably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pr-~sure at a temperature between 50'C and
250 C, and prefQrably b-tween lOO C and 200 C until
cryst~ls of th- TiAPSo product are obtained, usually a
p-riod of from houra to -~everal weeks Generally, the
` D-14642
13292~3
-29-
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.
In synthesizing the TiAPSOs, it is preferred
to Qmploy a reaction mixture composition expressed in
terms of the molar ratios as follows:
aR : (TiWAlxpysiz)o2 bH2O
wherein "R" is an organic tQmplating agQnt; "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 batwè~n about 2 and about 300; and "wn, "x",
"y" and "z" repres~nt the mole fractions of.titanium,
aluminum, phosphorus and silicon, respectively, and each
has a valuQ of at least 0.01.
In onQ Qmbodiment th~ reaction mixture is
selected such that the mole fractions "w", "x", "y"
; 20 and "z" ara generally defined as being within the
limiting compositional valuQs or points as follows:
D-14642
_ 30 _ 1329213
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
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 ~wn, nxn, nyn and ~zn such
that ~w ~ x ~ y ~ z) ~ 1.00 mole. Molecular sieves
containing titanium, aluminum, phosphorus and silicon
as framework tetrahedral oxides are prepared as
follows:
~L5L~ L Reagents
TiAPSO compositions are prepared using
numerous reagents. Typical reagents which may be
employed and abbreviations employed in U.S. Patent
: No. 4,684,617 for such reagents are as follows:
(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 Na20;
(C) H3PO4: 85 weight percent aqueous
phosphoric acid:
(d) Tiipro: titanium isopropoxide;
-
~ D-14642-C
,L~
''` , ` ' ' `. ' `, ' ' ` ' ` :. `"
` 1329213
31-
(e) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
S (g~ Pr3NH: tri-n-propylamine, (C3H7~3N;
(h? Quin: Quinuclidine, (C7H13N);
li) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH); and
(j) C-hex: cyclohexylamine.
Pre~arative 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
blend~d (about 2 minutes) until a homogeneous mixture is
observed.
The titanium isopropoxide is added to the
above mixture and the reQulting 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 minute$. When the organic
templating agent iQ quinuclidine the procedure is
modi~ied such that the quinuclidine is dissolved in
D-~4642
1329213
- 32 -
about one half the water and accordingly the H3PO4 is
mixed with about one half the water. (The pH of the
mi~ture is measured and adjusted for temperature).
The mi~ture is then placed in a lined
(polytetrafluoroethylene) lined stainless steel
pressure vessel and digested at a temperature (150C
or 200C) for a t~me 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 MO~ECULAR 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 o~ide units and have an empirical
chemical composition on an anhydrous basis expressed
by the formula:
mR : (M9WAlxPysiz)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 o~ides and
D-14642-C
`- 1329213
33-
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 ~ y r2 + W)
A Ø60 0.38 0.02
B 0`.39 0.59 0.02
C 0.01 0.50 0.39
10 D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the MgAPSO
molecular sieves th~ values "w", "x", -y" and "z" in ~he
above formula are within the limiting compositional
values or points as follows:
Mole Fraction
Point ~ ~ fz + w~
a 0.55 0.43 0.02
b 0.43 0.55 0.02
20 c 0.10 0.55 0.35
d 0.55 0.10 0.35
MgAPS0 compositions are generally synthesized
by hydrothermal crystallization for an e~fective time at
effRctive pressures and temperatures from a reaction -
mixture containing reactive sources of magnesium,silicon, aluminum and phosphorus, an organic templating,
D-14642
1329213
i.e., structure-directing, agent, preferably a compound
of an element of Group VA o~ the Periodic Table, and may
be an alkali or other metal. The reaction mixture is
generally placed in a sealed pressure vessel, prefera~ly
lined with an inert plastic material such as polytetra-
fluoroethylene and heated, preferably under autogenous
prassure at à temperature between 50-C and 250'C, and
preferably between lOO'C and 200'C until crystals of the
MgAPS0 product are obtained, usually a period of from
several hours to several weeks. Genarally, the
crystallization pQriod will be from about 2 hours to
about 30 days with it typically being from about 4 hours
to about 20 days for obtaining ~gAPS0 crystals. The
product is recovered by any convenient method such as
centrifugation or filtration.
: In synthesizing the MgAPS0 compositions, it is
proferr~d to employ reaction mixture compositions
expressed in terms of the molar ratios as follows:
aR : (MgwAlxPysi8)o2 bH2
wher~in "R" is an org~nic templating agent; "a" is the
amount of organic templating agent "R" and can have a
value within the range of from zero (0) to about 6 and
is morQ preferably an effQctivQ amount greater than zero
to about 6; "b" has a value of from zero (0) to about
25 500, prefQrably betweQn about 2 and about 300; and "w",
"xn, "y" and "z" represQnt the mole fractions of
D-14642
1329213
-35-
~ magnes-um, 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 "wn, "xn, ~y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point ~ y ~ Z I 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 n Z n 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 Reaqents
MgAPSO compositions ara 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 pseudobaehmite;
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1329213
-36-
(c) LUDOX-LS: Trademark of DuPont for
an aqueous solution of 30 weight
percent SiO2 and 0.1 weight
percent Na20;
td~ Mg(Ac)2: magnesium acQtate
tetrahydrate. Mg(C2H302).4~20;
(~) H3P04: 8~ weight p~rcent
aqueous phosphoric acid in water:
- (f) TBAOH: tetrabutylammonium hydroxide (40
wt. % in water);
(g) Pr2NH: di-n-propylamine;
th) Pr3NH: tri-n-propylamine;
~i) Quin: Quinuclidine;
(;) MQuin: Mothyl Quinuclidine hydroxide,
(17.9% in water);
(~c) C-nex: cyclohsxylaminQ;
1) TEAOH: t~traethylammonium hydroxide
(40 wt. % in wat~r);
(m) DEEA: Diethylethanolamine;
(n) i-Pr2NH: di-isopropylamine:
~o) TEABr: tetraethylammonium bromide; and
(p) TPAOH: tetrapropylammonium hydroxide
(40 wt. % in water).
D-14642
1329213
-37-
- Preparative Procedures
The MgAPSO compositions may be prepared by
preparing reaction mixtures having a molar composition
expressed as:
eR:fMgo:hAl2o3:ip2os:gsio2:~H2o
wherein e, f, g, h, i and j represent the moles of
template R, magnesium (expressed as the oxide), SiO2,
A1203, 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.
Nethod 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 homogeneQus mixture is observed. When
the aluminum source is CATAPA~ the water and H3PO4 are
f~rst mixed with the CATAPAL added thereto. The
magnesium acetatQ 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-14642
1329213
reaction mixt~~e) is placed in a lined (polytetrafluoro-
ethylene) stainless steel pr~essure vessel and digested
at a temperature (150-C or 200-C) ~or an effective time.
Alternatively, if the digestion temperature is 100-C the
final reaction mixture is placed in a lined
Ipolytetrafluoroethylene) screw top bottle for a time.
Digestions are typically carried out under autogenous
pressure. The products axe removed from the reaction
vessel, cooled and evaluated as set forth hereinafter.
Nethod B
When mathod B is employed the organic
templating agent is di-n-propylamine. The aluminum
source, silicon source and one-half of the water are
fir~t mixed and blended until a homogeneous mixture is
observed. A second solution was prepared by mixing the
rQmaining water, the H3PO4 and the magnesium acetate.
T~is 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
mixtur- is observed. The organic templating agent(s)
is/àre then added and the resulting reaction mixture
digested and product recovered as in Method A.
Metho~ C
~ethod 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-14642
- 39 - 132~213
followed by addition of the LUDOX LS. H3PO4 and
magnesium acetate are then added to the resulting
mi~ture. The organic templating agent is then added
to the resulting mixture and digested and product
recovered as in Method A.
NnAPSO MOLECULAR SIEVES
The MnAPSO molecular sieves of U.S. Patent
No. 4,686,092 have a framework structures of
MnO2 -2, AlQ2 ~, PO2 + and SiO2 tetrahedral units and
have an empirical chemical composition on an
anhydrous basis e~pressed 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", ~", "y" and "z-- are generally
defined, as being within the limiting compositional
values or points as follows:
D-14642-C
1329~13
-40-
Mole Fraction
Point x y k + 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
The values of w, x, y and z may be as follows
Mole Fraction
10 Point ~ y fz + 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
MnAPS0 compositions are generally synthesized
by hydrotherm~l crystallization from a reaction mixture
containing reactiv~ sources of manganese, silicon,
aluminum and phosphorus, prefQrably an organic
templating, i.e., structure-directing, agent, preferably
a co~pound of an l~m nt of Group VA of the Periodic
Tabl~, 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
betwe n about SO C and about 250~C, and preferably
D-14642
.
.
1329213
-41-
between about lOO C and about 200 C until crystals of
the MhAPS0 product are obtained, usually a period of
from several hours to several weeks. Typical ef~ective
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 MnAPS~ compositions, it is
preferred to employ a reaction mixture composition
0 expressed in terms of the molar ratios as follows:
aR : (MnwAlxpysiz)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 sQro ~0) to about 500,
prefQrably between about 2 and about 300; and "w", "x",
"y" and ~z" represont the mole fractions of manganese,
aluminum, phosphorus and -~ilicon, respectively, and each
has ~ value of at least 0.01.
In one embodiment the reaction mixture is
selectQd such that the mole fractions "w", "x", "y" and
NZ~ are generally defined as being within the limiting
compositional values or points as follows:
D-14642
1329~13
-42-
` Mole Fraction
Point x y .rz + 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 ` 0.50 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. ~olecular sieves
containing manganese, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follows:
Preparative Reaaents
NnAPSO compositions may be preparèd by using
numerous reagents. Reagents which may be employed to
prepare NnA~SOs include:
(a) Alipro: aluminum isopropoxide:
(b) CATAPAL: Trademark of Condea Corporation
for hydrated pseudoboehmite;
tc) LUDOX-LS: LUDOX-LS is the tradename of
DuPont for an aqueous solution of 30
weight percent sio2 and 0.1 weight
percent Na2O:
D-14642
.
132g213
-43-
(d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e) MnAc: Manganese acetate,
Mn(C2H3O2)2.4H2o;
(f~ TEAOH: 40 weight percent aqueous solution
of tetra~thylammonium hydroxide:
(g) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH:
(i~ ~r3N: tri-n-propylamine, (C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(1) C-h~x: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEEa: 2-diethylaminoethanol.
Pr~oarative ProcQdures
~ MnAPSOs are prepared by forming a starting
reaction mixture by adding the H3PO4 to one hal~ of tha
quantity of water. This mixture is mixed and to this
mixture the aluminum isopropoxide or CATAPAL is added.
This mixtur~ is then blend~d 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-14642
, .
.: ; . ;: .,
.: . : .......... .
1329213
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-14642-C
1~29213
-45-
0.3, and llwl',-''x'', "y" and "z" represent the mole
fractions of cobalt, aluminum, 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 ~ y fz + 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
0.60 0.01 0.39
In a prefRrred subclass of the CoAPS0
molecular sieves the values of "wn, "x", "y", and "z" in
the above`formula are within the limiting compositional
vàlues or points as follows:
Mole Fraction
Point ~ y rz I w)
~ 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
CoAP50 compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of cobalt, silicon, aluminum
D-14642
1~29213
-46-
and phosphorus, an organic templating, i.e., structure-
directing, agent, preferably a co~pound of an element of
Group ~A of the Periodic Table, and optionally an alkali
metal. The reaction mixture is generally placed in a
-5 sealed pressure vessel, preferably lined with an inert
plastic material such as polytetrafluoroethylene and
heated, prefèrably under autogenous pressure at an
effactive temperature which is generally between so c
and 250~C and preferably between lOO-C and 200-C until
crystals of the CoA*SO 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:
( 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 (O) to
about 6; "b" has a value of from zero (O) to about 500,
preferably between about 2 and 300; and "w", "x", "y"
D-14642
13292~
-47-
and ''zl' represent the mole fractions of cobalt,
aluminum, phosphorus and si~icon, 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 nwn, nxn, nyn and nZ~ are generally defined as
being within the limiting compositional values or points
as follows:
` 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
In the foregoing expression of the reaction
composition, the reactants`are normalized with respect
to tha total of "w", "xn, "y" and "z" such that
(w + x + y + z) ~ 1.00 mola. Nolecular sieves
containing cobalt, aluminum, phosphorus and silicon as
framework tetrahedral oxide units are prepared as
follows:
PreDarative Reaaents
CoAPSO compositions may be prepared using
numerous reagents. Reagents which may be employed to
prepared CoAPSOs include:
~a) Alipro: aluminum isopropoxide;
D-14642
1329213
-48-
(b) CATAPAL: Trademark of Condea Corporation
for pseudoboehmite;
(c) `LUDOX-LS: Trademark of DuPont for an
aqueous solution of 30 weight percent
-5 sio2 and 0.1 weight percent Na20:
(d) Co(Ac)2: cobalt acetate,
Co(C2H302)2 4H20
(e~ CoS04: co~alt sulfate, (CoS04.7H20):
(f) H3P04: 85 weight percent phosphoric acid
in water:
(g) T3AOH: tetrabutylammonium hydroxide ~25
wt S in methanol);
(~) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3~7)3N;
(;) Quin: Quinuclidine (C7H13N);
(k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-hex: cyclohexylamine;
(m) TEAOH: totraethylammonium hydroxide
(40 wt. % in water);
(n) DEEA:` diethanolam~ne:
(o) TPAOH: tetrapropylammonium hydroxide
(40 wt. % in water); and
. (p) TMAOH: tetramethylammonium hydroxide
-` 25 (40 wt. % in water).
~`
D-14642
~ .
- ~29~3
Pre~arative irocedure
Co~PSo compositions may be prepared by
preparing reaction mixtures having a molar composition
expressed as:
eR:fcoo:hAl2o3:ip2os:gsio2:iH2o
wherein e, f, h, i, g and j represent the moles of
template R, cobalt (expressed as the oxide), A1203, P205
(H3PO4 expressed as P205), SiO2 and H20, respectively.
The reaction mixtures are prepared by forming
a starting reaction mixture comprising the H3PO4 and one
half of the water. This mixture is stirred and the
aluminum source (Alipro or CAT~PAL) added. The
resulting mixture is blended until a homogeneous mixture
is observed. Tha 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~SO4) or mixtures thereof) is
dissolved in tho rQmaining water and combined with the
first mixturo. The combined mixture is blended until a
homogonoous mixtur~ is observed. The organic templatin~
agent is added to this mixture and blended for about two
to four minutes until a homogonoous mixture is observed.
Tho resulting mixturo (final reaction mixture) is placed
in a lined (polytetrafluoroothylene) stainless steel
prossure vossol and digosted at a temperature (150-C,
200'C or 225'C) for a time. Digestions are typically
D-14642
.... ,,~- - . . ` ' .`: '
- ., '' ,, .:
. .
- 50 1329213
carried out at the autogenous pressure. The products
are removed from the reaction vessel and cooled.
ZnAPSO MOLECULAR SIEVES
The ZnAPSO molecular sieves of U.S. Patent
No. 4,935,216 comprise framework structures of
ZnO2~2, AlO2 ~, PO2 + and SiO2 tetrahedral units
having an empirical chemical composition on an
anhydrous basis expressed by the formula:
mR : (ZnwAlxPySiz)2
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 (ZnwAl~PySiz)O2 and has a value
of zero to about 0.3; and "w", NX~ ny~ and ~ZH
- 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 nWH~ n~n~ nyn and ~zH are
generally defined being within the limiting
compositional values or points as follows:
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
. ~ .
:' D-14642-C
'` : t'
!7~
- . ........................ ~". : :,
13292~3
In a preferrad subclass of ZnAPS0 molecular
sieves the values "w", "x",~ny" and "z" in the above
formula are within the limiting compositional values or
points as follows:
Mole Fraction
Point ~ 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 0.3S
ZnAPS0 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, prefQrably a compound of an
~ element or Group ~A 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 50~C and
250-C, and preferably between lOO-C and 200-C until
cryQtals of the ZnAPS0 product are obtained, usually a
period of from ~everal hours to several weeks.
Generally the effective crystallization period is from
D-14642
.
`. ',: ' " . . :
~ - ' `
1329213
-52-
about 2 hours to about 30 days with typicai periods o~
from about 4 hours to about~20 days ~eing employed to
obtain ZnAPS0 products. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthèsizing the ZnAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
( w x y z) 2 2
wherein ~R" is an or~anic t~mplating agent: "a" is the
amount of organic templating agent "R" and has a value
of from zaro to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
about 6: nb" has a value of fro~ zero ~0) to about 500,
~ ~ore preferably`between about 2 and about 300; and "w",
: 15 "xn, "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
th~ reaction ~ixture is sQlQctQd such that the mole
fractions nwn, nxn, nyn and nzn are generally defined as
bein~ within the limiting compositional values or points
as follows:
D-14642
:
-
1329213
Mola Fraction
Point x ~ y (z + w~ ~
F 0.60 0.38 0.02
G 0.38 0.60 0.02
`5 H 0.01 0.60 0.39
I 0.01 0.01 0.98
~ 0.60 o.ol 0.39
- In th~ foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w I x ~ y I z) ~ 1.00 mole. Molecular sieves
containing zinc, aluminum, phosphorus and silicon as
framQwork tetrahedral oxide units are prepared as
follows: `
Preparative Reaaents
ZnAPS0 compositions are typically prepared
using numerous reagQnts. Reagents which may be employed
to preparQ ZnAPSOs include:
ta) Alipro: aluminum isopropoxide;
(b) LUDOX-~S: LUDOX-LS is the trade name of
-` DuPont for an aqueous solution of 30
w~ight percent sio2 and 0.1 weight
: percent Na20;
~c) CATAPA~: Trademark of Condea Corporation
for hydrated pseudoboehmite;
. ~
D-14642
.
. . ~ . . . i , . ..
- 1329213
-54-
(d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e~ ZnAc: iinc Acetate, Zn(C2H3O2)2.4H2O:
(f) TEAOH: 40 weight percent aqueous solution
of tstraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(h) ~AOH: Tetramethylàmmonium hydroxide
pentahydrate, (CH3)4NOH.5H2O;
(i~ TPAOH: 40 weight parcent aqueous solution
of ~etrapropylammonium hydroxide,
~C3H7)4NOH;
(;) Pr2NH: di-n-propylamine, (C3H7)2NH;
(X) Pr3N: Tri-n-propylamine, (C3H7)3N;
(1) Quin: Quinuclidine, (C7H13N);
(m) C-hex: cyclohaxylamine: and
~ (n) DEEa: diethylethanolamine,
;` ' (C2:H5) 2NC2H50H,
Pre~arative Procedure
`. 20 ZnAPSO compositions are typically prepared by
forming reaction mixtures having a molar composition
expressed as:
eR:fZnO:gA1203:hP205:isiO2:iH2o
whQrQin e, f, g, h, i and ~ represent the moles o~
template R, zinc (e~pressed a~ the oxide), A12O3, P2O5
(H3PO4 express~d as P2O5), sio2 and H2O, respectively.
D-14642
.,
~ 55 ~ 1329213
The reaction mi~tures are generally
prepared by forming a starting reaction mixture
comprising the H3P04 and a portion of the water.
This mixture is stirred and the aluminum source
added. The resulting mi~ture is blended until a
homogeneous mixture is observed. The LVDOX LS is
then added to the resulting mi~ture 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 mi~ture. The combined mixture is blended
until a homogeneous mi~ture 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 MOLECU~AR 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 ~, P02 ~ and SiO2 tetrahedral units,
and having a unit empirical formula, on an anhydrous
basis, of:
~-14642-C
: ;''~'il~
1329213
-56-
mR : tFewAlxPySiz)02
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents ~he moles of "R" present per mole of
S (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 mol~cular dimensicns of the templating agent
and the availablQ 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
tetrahadral oxides, said mole fractions being such that
they are within the limiting compositional values or
points as follows:
- 15 Mole Fraction
Point ~ y ~z I 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-14642
`` 1329~13
-S7-
The values of w, x, y and z may be as follows:
Mole Fraction
Point ~ ~ y rz + 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 FeAPgOs of the instant invention are
generally synthesized by hydrothermal crystallization
from a reaction mixture comprising reactive sources of
iron, aluminum, phoephorus and silicon, and preferably
one or more organic te~plating agents. Optionally,
alkali ox other metal(s) may be present in the reaction
mixture and may act as templating agents. The reaction
- 15 mixture is generally placed in a pressure vessel,
preferably lined with an inert plastic material, such as
polytetra~luoroethylene, and hQatQd, preferably under
autogenous prQssurQ, at an effectivQ temperature which
is gQnerally betwQQn about 50'C And about 250'C, and
prefQrably b~tweQn about lOO'C and 200'C, until crystals
- of thQ FeAPSO product are obtained, usually a period of
from sQveral hours to several weeks. Molecular sieves
` containing iron, aluminum, phosphorus and silicon as
framQwork tQtrahedral oxide units are typically prepared
as follows:
D-14642
'. '.' . . , .
~32g21~
-58-
PreDarative Reagents
FeAPSO compositions may ~e 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 ~u
Pont for an aqueous solution of 30 weight
percent SiO2 and 0.1 weight percent Na20;
(c) CATAPAL: trademark for hydrated aluminum
oxide containing about 75 wt. percent
A1203 ~pseudoboehmite phase) and about
25 wt. percent water;
(d) `Fe~Ac)2: Iron (II) acetate;
(e) FeS04: Iron (II) sulfate hexahydrate;
` (f) H3P04: 85 weight percent phosphoric acid
in water:
(g) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(h) TBaOH: 40 weight percent aqueous solution
of tetra~utylammonium hydroxide;
(i) Pr2NH: di-n-propylamine ~C3~7)2NH);
(j) Pr3N: tri-n-propylamine ((C3H7)3N);
(k) Quin: Quinuclidine (C7H13N);
(1) NQuin: Methyl Quinuclidine hydroxide
(C7H13NCH30H);
D-14642
132g213
(m) TMAOH: tetramethylammonium hydroxide
pentahydrate~ and
(o) C-hex: cyclohexylamine.
Pre~arative 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., L~DOX-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 onQ Q~bodiment, the number of moles of
each component in thQ reaction mixture is as follows:
15Com~onent ~oles
A123 O.9
`` P205
SiO~ 0.2
~` FQO* 0.2
;~ 20TEAOH 1.O
H20 50
* Iron (II) acetatQ reported as Iron (II) oxide.
ThQ r~action mixture is sealed in a stainless
steel pressure vessQl lined with polytetrafluoroethylene
and ~eated in an oven at a temperature, time and under
autogenous pressure. The solid reaction product is
D-14~42
~;
: `
1329213
-60-
recovered by filtration, washed with water and dried at
room temperature.
b) In another embodiment, reaction mixture~
are prepared by grinding the aluminum isopropoxide in a
S 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
e~bodiment the number of moles of each component in the
reaction mixtura is as follows:
Comoonent ~QLQ~
A12O3 0.9
20 P2O5 0.9
sio2 0.2
FeO* 0.2
Template 1.0
H20 so
* Iron(II~ acetate reported as Iron(II) oxide.
D-14642
- 61 - 1329213
OUINARY MOLECULAR SI~VES
The QuinAPSO quinary molecular sieves of
Canadian Patent No. 1 298 080 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 e~pressed by the
formula:
mR : ~MwAlxPySiz)2
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 (NwAl~PySiz)02 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",
~ y~ and "z" represent the mole fractions of M,
aluminum, phosphorus and silicon, respectively,
present as tetrahedral o~ides. Preferably, M
represents the combination of cobalt and manganese.
The mole fractions ~wn ~ n~n ~ nyn and nzn are
generally defined as being within the limiting
compositional values or points as follows:
D-14642-C
.J;~
. ~
': '' . ' : ': .
., .
1329213
-62-
Mole Fraction
Point ~ ~ y (z + w
A 0.60 0.37 0.03
B 0.37 0.60 0.03
`5 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 ~ y rz + 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 0.39 0.60
Q 0.39 0.01 0.60
f 0.60 ~.01 0.3g
QuinAPSO compositions are generally
synthQsi2ed by ~ydrother~al crystallization from a
reaction mixture containing reactive sources of the
elements N, aluminum, phosphorus and silicon and
preferably an organic templating agent, i.e.,
structure-directing, agent. The structure-directlng
agents are prQferably a compound of an element of Group
VA of the Periodic Table, and may be an alkali or other
D-14642
. ~ .
. ~,, ,
: .~ ...
1329213
-63-
metal. The reaction mixture is generally placed in a
sealsd pressure vessel, pre~erably lined with an inert
plastic material such as polytetrafluoroethylene and
heated, preferably under autogenous pressure and at
typical effective temperatures between 50'C and 250-C,
preferably between lOO'C`and 200'C, until crystals of
the QuinAPS0 product are obtained, usually over a period
of from several hoùrs to several weeXs. Typical
effective crystalli2ation 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:
a~ : (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 n Z n represent the mole fractions of elements M,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
D-14642
.
` 13292~3
6~-
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 F~action
Point ~ 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 o.~o 0.01 0.39
In the foregoing expression of the reaction
composition, the r~actants are normalized with respect
to the total of "w", "x", "y" and "z" such that
(w I 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
SieVeQ containing the Qame elements, as described in
datail above and below.
Reagents which may be employed to prepare
QuinAPSOs include:
(a) Alipro: aluminum isopropoxide:
(b) LUDOX-LS: LUDOX-LS is the tradename of
DuPont for an aqueous solution of 30
D-14642
.... . - . .
'
- 13292~
-65-
weight percent SiO2 and 0.1 weight
percent Na2O~
(c) H3PO4: 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate,
Mn~C2H32)2 4H2 (for QuinAPSOs
containing manganese);
te) CoAc: Cobalt Acetate, Co(C2N3O2)2.482O
(for QuinAPSOs containing cobalt);
(f) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide; and
(g) Pr2NH: di-n-propylaminQ, (C3H7)2NH-
Preparative Procedures
QuinAPSOs may be preparQd by forming a
starting reaction mixture by adding H3PO4 and one half
of the quantity of water. To this mixturQ an aluminum
isopropoxide is add~d. This mixture is then blended
until a homogenQous mixture is obs~rved. To this
mixture a silica (e.g., LUDOX-~Q) is added and the
r~sulting mixturQ blended ~about 2 minutes) until a
homogeneous mixture is obser~ed. 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 sourcQ of another
Qlement M) and one half of the remaining water. The
three mixtures are admixed and the resulting mixture
D-14642
.
. ' , , "
- 66 - 1329~3
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 mi~ture
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 MOLECU~AR SIEVES
The CoMnMgAPSO senary molecular sieves have
three-dimensional microporous framework structures
of CoO2~2, MnO2~2, Mgo~~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,
D-14642-C
1329213
-67-
respectively, present as tetrahedral oxides and each has
a value of at least 0~01. The mole fractions "t", "u",
"vn, "x", "y" and "z" are generally defined as being
within the limitinq compositional values or points as
follows (where w = t + u + v):
Mole Fraction
Point . ~ 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 prQ~erred su~class of the CoMnMgAPS0
molecular sievss the vàlues of "w", "x", "y" and "z" in
th~ above formula are within thQ limiting compositional
~alues or points as ~ollows:
MO1Q Fraction
Point ~ y ~3~ L
a O.S5 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-14642
; ' : ' . :
` 13~9213
-68-
CoMnMgAPS0 compositions are generally
synthesized by hydrothermal crystallization from a
reaction mixture containing reactive sources of cobalt,
manganesQ, magnesium, aluminum, phosphorus and silicon,
5 and preferably an organic templating agent, i.e.,
structure-directing, agènt. 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 2QO-C, until crystals of the
CoNnMgAPS0 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 CoMnMgAPS0 products. The
product is recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the CoMnMgAPS0 eompositions,
it is preferred to employ a reaction mixture composition
~xpressed in terms of the molar ratios as follows:
aR : (cotMnuMgvAlxpysi2)o2 bH2
D-14642
-
1329213
.-69-
wherein "R" is an organic templating agent; "a" is the
amount of organic templating agent 11~ 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 valuè of from zero (0) to about 500,
preferably bètween about 2 and about 300; and "t", "u",
"v", "x", "y", and nZ~ represent the mole fractions of
cobalt, manganesQ, magnesium, 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 "wn, "x", "y"
and ~zn~ wherè "w" is the sum of "t" + "u" + "v", are
generally defined as being within the limiting
compositional valùes or points as follows:
Mola Fraction
Point ~ v rz + 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 tha foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "tn, "u", "vn, "x", "y" and "z" such
D-14642
1329213
-70-
that (t ~ u + v + x + y + z) = 1.00 mole. Molecular
sieves containing cobalt, manganese,~magnesium,
aluminum, phosphorus and silicon as frameworX
tetrahedral oxide units are prepared as follows:
Preparative Reaaents
CoMnMgAPSO compositions may be prepared by
using numeroùs reagents. Reagents which may be employed
to prepare CoMnAPSOs include:
(a) ~lipro: aluminum isopropoxide;
(b) LU W X-LS: LUDOX-LS is the tradename of Du
Pont for an aqueous solution of 30 weight
percent SiO2 and 0.1 weight percent Na2O;
(c) H3PO4: aqueous solution which is 85
weight percent phosphoric acid;
(d) MnAc: Manganese acetate,
Mn(c2H3o2)2~4H2o
(e) CoAc: Cobalt Acetate, Co(C2H3O2)2.4H2O;
f) MgAc: Magnesium Acetate Mg(C2H302).4H20;
(g) TEAOH: 40 weight percent aqueous solution
20 of tetraQthylammonium hydroxide; and
(h) Pr2NH: di-n-propylamine, (C3H7)2NH.
Pre~arative Procedures
CoMnMgAPSOs may be prepared by forming a
starting reaction mixture by adding H3PO4 and one half
of the guantity of water. To this mixture an aluminum
isopropoxide is added. This mixture is then blended
D-14642
- 71 - 1329~3
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 mi~ture 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 mi~ture is observed~ An organic
templating agent is then added to the resulting
mi~ture 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-14642-C
l~i9213
.
-72-
where~n "R" represents at least one organic templating
agen~ present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(MwAlxPySiz)02, 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
10 of nMn; and ~wn, nxn, nyn and nz-- 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 th~ limiting compositional
values or points as follows, wherein "w" denotes the
co~bined mole fractions of the three elements "M" such
that ~wn ~ nwl~ + ~W2 n + ~W3 n and each element "M" has a
mole fraction of a~ least 0.01:
Mole Fraction
20 Poin~ ~ y (2 + 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
D-14642
- 13292~3
-73-
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:
s ~ole Fraction
Point x y ~z ~ w
a 0.60 0.36 0.04
b 0.36 0.60 0.04
~ 0.01 0.60 0.39
10 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
containing reactive sources of elements "M", aluminum,
p~osphorus and silicon, and preferably an organic
templating, i.e., structure-directing, agent. The
structure-directing agent~ are preferably a compound of
an ele~ent 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
25 250'C, and prefQrably between lOO-C and 200-C, ùntil
crystals of the SenA~S0 product are obtained, usually
D-14642
-- . .
- ~:329213
-74-
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 SenAPS0 products.
S The product is recovered by any convenient method such
as centrifugation or filtration.
In synthesizing the SenAPS0 co~positions, it
is preferred to e~ploy a reaction mixture composition
expressed in terms of the molar ratios as follows:
t 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 zaro to about 6 and is praferably an e~fective
amount within the range of greater than zero (0) to
about 6 and more preferably from greater than zero to
about 2: "b" has à value of from zero tO) to about 500,
preferably between about 2 and about 300; and "wn, "x",
"yn~ and "z" represent the mole fractions of elements
"Hn, aluminum, phosphorus and silicon, respectively, and
each has a value of at least 0.01, with the proviso that
aach "N" is present in a mole fraction of at least 0.01.
In a preferred embodiment the reaction mixture
is salected such that the mole fractions "w", "x", "y"
and "z" are gen~rally defined as being within the
limiting compositional values or points as follows:
D-14642
- 75 - 1329213
Mole Fraction
Point ~ y (z + w)
F 0.60 0.36 0.~4
G 0.36 0.60 0.09
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 reactan~s 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. Patent
No~ 4,701,281 have a framework structure of AsO2 n,
AlO2 ~, PO2 ~ and SiO2 tetrahedral units having an
empirical chemical composition on an anhydrous basis
e~pressed by the formula:
mR : ~ASwAlxpysiz)o2
`:'
wherein ~R~ represents at least one organic
templating agent present in the intracrystalline
pore system; nmn represents the molar amount of "R~'
present per mole of (AswAlxPySiz)O2 and has a value
of zero to about 0.3,
D-14692-C
.
::
1329213
-76-
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",
"xn, "y" and ~zn. are generally de~ined as being within
the limiting compositional values or points as follows:
Mole Fraction
Point ~ y ~z + w)
A 0~60 0.38 0.02
B Q.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 ~ y lz + w)
~ 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
Q 0.39 0.01 0.60
f 0.60 0.01 0.39
D-14642
.
- 132~213
-77-
In an especially preferred subclass of the
AsAPSO molecular sieves, the values of w, x, y and z are
as follows:
Mole Fraction
5 Point x ~ ~z + w)
g 0.5~ 0.40 O.lo
h 0.42 0.48 o.lo
i 0.38 0.48 0.14
; 0.38 0~3~ 0.25
k 0.45 0.30 0.2s
1 0.50 0.30 0.20
AsAPS0 compositions are generally synthesized
by ~ydrothermal cr~stallization from a reaction mixture
containing reactive sources of arsenic, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., ctructure-directing, agent, preferably
a compound of an elemQnt of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. ~he
reAction mixture is genQrally placed in a sealed
pressure vessQl, pr-ferably lined with an inert plastic
material such as polytetrafluoroQthylenQ 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-14642
.~
. ..
;: .
1329213
-73-
times of from 2 hours to about 30 days, generally from
about 12 hours to about 10 days, 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)02 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 àbout 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,
pref~rably between about 2 and about 300, most
preferably not greater than about 60; and "w", "x", "y"
and ~z" repres~nt the mole fractions of arsenic,
aluminum, phosphorus and silicon, respectively, and each
has a value of at lQast 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-14642
1329213
-79-
Mole Fraction
Point x y rz + w)
F 0.60 0.38 0.02
~ 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 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 th~ total of "w", "x", "y" and "z" such that
(w ~ x ~ y 1 z) = 1.00 mole. Molecular sieves
containing arsenic, aluminum, phosphorus and silicon as
framQwork tetrahedral oxide units are prepared as
follows:
Preparative Rea~ents
AsAPS0 compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare AsAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) ~ATAPAL: Trademark of Condea Corporation
~or hydrated pseudoboehmite,
.
D-14642
.
.
. .
1329213
- 80 -
(c) LUDOX-LS: LVDOX-LS is the trademark of
DuPont for an aqueous solution of 30
weight percent SiO2 and 0.1 weight
percent Na2O;
(d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e) As2O5, 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,
(C7H13NCH3OH);
(1) C-hex: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
~n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
PreDarative Procedures
AsAPSOs may be prepared by forming a
starting reaction mixture by dissolving the arsenic
(V) o~ide and the H3PO4 in at least part of the
water. To this
D-14642-C
t
- 81 - 1329213
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 (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
~APSO MQL~CULAR SIE~ES
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 (BwAl~P~Siz)02 and has a value
of zero to about 0.3, but is preferably not greater
than 0.15; and "wn, "xn, "y~ and "z" represent the
mole fractions of the elements boron, aluminum,
phosphorus and silicon, respectively,
D-14642-C
. ~
.
,
: ~ "
13292~3
-82-
present as tetrahedral oxides. The mole fractions "w",
"xn, "y" and "z" are generally defined as being within
the limiting compositional values or points as follows:
Mole Fraction
5 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 ~he 2APSO molecular
sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point ~ v (z + w)
a 0.60 0.38 0.02
b Q.38 0.60 0.02
c 0.01 0.60 0.39
d 0.01 0.39 0.60
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-14642
1329213
--83--
Mole Fraction
~ Point ~ 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 g~nerally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of boron, silicon, aluminum
and p~osphorus, 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 m~tal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inart plastic material such as
polytetrafluoroethylene and heated, preferably under
- autogenous pressurQ 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 BAPS0 product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 haurs
to about 30 days, generally from about 4 hours to about
20 days, have been obs~rved. The product is recovered
D-14642
'
1329~13
-84-
by any convenient method such as centri~ugation or
~ filtration.
In synthesizing the BAPS0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (B3 1xPySiz)02 bH20
wherein "~" is an organic templating agent; "a" is the
amount of organic ~emplating agent "~" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of greater than sero (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 "z~ represent the mole fractions of boron, aluminum,
pho-~phorus and silicon, respectively, and each has a
value of at least 0.01.
In one embodiment the reaction mixture is
solected such that the mole fractions "w", "x", "y" and
~z" are generally defin~d as being within the limiting
compositional values or points as follows:
D-14642
:
- 1329213
~5
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
Especi~lly preferred reaction mixtures are
t~ose 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 reactant-~ are normalized with respect
to the total of Nw", ~x", "y" and "z-- such that
(w + x ~ y + z) ~ 1~00 mole. Molecular sieves
containing boron, aluminum, phosphorus and silicon as
framework tatrahedral oxide units are prepared as
.
follows:
PreDarative Reaaents
: 20 BAPS0 compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare BAPSOs include:
~a) Alipro: aluminum isopropoxide;
(b) CATAPA$: Trademark of Condea Corporation
for hydrated pseudoboehmite;
, .
D-14642
'
- 86 - 1329213
(c) LUDOX-LS: LUDOX-LS is the trademark
of nupont 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
hydro~ide;
(h) Pr2NH: di-n-propylamine, (C3H7)2NH;
(i) Pr3N: tri-n-propylamine, (C3H7)3N;
i~ Quin: Quinuclidine, (C7H13N);
(k~ MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
~1) C-hex: cyclohexylamine;
~m) TNAOH: tetramethylammonium hydroxide;
` ~n) TPAOH: tetrapropylammonium hydroxide;
and
t ~O) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
~ tetraethylorthosilicate.
; Preparative Procedures
~APSOs may be prepared by forming a
starting reaction mixture by dissolving aluminum
isopropo~ide in an alcohol such as isopropanol,
adding the H3PO4 and
.
''`~
D-14642-C
,,
.
- 87 - 1329213
recovering the solid which precipitates. This solid
is then added to water, and trialkylborate (for
example trimethyl 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 MOL~CUhAR SIEVES
The BeAPSO molecular sieves of U.S. Patent
No. 4,737,353 have a framework structure of BeO2 ~ ,
AlO2 ~, PO2 ~ and SiO2 tetrahedral units having an
empirical chemical composition on an anhydrous basis
e~pressed 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 o~ides. The mole
.
D-14~42-C
i
- 1329213
-88-
fractions "w", "x", "y" and "z" are generally defined
as being within the limitin~ compositional values or
points as follows:
` Mole Fraction
5 Point ~ y (z + w)
A 0.60 0.33 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~oint ~ y (z + w)
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
~ 0.39 0.01 0.60
f 0.60 0.01 0.39
BeAPS0 compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources o~ b~ryllium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
D-14642
13292~3
-39-
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
5 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 BeaPS0 product are obtained, usually a period of
10 from several hours to several weeks. Typical effective
times of fro~ 2 ~ours to about 30 days, generally from
about 4 hours to about 20 days, have been observed, with
fro~ 1 to 10 days being preferred. The product is
recovered by any convenient method such as
15 centrifugation or filtration.
In synthesizing the BeAPS0 compositions, it is
prQfQrred to Qoploy a reaction ~ixture composition
t expres~ed in ter~s of the molar ratios as follows:
aR : (BowAlxpysi2)o2 bH2
whoroin ~R" is an organic t~mplating agent; "a" is the
a~ount of organic templating agent "R" and has a value
of from zQro to about 6 and is preferably an effective
amount within the range of greater than zero (0) to
bout 6, and most preferably not more than about 0.5;
"b" has a value of fro~ zero (0) to about 500,
preferably betw~en about 2 and about 300, most
D-14642
1~29213
--so--
preferably not greater than about 20; and l'wl', "x", I~y
and "z" represent the mole fractions of beryllium,
aluminum, phosphorus and silicon, respectively, and each
has a value of at least o 01
S In one embodiment the reaction mixture is
s~lected such that the mole fractions "wn, "xn, "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows
Nole Fraction
~ ~ y ~ z I 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 thQ foregoing expr~ssion of the reaction
composition, the reactants are normalized with respect
to tho total of "w~, "x", "y" and "z" such that
(w + x + y + z) ~ 1 00 mole ~ol~cular sieves
containing beryl`lium, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follow~
Pre~arative Rea~ents
BeAPSO compositions may be prepared by using
numerous reagents Reagents which may be employed to
preparQ BeAPSOs include
D-14642
.. ... . .. . .
- 9 - 1329213
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea
Corporation for hydrated
pssudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the trademark
of DuPont for an aqueous solution of
30 weight percent SiO2 and O.l weight
percent Na20;
-: (d) H3PO4: 85 weight percent aqueous
phosphoric acid;
(e) beryllium sulfate, BeSO4:
. (f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydro~ide;
(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) NQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-he~: cyclohe~ylamine;
~ (m) TMAOH: tetramethylammonium hydroxide;
~ (n) TPAOH: tetrapropylammonium hydroxide;
;~ and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate.
D-14642-C
'
- 92 - 132921~
Preparative Procedures
BeAPSOs may be prepared by forming a
starting solution by mi~ing H3PO4 in at least part
of the water. To this solution is added beryllium
sulfate (or another beryllium salt) and the
resultant mi~ture stirred until a homogeneous
solution is obtained~ To this solution may be added
successively the aluminum o~ide, the silica and the
templating agent, with the mixture being stirred
between each addition until it is homogeneous. The
mixture is then placed in a lined (polytetra-
fluoroethylene) 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 MOLE~ULAR SIEVES
The CAPSO molecular sieves of U.S. Patent
No. 4,738,837 have a framework structure of CrO2 n,
AlO2 ~, PO2 + and SiO2 tetrahedral units (where "n"
is -1, 0 or tl) 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; nmn
D-14642-C
1329213
93-
represents the molar amount of "R" present per mole of
(CrwAlxPySiz)02 and has a value of zero to about 0.3,
but is preferably not greater than 0.15: and "wn, "xn,
ny" and "z" represent the mole fractions of the elements
chromium, aluminu~, 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 Praction
y r z I w)
0.60 0.3a 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 CAPSO molecular
siov~s, th~ valuQs of w, x, y and 2 are as follows:
Mol~ Fraction
. 20 Point ~ y fz ~ 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
~ 0.39 0.01 0.60
f 0.60 0.01 0.39
D-14642
9~ 13292~3
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 I w~ is in the range of about 0.02 to 0.15.
Since the exact nature of the CAPS0 molecular
sieves is not clearly understood at present, although
all are belièved to contain CrO2 tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the CAPS0
molecular sieves by means of their chemical composition.
This is due to the low level of chromium present in
certain of the CAPS0 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
b~lieved that CrO2 tetrahedra are substituted
isomorphously for A102, P02 or SiO2 tetrahedra, it is
appropriate to characterize certain CAPS0 compositions
by refer~nce to th~ir chemical composition in terms of
the mole ratios of oxides.
CAPS0 compositions are genexally synthesized
by ~ydrother~l 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-14642
1329213
ss
Table, and/or optionally an al~ali or other ~etal. 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 CAPSO product are obtained, usually a pariod 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 i5 recovered
by any convenient method such as centrifugation or
; filtration.
In synthesizinq the CAPSO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
( w x y z 2 2
whQrain "R" is an organic t~mplating agent; "a" is the
amount of organic te~plating agent "R" and has a value
of from zero to about 6 and is preferably an effective
amount within the range of graater than zero (0) to
about 6, and most preferably not more than about O.S;
"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-14642
_
13292~3
96--
and "z~ represent the mole fractions of chromium,
al~min~m, phosphorus and silicon, respectively, and each
has a value of at least 0.01.
In one em~odiment 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:
~ole Fraction
Point ~ ~ rz + w)
F O.S0 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 preferrad 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
1.2S molQs of aluminum, per mole of phosphoru~.
In th~ foregoing expression of the reaction
composition, th~ reactants are normalized with respect
to thQ total of "w", "x", "y" and "z" such that
~w ~ x + y + z) ~ 1.00 mole. Molecular sieves
containing chro~ium, aluminum, phosphorus and silicon as
framework tetrahQdral oxide units are prepared as
follow~:
D-14642
... : ~ ;
. ~ ' '
` -` 13292~3
- 97 -
Pre~arative Rea~ents
CAPSO compositions may be prepared by using
numerous reagents. Reagents which may be employed
to prepare CAPSOs 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: 90 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydro~ide;
(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-he~: cyclohexylamine;
; (m) TMAOH: tetramethylammonium hydroxide;
D-14642-C
'' ~
.
.
` 1329213
-98-
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEEA: 2-diethylaminoethanol;
(p) ~etraalXylorthosilicates, such as
tetraethylorthosilicate.
Pre~arative 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 blanded until a homogeneous
lo mixture is o~served. ~o this mixture the silica, the
c~romium acetatQ or chromium acetate hydroxide and the
templating agent are successivaly added and at each step
the resulting mixtura is blendQd until a homogeneous
mixture is obsarved.
Alternatively, the water and aluminum
isopropoxide may first be mixed, and then the silica,
thQ chromium ac~tat~ or chromium acetate hydroxide, the
phosphoric acid and the tamplating agent added, and
again at Qach stcp the rasulting mixture is blended
un~il a homogQn~ous mixture is observed.
In either c~sa, the mixture is then placed in
a lined (polytatrafluoroethylene) stainless steel
; pressurQ vessel and digested at a temperature (150-C or
200-C) for a time or placed in lined screw top bottles
for digestion at lOO'C. Digestions are typically
carriad out under autogenous pressure.
D-14642
:
.
.
- ,
, ` . :.. ' ., .. . 1~.' :
99 1329213
GaAPSO ~OLECULAR SIEVES
The GaAPSO molecular sieves of U.S. Patent
No. 4,735,806 have a framework structure of GaO2 ~,
AlQ2 ~, 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 o~ides. 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 ~ ~ tz ~ 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-14642-C
` ` ~329~13
--100--
In a preferred subclass of the GaAPSO
molecular sieves, the values of w, x, y and z are as
follows:
Mole Fraction
5 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 0.39 0.60
e 0.39 0.01 0.60
f 0.~0 0.01 0.39
In an especially preferred subclass of the
GaAPSO molec~lar si~v~s, th~ values of w, x, y and z are
as follows:
Mole Fraction
Point ~ Y 13_~_YL
g 0.45 0.40 0.15
h 0.33 0.52 0.15
i 0.20 0.52 0.28
~ 0.20 0.45 0.35
k 0.36 0.29 0.35
1 0.45 0.29 ` 0.26
GaAPS0 compositions are generally synthesized
by hydrothermai crystallization from a reaction mixture
containing reactive sources of gallium, silicon,
aluminum and phosphorus, preferably an organic
D-14642
-lol- 1329213
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
betw~en about 50'C and about 250-C, and preferably
between about lOO'C and about 200-C, until crystals of
the &aAPS0 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.
ln 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 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, and most prefQrably not more than about 1.0;
"b" has a value of from zero tO) to about 500,
D-14642
-1329213
-102-
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 embodimènt 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 ~ 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
Esp~cially preferred reaction mixtures are
thosa containing from about 0.5 to about 1.0 total moles
of silicon and gallium, and from about 0.75 about 1.25
molos of aluminum, per molQ 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 I x ~ y + z) - 1.00 mole. Molec~lar sieves
containing gallium, aluminum, phosphorus and silicon as
D-14642
.. .
~" - 103 - 1329213
framework tetrahedral oxide units are prepared as
follows:
PreParative Reaaents
GaAP~O 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: LUDOX-LS is the trademark
of DuPont for an aqueous solution of
30 weight percent SiO2 and 0.1 weight
percent Na2O;
(d) H3PO9: 85 weight percent aqueous
phosphoric acid;
(e) gallium hydroxide, or gallium sulfate;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydro~ide;
~9) TBAOH: 90 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: Nethyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(1) C-hex: cyclohexylamine;
D-14692-C
'-t
1329213
-104-
(m) T~AOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide; and
(o) DEEA: 2-diethylaminoethanol;
(p) TetraalXylorthosilicates, such as
tetraethylorthosilicate.
Preparative Procedures
GaAPSOs may be prepared by forming a starting
solution by dissolving the H3P04 in at leas~ part of the
water. To this solution the aluminum hydroxide or
isopropoxida is added. This mixture is then blended
until a homogeneous mixture is observed. To this
mixture is added a second solution prepared ~y adding
silica to a solution containing the gallium hydroxide
and the templating agent and then the combinad mixture
is blended unt.l 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 th~n the co~bined mixture is blended until a
homogenQous 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
D-14642
, - ., ~ . . .:
. ~
.. : ` ' ...... , . ,. :
. ~
.. . . . . ...... ..... . . . .. .. . .
- 105 - 1329213
for digestion at 100C. Digestions are typically
carried out under autogenous pressure.
GeAPSO MOLECULAR SIEVES
The GeAPSO molecular sieves of U.S. Patent
No. 4,992,250 have a framework structure of GeO2,
AlO2 ~, PO2 + and SiO2 tetrahedral units having an
empirical chemical composition on an anhydrous basis
e~pressed by the formula:
mR : (GewAlxpysiz)o2
wherein nR" 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 Nwn, "x~, "y" and -z" represent the
mole fractions of the elements geranium, aluminum,
phosphorus and silicon, respectively, present as
tetrahedral o~ides. The mole fractions "w", "x",
~y~ and ~z" are generally defined as being within
the limited compositional values or points as
follows:
D-14642-C
,
:,
...
~. ,~ , '
` 1329213
-iO6-
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:
Mol~ Fraction
P~ ~ y ~z + w)
a 0.60 0.38 0.02
b 0.38 0.60 0.02
c 0.01 0.60 Ø39
d 0.01 0.39 0.60
e 0.39 0.01 0.60
f 0.60 0.01 0.39
` In an esp~cially preferred subclass of the
G~APSO molecular ~ieves, t~e values of w, x, y and z are
as follows:
D-14642
, . ., . . , :
' ~' ' ,,, ~, - .
.
1329213
-107-
Mole Fraction
Point ~ ` v ~z + w)
g 0.60 0.3S 0.05
h 0.4i 0.48 0.05
i 0.40 ~.48 0.12
j 0.40 0.36 0.24
k 0.46 0.30 0.24
`1 0.60 0.30 0.10
GeAPSO compositions are generally synthesized
by hydro~hormal crystallization from a reaction mixture
containing reactive ~ources of germanium, silicon,
aluminum and phosphorus, preferably an organic
templating, i.e., structure-directing, agent, preferably
a compound of an element of Group V~ of the Periodic
lS Table, and/or optionally an alkali or other ~etal. The
. reaction mixture is generally placed in a sealed
pressura vessel, preferably lined with an inert plastic
material such as polytetrafluoroethylene and heated,
pr~ferably under autogenous pressure at a temperature
20 betweQn about 50'C and about 250'C, 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
25 about 4 hours to about 20 days, and preferably about 12
hours to about 7 days have been observed. The product
D-14642
.
. : . .
. ~ .
1329213
-108-
is recovered by any convenient method such as
centrifugation or filtratioh.
In synthesizing the GeAPSO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
a~ : (GeWAlxpysiz)o2 bH2
wherein "R" is an organic templating agent; "a" is the
amount of organic tamplating 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 t~an about 20, and desirably not
greater than about ~0; and l'wn, "xn, "y" and~"z"
represent the mola fractions of ~ermanium, aluminum,
phosphorus and silicon, respectively, and each has a
- value of at least 0.01.
In one embodiment the reaction mixture is
s~lected such that the mole fraction~ nwn, "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
D-14642
. ,
' ' , .
.
1329213
--109--
Mole Fraction
Point x ` ~ (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 th8 foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total o~ "wn, "xn, "y" and "z" such that
15 (w + x I y + z) - 1.00 mole. Molecular sieves
containing germanium, aluminum, phosphorus and silicon
as framework tetrahedral oxide units are prepared as
follows:
preparative Reaaents
&QA*SO compositions may be prepared by using
numerous rQagents~ Reagents which may be employed to
prepare GeAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation
for hydrated pseudoboehmite;
D-14642
llo 13292~3
(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) NQuin: Nethyl Quinuclidine hydroxide,
(C7H13NCH30H);
(1) C-he~: cyclohe~ylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydro~ide;
and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate~
(~) aluminum chlorhydrol~
.--
D-14642-C
-` . . ' - ., .: :
., , . .. , , .. :
: . . . . . ~ .. ~
~ .. I . .
1329213
.
--111--
Preparative Proced~res
In some cases, it may be advantageous, when
synthesizing the GeAPSO compositions, to first combine
sources of germanium and aluminum, or of germanium,
aluminum and silicon, to form a mixed germanium/aluminum
or germanium/alu~inum/silicon compound (this compound
being typically a mixed oxide) and thereafter to combine
this mixQd compound with a source of phosphorus to form
the final Ge~PSO composition. Such mixed oxides may be
prepared for examplQ by hydrolyzing aqueous solutions
containing germanium tetrachloride and aluminum
chlorhydrol, or germaniu~ ethoxide,
tetraethylorthosilicate, and aluminum tri-sec-butoxide.
Ge~PSOs 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
CAT~PAL is added. T~is mixture is then blended until a
homogQneou~ mixture is observQd. To this mixture the
t-mpla~ing ag~nt and then a solution containing
tetraQthylort~osilicatQ and g~rmanium ethoxide, and the
resulting mixture blended until a homogeneous mixture is
obsenred.
Alternatively, the phosphoric acid may first
be mixed with th~ templating agent, and then a solution
containing tetraethylorthosilicate and germanium
ethoxide combine~d with the phosphoric acid/templating
D-14642
1329213
- 112 -
agent solution. Then the aluminum oxide is added
and the resultant mixture blended until homogeneous.
In a third procedure, the phosphoric 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 (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.
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-14642-C
1 `
.
:, ' ' ' .: ` .
`` 132~213
-113-
(LiwAlxPySiz)02 and has a value of zero to about 0.3,
but is preferably not greate`r than 0.15: and "w", "x",
I'yl' and ~Zll represent the mole fractions of the elements
iithium, 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:
` Nol~ Fra~tion
Point ~ y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.~1 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the LiAPSO
molecular sieves, t~e values of w, x, y and z are as
follows:
Mole Fraction
~ z + w)
~ 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-14642
1329213
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In an especially preferred subclass of the
LiAPSo molecular sieves, the`value of w+z is not greater
than about 0.20.
Since the exact nàture of the LiAPS0 molecular
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 LiAPS0
molecular sieves by means of their chemical composition.
This is due to thQ low level of lithium present in
certain of the LiAP0 molQcular siev~s prepared to date
which maXes 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 A102,
P02 or SiO2 tetrah~dra, it is appropriata to
charactQriz~ cQrtain LiAPS0 compositions by reference to
their chQmical 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-dirQcting, agent, preferably
a compound of an elemQnt of Group VA of the Periodic
Table, and/or optionally an alkali or other metal. The
D-14642
- . - . ...................... ~
' ' ':
.
132~213
--115--
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 LiAPSo product are obtained, us~ally 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 bout 20 days, and preferably about l
to about 10 days, have been observed. The product is
recovered by any convenient me~hod such as
centrifugation or filtration.
In synthesizing t~e LiAPS0 compositions, it is
preferred to employ a reaction mixtura composition
expressed in terms of the molar ratios as follows:
aR : ~LiwAlxPySi2)02 bH2
wherein "R" is an organic templating agent; "a" is the
amount of organic te~plating agent "~l- 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-14642
~329213
-116-
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
selectad such that the mole fractions "w", "x", "y" and
"z" are generally defined as being within the limiting
compositional valu-s or points as follows:
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
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to th~ total of "w", "x", "y" a~nd " 8 'I such that
(w + x + y + z) ~ 1.00 mole. Molecular sieves
containing lithium, aluminum, phosphorus and silicon as
framework tetrahQdral oxide units are prepared as
follows:
Preparative Rea~ents
LiA2S0 composition~ may be prepared by using
numerous reagents. Reagents which may be employed to
prepare LiAPSOs include:
(a) Alipro: aluminum isopropoxide;
D-14642
-- - 117 - 1329213
(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
agueous-phosphoric acid;
(e) lithium orthophosphate;
(f) TEAOH: 40 weight percent aqueous
solution of tetraethylammonium
hydroxide;
(g) TBAOH: 40 weight percent aqueous
solution of tetrabutylammonium
hydro~ide;
(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-hes: cyclohexylamine;
(m) TMAOH: tetramethylammonium hydroxide;
(n) TPAOH: tetrapropylammonium hydroxide;
and
(o) DEEA: 2-diethylaminoethanol;
(p) Tetraalkylorthosilicates, such as
tetraethylorthosilicate~
Preparative Procedures
LiAPSOs may be prepared by forming a
starting
D-14642-C
... . . .
- 118 - 1329213
reaction mixture mixing lithium phosphate and
aluminum oxide, then adding the resultant mixture to
the H3PO4. To the resultant mixture is added silica
and the templating agent and the resulting mi~ture
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.
ALUMINOPHOSPHATE MOLECULAR SI~VES
The AlPO4 aluminophosphate molecular sieves
of U.S. Patent No. 4,310,440are disclosed as
microporous crystalline aluminophosphates having an
essential crystalline ramework structure whose
chemical composition, expressed in terms of molar
ratios of o~ides, 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-14642-C
.. , ~,~, .
.
, ~ , ' . : . .... ...
1329213
--119--
retaining the same essential framework topology in both
the hydrated and dehydrated~state. By the term
"essential framework topology" is meant the spatial
arrangement of the primary Al-O and P-o bond linkages.
No change in the frameworX topology indicates that there
is no disruption of these primary bond linkages.
~ he aluminophosphates are prepared by
hydrothermal crystallization of a reaction m~xture
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 frameworX structure of the aluminophosphate in
a~ounts which vary from species to species but usually
do not axceed one mole par 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
evidencQd by essentially complete absencQ 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-dirQcting agent is a critical constituent is
contained in certain of the Examples of the Patent
D-14642
1329213
--1..0--
4,310,4~0, wherein reaction mixtures, otherwise
identical to those which yield the AlP04 products except
for the presence of templating agents, yield instead the
previously ~nown aluminophosphate phases AlP04.1.I-1.3
H20, AlP04-tridymite, AlP04-quartz and
AlP04-cristobalite.
The AlP04 aluminophosphates are prepared by
forming a reaction mixture which contains, in terms of
molar ratios of oxidas:
A123 S 1-5 P205 7-100 H20
and contains from about 0.2 to 2.0 moles of templating
agent per mole of A1203. The reaction mixture is placed
in a reaction vessel inert toward the reaction system
and heated at a temperature of at least about lOO'C,
preferably between lOO~C and 300~C, until crystallized,
usually a period from 2 hours to 2 weeXs. The solid
crystalline re~ction 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.
M~AP0 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. Members of
D-14642
1~2~213
-121-
this novel class of compositions have a three-
dimensional microporous crys`tal framework structure of
M02 2, A10 2 and ~ 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 thQ intracrystalline pore system: "m"
represents the moles of "R" prQsent per mole of
(~ AlyPz)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 tetrahQdral oxides, said mole
fractions being such that they are representing the
following values for "xn, "y", and "z":
Mole Fraction
~g~nt ~ Y
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
D-14642
13~g213
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When synthesized the minimum value of "m" in the formula
above is 0.02. In a preferred 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 "xn, "y" and ~Izn
~ole Fraction
point ~ Y
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
~ he as-synthesizQd compositions are capable of
withstanding 350'C calcination in air for extended
periods, i.e., a`t least 2 hours, without becoming
amorphous. While it is believed that the M, Al and P
framework constituents are present in tetrahedral
coordination with oxygen, it is theoretically possible
that some minor fraction of these framework constituents
ar~ 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 o~ coordination with oxygen. Some of
each constituent may be merely occluded or in some as
2S yet undetermined form and may or may not be structurally
significant.
D-14642
'' '` ' :
.,.~' ' :. ,
-
1 329213
-123-
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
employed hereinafter. Also in those cases where the
~etal "Me" in the composition is magnesium, the acronym
NAPQ is applied to the composition. Similarly, ZAPO,
NhA~O, and CoAP0 are applied to the compositions which
contain zinc, manganese and cobalt, respectively. To
identify the various structural species which ma~e up
each of the subgeneric classes MAPO, ZAPO, CoAPO and
NnAP0, each species is assigned a number and is
identified, for example, as ZAP0-5, MAP0-11, CoAP0-11
and so forth.
~he term "essential empirical chemical
composition" is mean~ to include the crystal framework
and can include any organic templating agent present in
the pore systeo, but does not include alkali metal or
other ions which can be presQnt by virtue of being
contained in the reaction mixture or as a result o~
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-14642
. - .
` 1~29~13
--124--
The metal aluminophosphates ("~eAPOs") are
synthesized by hydrothermal ~rystallization from a
reaction mixture containing reactive sources of the
metal "Mn, 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 100'C and 225'C, and
preferably between 100'C 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
lS recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the MeAPO compositions, it is
preferrQd to ~mploy a reaction mixture composition
expressQd in t~rms of molar ratios as follows:
aR : (MXAlyPz)O2 : bH20
wh~rein "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 30;
"M" represents a metal of the group zinc, magne~ium,
manganese and cobalt, "x", "y" and "z" represent the
D-14642
1329213
-125-
mole fractions, respectively, of "M", aluminum and
phosphorus in the (~XAlyPz)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
~zn
Mole Fraction
Point ~ y
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 I P) ~ (x + y + z) ~ 1.00 mole.
In for~ing 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 prefQrably N, which compounds also contain at least
one alkyl or aryl group having from 1 to 8 carbon atoms.
D-14642
1323213
-126-
Particularly preferred nitrogen-containing compounds for
use as templatin~ agents are the amines and quaternary
ammonium compounds, the latter being represented
generally by the formula R4N wherein each R is an alkyl
`5 or aryl group containing from 1 to 8 carbon atoms.
Polymeric quaternary ammonium salts such as
t(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 te~plàting species may control the course of
the reaction with the other templating species serving
primarily to establish the pH conditions of the reaction
gel. ReprQsentative templating agents include
tetramethylam~oniu~, tetraethylammonium,
t~trapropylammonium or tetrabutylammonium ions;
di-n-propylamine; tripropylamine; triethylamine;
triQt~-anolamine; pip~ridine; cyclohexylamine;
2-methylpyridine; N,N-dimethylbenzylamine;
N-N-dimethylethanolamine; choline;
N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2)
octane; N-m~thyldiethanolamine; N-methylethanolamine;
N-methylpip~ridine; 3-methylpiperidine;
D-14642
1329213
-127-
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;
S isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating
agent will direct the formation of every species of
~etal aluminophosphate (MeAPO), i.e., a single
templating agent can, with proper manipulation of the
reaction conditions, direct the formation of several
MeAP0 compositions, and a given MeAP0 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
AlP04 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 thesa compounds do function
as t-mplating agents. Conventional phosphorus salts
such as sodium metaphosphate, may be used, at least in
part, as the phosphorus source, but are not preferred.
The aluminu~ source is preferably either an
aluminum alkoxide, such as aluminum isopropoxide, or
pseudoboehmite. The crystalline or amorphous
D-14642
132~213
-128-
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
`5 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 formata, zinc iodide, zinc sulfate hep~ahydrate,
magnesium ~cetate, magnasium bromida, magnesium
chloride, magnasium iodide, magnesium nitrate, magnesium
sulfata, manganous acetata, manganous bromide, manganous
sulfata, and the liXa.
Whila not assential to the synthesis of MeAPO
composition~, it has been found that in general,
stirring or other moderate agitation of the reaction
mixture and/or seeding the reaction mixture with seed
crystal~ of eithar the MeAPO species to be produced or a
topologically similar aluminophosphate or
D-14642
.
1329213
-129-
aluminosilic~te composition, facilitates the
crystallization procedure.
After crystallization the MeAPO product is
isolated and advantageously washed with water and dried
in air. The as-synthesized MeAPO 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 raaction systems. It is possible,
however, that some or all of the organic moiety is an
occluded molecular species in a particular MeAPO
species. AS a general rule, the templating agent, and
- 15 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 MeAPO at temperatures
of 200'C to 700 C to th~rmally degrade the organic
speci~s~ In a few instanc~s the pores of the MeAP0
product are sufficiently large to permit transport of
the templating agent, particularly if the latter is a
small molecul~, and accordingly complete or partial
removal ther~of can be accomplished by conventional
desorption procedures such as carried out in the case of
zeolites. It will be understood that the term
"as-synthesi2ed" as used herein does not include the
.
` D-14642
- . :
-130- 1329213
condition of the MeAP0 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 value5 of "m" in the composition formula:
mR : tMX~lyPz)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 aluminum alXoxide 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 ~his 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 pr~sent in the as-synthesized NeAP0
material.
Since thQ MeAP0 compositions are formed from
A102, P02, and N02 tetrahedral units which,
resp~ctively, 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 A102 tetrahedra and
charge-balancing cations. In the MeAP0 compositions, an
D-14642
_ 131 - 1 329213
A102- tetrahedron can be balanced electrically
either by association with a PO2+ 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 ar. 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 form
an extraneous source. It has also been postulated
that non-adjacent ALO2- and PO2+ tetrahedral pairs
can be balanced by Na+ and OH-, respectively
tFlanigen and Grose, Molecular Sieves Zeolites-I,
ACS, Washington, D.C. (1971)].
FAPO M~LECULAR SIEVES
Ferroaluminophosphates are disclosed in
U.S~ Patent No. 4,554,143 and have a
three-dimensional microporous crystal framework
structure of FeO2n, ALO2- and PO2+ tetrahedral units
and have an essential empirical chemical
composition, on an anhydrous basis, of:
mR : (FeXAlyPz)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 (FexAlyPz)02 and has a value of from
zero to 0.3, the
D-14642-C
~.'*
1329213
-132-
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 ~ ~ ~
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 synthasizad the minimum value of I'm" in the formula
above is 0.02. In a preferred subclass o~ the
fQrroaluminophosphates the valu~s of "x", "y" and "z" in
the formula above are representing the following values
for ~xn, nyn and nzn
Mole Fraction
20 Point ~ y
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 fQrric or ferrous valence state, depending
D-14642
1 3292t3
133-
largely upon the source of t~e 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 tha 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, moreo~er, necessarily the
case that all of the Fe, Al and/or P content of any
given synthesizQd 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
ferroaluminophosphat~s, the "short-hand" acronym IlFAPO"
is sometimes employed hereinafter. To identify the
; various structural species which make up the generic
class FAPO, each species is a~signed a number and is
identified, for example, as FAPO-ll, FAPO-31 and so
forth.
The tQrm "essential empirical chemical
composition" is meant to include the crystal framework
and can include ar.y organic templating asent present in
the pore system, but does not include alkali metal or
D-14642
1~29213
-134-
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
FeO2 and/or A102 2 tetrahedra, FeO2 2 tetrahedra
associated vith PO2 tetrahedra or not associated with
PO2+ tetrahedra or an organic ion derived from the
organic templating agent.
The aforesaid ferroaluminophosphates are
synthesiz~d 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-
; fluoroethylenQ and heated, preferably under autogenous
pr-ssur~ at a temperature of at least lOO~C, and
prQf rably betweQn lOO'C and 250'C, until crystals of
the metal aluminophosphate product are obtained, usually
a period of from 2 hours to 2 waeks. The product is
recovered by any convenient method such as
centrifugation or filtration.
In synthesizing the FAPO compositions, it is
D-14642
1329213
~ 35-
preferred to employ a reaction mixture composition
expressed in terms of molar~ratios as follows:
( x y z) 2 2
wherein "R" is an organic templating agent; "a" has a
value great enough to constitute an effe~tive
concentration of "~" and is within the range of >0 to 6;
"b" has a value of from zero to 500, preferably 2 to 80;
"xn, "y" and "z" represent the mole fractions,
respectivaly, of iron, aluminum and phosphorus in the
(FexAlyPz)02 constituent, and each has a value of at
least 0.01, and representing the following values for
~X~ ~ nyn and ~z n
Mole Fraction
Point ~ ~ ~
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 O.S9 0.01
J 0.29 0.70 0.01
In the foreqoing 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 ~rom which the
ferroaluminopho~phates are crystallized, the organic
templatinq agent can be any of those heretofore proposed
D-I4642
132g213
-1'6-
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
us~ 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
ttCl4H32N2)(0H)2]x wherQin "x" has a value of at least 2
are also suitably employed. ~ono-, di- and triamines
are advantag~ously utilized, either alone or in
combination with a quaternary ammonium compound or other
t~mplating compound. Mixtures of two or more templating
agents can eith~r produc~ mixtur~s of the desired metal
aluminophosphates or the more strongly directing
t~mplating species may control the course of the
reaction with the other templating species serving
primarily to establish the pH conditions of the reaction
g~l. Repr~sentative templating agents include
tetramQthylammonium, tetraethylammonium,
tetrapropylammonium or tetrabutylammonium ions;
D-14642
1329213
-137-
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
ferroalumino~hosphate (FAPO), i.e., a single templating
agent can, with proper manipulation of the reaction
conditions, dir~ct the formation of several FAPO
compositions, and a giv~n 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
AlPO4 composition of U.S. Patent No. 4,310,440.
Organo-phosphorus compounds, such as tetrabutyl-
phosphonium bromide do not, apparently serve as reactive
D-14642
` 1329213
-138-
sources of phosphorus, but these compounds do function
as templating agents. Conventional phosphorùs 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 tric~loride, 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 re~ctive f~rroùs or ferric ions. Advantageously
iron salts, oxides or hydroxides are employed such as
iron sulfate, iron acetate, iron nitrate, or the like.
Oth~ sources such as a freshly precipitated iron oxide
r-FeOOH, arQ 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 Qither the FAPO species to be produced or a
topologically similar aluminophosphate or
D-14642
1329213
~ 139-
aluminosilicate COmpositiQn, facilitates the
crystallization procedure.
After crystallization the FAP0 product is
isolated and advantageously washed with water and dried
`5 in air. The as-synthesized FAP0 contains within its
internal pore system at least on~ form of the templating
agent employed in its formation. Most commonly th~
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 FAP0 species.
As a general rule, the templating agent, and hence the
occluded organic species, is too large to mQve freely
through the pore system of the FAPO product and must be
r~moved by calcining thQ FAPO at temperatures of 200 C
to ~00~C to thermally degrade the organic species. In a
few instances the pores of the FAP0 product are
sufficiQntly 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-14642
` ~329213
-l~o-
FAPO phase wherein the organic moiety occupying the
intracrystalline pore system as a result of the
hydrothermal crystallization procass 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 hereina~ove. In those
preparations in which an aluminum alXoxide is employed
as the source of aluminum, the corresponding alcohol is
necessarily presQnt 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 FAP0
material.
Since the FAP0 compositions are formed from
A102 , P02 , FeO2 and/or FeO2 2 units the matter of
cation exchangeability is consid~rably more complicated
than in the case of zeolitic molecular sieves in which,
ideally, thQre is a stoichiometric relationship between
A102 tetrahedra and charge-balancing cations. In the
FAP0 compositions, an A102 tetrahedron can be balanced
electrically either by association with a PO2+
D-14642
_, . .
- 141 - 1329213
tetrahedron or a simple cation such as an alkali
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 FeO2~ or FeO2~2
tetrahedron can be balanced electrically by
association with P02+ tetrahedron, a Fe+2 or Fe+3
cation, organic cations derived from the templating
agent, or other metal cation introduced ~orm an
extraneous source. It has also been postulated that
non-adjacent A102- and P02+ tetrahedral pairs can be
balance by Na~ and OH-, respectively tFlanigen and
Grose, Molecular Sieve Zeolites-I, ACS, Washington,
D.C. (1971)~.
TAPO MOLECULAR SIEVES
TAPO molecular sieves are disclosed in U.S.
Patent No. 4,500,561 and comprise a
three-dimensional microporous crystal framework
structure of TiO2, AL02- 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; nmn 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-14642-C
.. . . . .
i329213
2--
availa~le void volume of pore system of the particular
titanium molecular sieve: "x", "y" and "z-l represent the
mole fractions of titanium, aluminum and phosphorus,
respectively, present as tetrahedr~l oxides,
representing the following values for "xn, -y" and "z":
Mole Fraction
Point ` ~ y z
A 0.001 0.45 0.549
B 0.88 0.01 0.11
C 0. g8 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 ~ollowing values for "x", "y" and "z":
Mole ~acti
~oin~ ~ Y
a 0.002 0.4g9 0.499
b 0.20 0.40 0.40
c 0.20 0.50 0.30
d 0.10 Ø60 0.30
0.002 0.60 0.398
The titanium-containing molecular sieves are
referred to h~reinafter, solely for point o~ reference
herein as "TAPO" molecular sievet, or as "TA~Os" if the
reference is to the class as a whole. This designation
is simply made for the sake of convenient reference
D-14642
132921~
-143-
herein and is not meant to designate a particular
structure for any given TAP0 molecular sieve. The
members of the class of TAPO's employed hereinafter in
the examples will be characterized simply by referring
to such members as TAP0-5, TAP0-11, 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 maaning to designate the
simplest for~ula which gives the relative number of
moles of titanium, aluminum and phosphorus which form
the tTi2], tP2] and tAlo2] tetrahedral unit within a
titanium-containing molecular sieve and which forms t~e
molacular ~ramework of the TAP0 composition(s). The
unit empirical formula $s given in terms of titanium,
aluminum and phosphorus as shown in Formula (1), above,
and does not include other compounds, cations or anions
which may ba present as a result of the preparation or
the ~xistence 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-14642
: , . ,
.
1329213
-1~4-
empirical formula is given, and water may also be
reported unless such is defined as the anhydrous for~.
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 by the total
moles of titanium, aluminum and phosphorus.
Thè unit empirical formula for a TAP0 may be
given on an "as-synthesized" basis or ~ay be given after
an "as-synthesized" TAP0 composition has been subjected
to some post treatment process, e.g., calcination. The
term "as-synthesized" herein shall be used to refer to
the TAP0 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 TAP0 will depend
on several factors (including: the particular T~P0,
template, severity of the post-treatment in terms of its
ability to remove the template from the TAP0, the
proposed application of the TAPO composition, and etc.)
and the ~alue for "m" can be within the range of values
as defined for the as-synthesized TAPO compositions
although such is generally less than the as-synthesized
TAP0 unless such post-treatment process adds template to
the TAP0 so treated. A TAP0 composition which is in the
calcined or other post-treatment form generally has an
D-14642
.,
-145- 1 329213
empirical fo~mula represented ~y Formula (1), except
that t~.e value of llml' is ~ge~erally less than about 0.02.
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 evQnt, ~he template, R, is undetectable by
normal analytical procedures.
The TAPO molecular sieves are generally
furthar characterized by an intracrystalline adsorption
capacity for water at 4.6 torr and about 24-C of about
3.0 weight percent. The adsorption of water has been
observed to be completely reversible while retaining the
same essential fra~ework 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 linXage~.
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-14642
. : ' . . ..
1329213
-1~6-
fluoroethylene, and heated, preferably under autogenous
pressure, at a temperature ~f at least about lOO~C, and
preferably between lOO C and 250~C, 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 TAP0 molecular sieves, it has
been found that in general stirring or other moderate
agitation of the rèaction mixture and/or seeding the
reaction mixture with seed crys~als of either the TAP0
to be produced, or a topologically similar composition,
facilitates the crystallization procedure. The product
is recovered by any convenient metho~ such as
centrifugation or filtration.
A~ter crystallization the TAPO(s) may be
isolated and washed with water and dried in air. As a
result of tha hydro~hermal crystallization, the
as-synthesized TAP0 contains within its intracrystalline
pore system at least one form o~ the template employed
in its formation. &enerally, 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.
GenQrally 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 TAP0 at temperatures of between
D-14642
1329213
~ 7-
akout 200-c and to about 7000C so as to ther~ally
degrade the templat2 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 TAP0 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 TAP0 compositions are generally formed from a
lS reaction mixture containing reactive sources of TiO2,
Al2O3, and P2O5 and an organic templating agent, said
reaction mixturQ comprising a composition expressed in
ter~s of molar oxid~ ratios of:
fR20 : ~TiXAlyPz)02 : g H20
wberein HR" is an organic te~plating agent; "f" has a
value large enough to constitute an effective amount of
"Rn, said effective amount being that amount which form
said TAP0 compositions: "g" ha~ a value of from zero to
500; nxn~ Hy~ and HZ~ represent the mole fractions,
respectively of titanium, aluminum and phosphorus in the
(TiXAlyPz)02 constituent, and each has a value of at
D-14642
---` 13292~3
-1~8-
least Q.ool and being within the following values for
"x", "y" and "z": ~ ~
Mole Fraction
Point ~ Y
h o.ool 0.989 0.01
i 0.001 o.Ol 0.989
j 0.32 0.24 0.44
X 0.98 O.ol o.ol
Although the TAPO 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:
oR20 wM20 (TixAlyPz)2 nH2
wh~rein "R" is an organic templàte; "o" has a value
great enough to constitute an effe~tive concentration of
"R" and is preferably within thQ range of from greater
than zero ~0) to about 5.0: "N" is an alkali metal
cation; "w" has a value of fro~ zero to 2.5; "n" hAs a
value betwQ~n about zero (0) and about 500; "x", "y" and
"z" represent the ~ole fractions, respectively, of
titanium, aluminum and phosphorus in the (TiXAlyPz)02
constituent, and each has a value of at least O.Ool and
being within the foliowing values for "x", "y" and "z":
D-14642
'
1329213
1~9-
Mole Fraction
Point ~ x ~ y ~ z
h 0.001 0.989 0.01
i o.OOl 0.01 0.989
j 0.32 0.24 0.44
k 0.98 0.01 0.01
When the TA~Os are synthesized by this method
the value of "m" in Formula (1) is generally above about
0.02.
Though the presence of alXali metal cations is
not pre~erred, 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 th~ phosphorus source to a basic
rQaction mixture containing the titanium source and
aluminum source, (as was done in most of the published
att~mpts to substitute isomorphously [P02] tetrahedra
for tsio2] tetrahQdra in zeolitic structures). Although
the reaction mechanism is by no means clear at this
time, the function of the template may be to ~avor the
incorporation of ~P02] and [A102] tetrahedra in the
framework structures of the crystalline products with
D-14642
.. . . .
1329213
--150--
[Tio2] tetrahedra isomorphously replacing [P02]
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, aralXyl, or
alkylaryl group and is preferably aryl or alkyl
containing between 1 and 8 carbon atoms, although more
; than eight car~on atoms may be present in the group "R"
of th~ template. Nitrogen-containing templates are
pref~rred, including amines and quaternary ammonium
compounds, the latter being represQnted generally by the
formula R'4~+ wherein each R' is an alkyl, aryl,
alkylaryl, or aralkyl group; wherein R' preferably
contains from 1 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 ~(C14H32N2)(OH)2]X
D-14642
, ,. . . - .
.. ..
132921~
--151--
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
S another template. The exact relationship of various
templates when concurrently employed is not clearly
understood. Mixturss of two or more templating agents
can produce either mixtures of TAPOs or in the instance
where one templata 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.
lS Representative templates include
tetramethylammonium, tetraethylammonium,
tetrapropylammonium or tetrabutylammonium ions;
di-n-propylamine; tripropylamine; triethylamine;
triethanolamine; piporidine; cyclohexylamine;
2-methylpyridine; N,N-dimèthylbenzylamine;
N,N-diethylethanolamine; dicyclohexylamine;
N,N-dimethylethanolamine; 1,4-diazabicyclo ~2,2,2)
octane; N-methyldiethanolamine, N-methyl-ethanolamine;
N-methylcyclohexylamine; 3-methyl-pyridine;
4-methylpyridina; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
D-14642
-152- 1 3 29 21 3
di-n-butylamine; neopentylamine; di-n-pentylamine;
~ isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine: and 2-imidazolidone. Not every template
will produce every TAP0 composition although a single
template can, with proper selection of the reaction
conditions, cause the formation of different TAP0
compositions, and a given TAP0 composition can be
produced using different templates.
In those instances where an aiuminum 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 TAP0 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 TAP0
composition, either as occluded (extraneous) cations
and/or as structural cations balancing net negative
charges at various sites in the crystal lattice. It
D-14642
13~9213
-153-
should be understood that although 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
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. ~hosphoric acid is the most suitable
phosphorus sourc~ employed to date. Accordingly, other
acids of phosphorus are generally believed to be
suitable phosphorus sources for use herein. organic
phosphates such as triathyl phosphate have been found
satisfactory, and so also have crystalline or amorphous
aluminophosphates such as the A1~04 compositions of U.S.
~atent 4,310,440. Organo-phosphorus compounds, such as
t~trabutyl-phosphonium bromide have not, apparently,
servQd as reactive sources of phosphorus, but these
compounds do function as templating agents and may also
be capable of boing suitable phosphorus sources under
propQr procRss conditions (yet to be ascertained).
Organic phosphorus compounds, e.g., esters, are believed
to be generally suitable since they can generate acids
D-14642
1329213
7 s ~
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
10 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 trichloridQ, can be employed but as generally
not preferred.
Sincs 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-dim~nsional microporous crystal framework
structure, it is advantageous to characteriz~ the TAPO
molecular sieves by mQans 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~, h~s substituted isomorphously for
D-14642
1329213
-15S-
~A102] or ~2] 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 : qA1203 : rP205
wherein "R"`represents at least one organic templating
agent present in the intracrystalline pore system; "v"
represents an effective amount of th~ organic templating
agent to form said TAPO compositions and preferably has
a value betweien and including zero and about 3.0; "p",
nqn and nrN represent moles, respectively, of titanium,
alumina and phosphorus pentoxide, based on said moles
being such ~at they are within the following values for
npn ~ nqn and "r":
MQ1Q~ Fraction
Point ~2. g
A 0.004 1.0 1.22
B 176 1.0 11.0
C 196 1.0 1.0
D 0 . 828 1. 0 0 . 0143
E 0.003 1.0 0.427
The parameterqi npn~ ~q~ and "r" are preferably within
thei following values for npn ~. nql~ and "r":
D-14642
,,. - . . . :
. ' ' : .
:
-
1329213
-155-
Mole Fraction
Poi~t
a 0.008 1.0 l.o
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
lo crystalline molecular sieves in which at least one
element capable of forming a throe-dimensional
microporous framework forms crystal framework structures
of AlO2 , P02 and M02n tetrahedral oxide units wherein
"MO2nn represents at least one different element (other
than Al or P) present as tetrahedral oxide units "M02n"
with charge "n" where `'n" may be -3, -2, -1, 0 or +1.
- The mo~bers of this novel class of molecular sieve
compositions havo crystal framowork structures of A102-,
P02+ ~nd M02n tetrahedral units and have an empirical
chomical composition on an anhydrous basis expressed by
tho formula:
mR : (MXAly~z)02
whor-in "R" reprosents at least one organic templating
agent presont in tho intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(MXAlyP2)02; "M" represents at least one element capable
D-14642
~ - 157 - 1329213
of forming framework tetrahedral oxides; and ~x",
-y" and "z-- represent the mole fraction 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 +. nMn 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 EhAPOs 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 "ELAPOn molecular sieves further
include numerous species which are intended herein
to be within the scope of the term Hnon-zeolitic
molecular sieves~ such being disclosed in the
following commonly assigned patents and applications
l(A) following a serial number
D-14642-C
- 158 _ 13292~3
indicates that the application is abandoned and ~C)
indicates a continuation of the immediately
preceding patent or application]:
,~
.,
.
D-14642-C
-` 1329213
- 159 -
U.S. Patent~Serial No. Filed NZMS
600,166(A) April 13, 1984 AsAPO
4,913,888 Feb. 19, 1986 AsAPO
599,812(A) April 13, 1984 BAPO
804,248(C)(A) Dec. 4, 1985 BAPO
4,952,383 March 24, 1987 BAPO
599,776(A) April 13, 1984 BeAPO
4,940,571 March 3, 1986 BeAPO
599,813(A) April 13, 1984 CAPO
4,759,919 Feb. 19, 1986 CAPO
599,771(A) April 13, 1984 GaAPO
830,890~A) Feb. 19, 1986 GaAPO
599,807(A) April 13, 1984 GeAPO
4,888,167 March 20, 1986 GeAPO
599,811(A) April 13, 1984 LiAPO
4,789,535 Feb. 28, 1986 LiAPO
4,686,093 April 13, 1984 FCAPO
600,172(A) April 13, 1984 ) ElAPO (M
) comprises
two
- different
846,088(A) March 31, 1986 ) elements)
599,824(A) April 13, 1984 FeTiAPO
4,917,876 September 2, 1986 FeTiAPO
599,810(A) April 13, 1984 XAPO
4,956,165 September 2, 1986 XAPO
The ELAPO molecular sieves are generally
referred to herein by the acronym "ELAPO" to
designate
D-14642-C
29213
--1 ,o--
element(sj "~" in a framework of AlO2 , PO2 and MO2n
tetrahedral cxide 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 A102 , PO2 , Mgo2 and BeO2 2 tetrahedral
units. To identify various structural species which
make up each of the subgeneric classes, each ~pecies is
assigned a number and is identified as "ELAPO-i" wherein
10 n 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 ELAP0 molecular sieves comprise at least
one additional element capable of forming framework
tetr~hedral oxide units (MO2n) to form crystal framework
structures with A102 and PO2+ tetrahedral oxide units
wherein "M" represents at least one element capable of
for~ing tetrahedral units "M02nn 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 ELAP0 molecular sieves have crystalline
three-dimensional microporous framework structures of
A102 , P02+ and N02n tetrahedral units and have an
D-14642
,, 1329213
-~61-
empirical chemical composition on an anhydrous basis
expressed by the formula: ~
mR : (MXAlyPz)02;
wherein "R" represents at least one organic templating
S 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
framework tetrahedral oxides where "N" is at least one
element selected from the group consisting of arsenic,
~eryllium, 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 empirical5 chemical formula (anhydrous):
mR : (MxAlyPz)02
where "xn, "y" and ~z" repres~nt the mole fractions of
said "M", aluminum and phosphorus. The individual mole
fractions of each "M" (or when M denotes two or more
ele~ents, Ml, M2, N3, etc.) may be represented by "xl",
~x2n, ~x3n, etc. wherein "xln, "x2n, and l'x3l' etc.
represent the individual mole fractions of elements Ml,
M2, M3, and etc. for "M" as above defined. The values
of "xln, "x2n, "x3l', etc. are as defined for "x",
hereinafter, where ~xl`' + ~`x2'` + llx3" . . . = "x" and
where xl, x2, X3, etc. are each at least 0.01.
D-14642
:
~ ,
1329213
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The EL~P0 molecular sieves have crystalline
three-dimensional microporo~s framewor~ structures of
M02n, A102 and PO2 tetrahedral units having an
empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2
wherein nRn represents at l~ast one organic templating
agent present in the intracrystalline pore system; "m"
represents a molar amount of NRn present per mole of
(MXAly~z~O2 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 ~2" are within the
following values for "xn, -y" and "z", although a~ will
appear hereinbelow, the limits for "x", "y" and -z" may
vary slightly with the nature of the element "M":
. Mole Fraction
Point ~ Y
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-14642
1329213
-153-
Also, in general, in à preferred sub-class of
the ELAPOs of this invention, the values of "x", "y" and
"z" in the formula above are within the following values
for "x", -y" and -z", although again the relevant limits
S may vary somewhat with the nature of the element "M", as
set forth hereinbelow:
Mole Fraction
~oint ~ Y
a 0.02 0.60 0.38
b 0.02 0.38 0.60
c 0.39 0.01 0.60
d 0.60 O.Ql 0.39
e 0.60 0.39 0.01
f 0.39 0.60 0.01
ELAPO 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
20 ` a compound of an el~ment of Group VA of the Periodic
Tabl~, and/or optionally an alXali or other metal. The
reaction mixture is generally placed in a sealed
pres~ure 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 prefarably between lOO C and
D-14642
': .
, . ,
-
13292~3
-164-
200 C, ùntil c-ystals of the ELAPo product are obtained,
usually a period of f-om sev~ral 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
being generally employed to obtain crystals of the ELAP0
products. The product is recovered by any convenient
method such as centrifugation or filtration.
In synthèsizing the ELAPo compositions of the
instant invention, it is in genaral preferred to employ
a reaction mixture composition expressed in terms of the
molar ratios as follows:
aR : (MXAlyP2)02 : 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 greàtQr than zero (0) to
about 6: "b" has a value of from zero (0) to about 500,
preferably bQtweQn about 2 and 300; "N" represents at
least onQ ~lement, as above described, capable of
forming tetrahedral oxide framework units, M02n, with
A102 and P02+ t~trahedral 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 Q.ol and "x"
has a value of at ieast 0.01 with each element "M"
having a mole fraction of at least 0.01. In general,
D-14642
1329213
165-
the mole fractions "x", "y" and "z" ars pr~ferably
within the ~ollowing values~for "x", "y" and "z":
Mole Fra~ion
Point ~ y
F 0.01 0.60 0.39
G 0.01 0.35 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 formin~ ELAPOs with various elements "M"
will be given below.
In th~ for~going expression of the reaction
composition, the reactants are normalized with respect
to a total of ~M + Al ~ P) ~ ~x ~ y + z) 5 l.Q0 mole,
wheraas in oth~r cas~s th~ reaction mixtures are
express~d in terms of molar oxide ratios and may be
normalized to 1.00 mole of P205 and/or A1203. This
latt~r form is readily converted to the form~r ~orm by
routine calculationQ by dividing the total number of
moles of "Nn, aluminum and phosphorus into the moles of
each of "~", aluminum and phosphorus. The moles of
template and water are similarly normalized by dividing
by the total moles of "M", aluminum and phosphorus.
In for~ing the reaction mixture from which the
instant molecular sieves are formed the organic
D-14642
,
1329213
-166-
templating agent can be any of those heretofore proposed
for use in the synthes.s of~conventional zeolite
aluminosilicates. In general these compounds contain
elements of Group V~ of the Periodic Table of Elements,
particularly nitrogen, phosphorus, arsenic and antimony,
preferably nitrogen or phosphorus and most preferably
nitrogen, which co~pounds also contain at least one
alkyl or aryl groùp having from 1 to 8 carbon atoms.
Particularly preferred compounds for use as templating
agents are the amines, quaternary phosphonium compounds
and guaternary 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
wit~ a quaternary ammonium compound or other templating
compound. Mixtures of two or more templating agents can
~ither 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-14642
1329213
~ 57-
tetrapr_pylammonium or tet.abutylammonium ions;
t~trapentylammonium 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-butyla~ine; ethylenediamine:
pyrrolidine; and 2-imidazolidone. Not every templating
lS agent will direct the formation of every species of
ELAPO, i~Q., a single templating agent can, with proper
manipulation of th~ reaction conditions, direct the
formation of several ELAPO compositions, and a given
E~APO composition can be produced using several
differ nt 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.~. 4,310,440. Organo-
phosphorus compounds, such as tetrabutylphosphoniumbromide, do not apparently serve as reactive sources o~
D-14642
1329213
~168-
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 zeoli~e
synthesis, such as gibbsite, sodium aluminate and
aluminum trichloride, can be employad 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 frameworX tetrahedral oxida unit of the
el~ment. The organic and inorganic salts, of "M" such
as oxides, alXoxides, hydroxides, halides and
carboxylates, may be e~ployed including the chlorides,
bromides, iodides, nitrates, sulfates, phosphates,
acetates, formates, and alXoxides, including ethoxides,
propoxides and the like. Specific preferred reagents for
introducing various elements "M" are discussed
hereinbelow.
D-14642
: ~ .
1329213
-159-
While not essential to the synthesis of ELAP0
composi~ions, stirrins or o~h~r mode.ate 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 t~e ELAP0 product may be
isolated and advantageously washed with water and dried
in air. The as-synthesi2ed ELaP0 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
lS case with as-synthesizQd aluminosilicate zeQlites
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 ELAP0 product
and must be removed by calcining the ELAP0 at
temperatures of 200-C to 700 C to thermally degrade the
organic species~ In a few instances the pores of the
E~AP0 product are sufficiently large to permit transport
of the templating agent, particularly if the latter is a
D-14642
.
. .
- 1329213
-170-
small mol~cule, and accordingly complete or partial
r~moval the-eof can be accomplished by conventional
desorption procedures such as carried out in the case of
zeolites. It will be understood that the term
S ~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 value0 of "m" in the composition formula:
mR : (~XAlyPz)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 HM~, aluminum or phosphorus, the
corresponding alcohol is necessarily present in the
reaction mixture since it is a hydrolysis product of the
alkoxide. It has not been deter~ined whether this
alcohol participates in the synthesis process as a
t~mplating agent. For the purposes of this application,
however, this alcohol i~ arbitrarily omitted from the
class of templating agents, even if it is present in the
as-synthesized ELAP0 material.
Since the present ELA~0 compositions are
for~ed from M02n, A102 and P02 tetrahedral oxide units
which, respectively, have a net charge of "n", (where
D-14642
- 171 - 1329213
~m~ may be -3, -2, -1, ~ or ~1), -1 and ~1, 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 instant
compositions, an A102- tetrahedron can be balanced
electrically either by association witll 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
mi~ture, organic cations derived from the templating
agent, a simple cation such as an alkali metal
cation, or other divalent or polyvalent metal
~ation, 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 U.S. Patent No.
4,913,888 have a framework
D-14642-C
. . .
. ,
''' '" ~ ' .
1329213
.
-172-
st.ucture of AsO2n, AlO2 and PO2+ tetrahedral units
(where "nl' is -1 or +1) and~have an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (ASxAlyPz~2
wherein "Rn` represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar a~ount 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 "xn, "y" and
"z" represent t~e mole fractions of the elements
arsenic, aluminum and phosphorus, respectively, present
as tetra~edral oxides~ The mole fractions "x", "y" and
"z" are generally defined as being within the limiting
compositional values or points as follows:
.~ ole Fraction
Point ~ Y
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
AsAPO molecular sieves, depending upon whether the value
of "n" is -1 or ll (i.e. whether the arsenic is
D-14642
` ` `` 1329213
-173-
trivalent or pentavalènt), it being understood that
mixtures o~ such are permitted in a given AsAP0. ~hen
"n" is -1, the preferred values of x, y and z are within
the limiting compositional values or points as follows:
-5 Mole Fraction
Point ~ ` Y
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 ll, the preferred values of x, y and z are
within the limiting compositional values or points as
follows:
Mole Fraction
15 Point ~ y
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
AsA~O molecular sieves in which "n" ~ Il, the values of
x, y and z are as follows:
D-14642
,
'
.-
.
1329213
-174-
Mole Fraction
Point ~ ~ y
i 0.03 0.52 0.4s
j 0,03 0.4s 0.52
k 0.08 0.40 0.52
l 0.33 ` 0.40 0.27
m 0.33 0.41 0.26
n 0.22 0.52 0.26
AsAP0 compositions are senerally synthesized
by hydrothermal crystalli2ation 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 genQrally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperaturQ between about 50-C
and about ~SO-C, and preferably between about lOO-C and
about 200'C until crystals of the AsAP0 product are
obtained, u-~ually 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
2S 20 days, and preferably about 12 hours to about 7 days,
D-14642
- 1329213
-175-
have been observed. The product is recovered by any
convenient mathod such as centrifugation 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:
. 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
lo amount within the range of greater than zero (0) to
about 6, and most preferably not ~ore 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-14642
.
~3292~3
_176-
~ole 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:
Mole Fraction
oin~ ~ y
a ` 0.20 0.55 0.25
b 0.20 O.So 0.30
c 0.30 0.40 0.30
d 0.40 0.40 0.20
0.40 0.50 0.10
f 0.35 0.55 0.10
In the foreqoing 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 sie~es containing
arsenic, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
D-14642
i329213
--' 77--
Pre~ar~tive Reagents
AsAPO compositions may be prepared by using
numerous reagents. Reagents which may be employed to
prepare AsAPOs include:
S (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) Pr2N8: di-n-propylamine, (C3H7)2NH;
(h~ Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinuclidine, (C7Hl~N);
(~) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(X) C-hex: cyclohexylamine;
(1) TNAOH: tetramethylammonium hydroxide;
~m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Pre~arative Procedures
~ AsAPOs 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-14642
'
,
1329213
- 178 -
solution the aluminum oxide or isopropoxide is
added. This mi~ture 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 MOLECU~AR SIEVES
The BAPQ molecular sieves of U.S. Patent
No. 4,952,383 have a framework structure of B02-,
AlO2- and P02~ tetrahedral units and have an
empirical chemical composition on an anhydrous basis
e~pressed by the formula:
mA : (B~AlyPz)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 (B~AlyPz)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
o~ides. The mole fractions "~", "y" and "z"
D-14642-C
~.~
- 1329213
--1~9--
are generally defined as being within the limiting
compositional values or poi~ts as follows
Mole Fraction
Point x ~ 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 BAP0 molecular
sieves the values of x, y and z are within the limiting
compositional valuQs or points as follows:
MQIç.Eraction
lS Point ~ v
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
~n especially preferred subclass of the BAP0
molecular sieves are those in which the mole fraction,
"xn, of boron is not greater than about 0.3.
BAPO compositions are generally synthesized by
hydrothermal crystallization from a reaction mixturs
containing reactive sources of boron, aluminum and
phosphorus, pre~erably an organic templating, i.e.,
D-14642
`
` 1329213
-180-
structure-dirPcting, agènt, preferably a compound of an
element o~ 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
- polytetrafiuoroethylene and heated, preferably under
autogenous pressure at a temperature between about 50 C
and about 250 C, and pref~rably bQtween about lOO C and
about 200-C until crystals of the BAP0 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 l to about 7 days, have
been observed. The product is recov~red by any
convenient mQthod such as centrifugation or filtration.
In synth~sizing the BAPO compositions, it is
proferred to Q~ploy a reaction mixture composition
expressed in terms of the molar ratios as follows:
t x y z) 2 2
wheroin ~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 l.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-14642
~U'?
-
1329213
1 ~ 1
not greater than about 10: and "x", "y" and "z"
reprasent 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 valuès or points as follows:
Mole Frac~ion
10~,Q~ ,~ y Z
& 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 ~.01
15 K 0.39 0.60 0.01
~ speciaily preferred reaction mixtures are
thos~ containing from 0.5 to 2.0 moles of B203 and from
0.75 to 1.25 molas of A12O3 for each mole of P205.
In th~ forQgoing expression of the reaction
co~position, the reactant~ are normalized with respect
to the total of Nxn, "y" and "z" such that
(X + y + 2) ' 1.00 mole.
The exact nature of the BAP0 molecular sieves
i3 not entirely understood at present, although all are
25 beliQved to contain BO2, A102 and PO2 tetrahedra in the
three-dimension21 microporous framework structure. The
D-14642
1329213
--132--
low level o~ bo-on present in so~e of the instant
molecular siaves makes it difficul' to asc2r~ain the
exact nature of the interactions among boron, aluminum
and phosphorus. As a result, although it is believed
that B02 tetrahedra are present in the three-dimensional
microporous frameworX structure, it is appropriate to
characterize certain BAPO compositions in terms of the
molar ratios of ox`ides.
Molecular sieves containing boron, aluminum
and phosphorus as framewor~ tatrahedral oxide units are
prepared as follows:
Pre~arative Reagents
B~PO 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) H3P04: 85 weight porcent aqueous
phosphoric acid;
(d) boric acid or trimethylborate;
te) 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, (C3H~)3N;
D-14642
.
13292~3
-1~3-
(i) Quin: Quinuclidine, (C7H13N);
(J ) MQuin: ~et~y~ Quinuclidine ~ydroxide,
(C7H13NCH3OH):
(k) C-hex: cyclohexylamine;
(1) TM~OH: tetramethylammonium hydroxide;
~m) TPAOH: tetrapropylammonium hydroxide; and
~n), DEEA: 2-diethylaminoethanol.
- Prepara~ive 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 n~cessary 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 alaments can be added during the later
heat treatmant; in particular, it has been found
convenient to add additional guantities of phosphorus to
thQ amorphous material before the heat treatment. The
praliminary formation of the amorphous material assists
" in the incorporation o~ 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-14642
- 184 - 1329213
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 of U.S. Patent
No. 4,940,570 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 : (B~AlyPz)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 (B~AlyPz)O2 and has a value of
zero to about 0.3, but is preferably not greater
than 0.15; and ~n~ ~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-14642-C
-
" 1329213
-135-
Mole Fraction
Point ~ ` y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 o.ol 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 O.ol
In a preferred subclass of the BeAPO molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
Point ~ Y
a 0.01 0.60 0.39
b Q.01 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
BQAPO molecular sieves the values of x, y and z are as
follow~:
. ~ole Fraction
~oint ~ y
0.02 0.46 0.52
f . 0.10 0.38 0.52
g 0.10 0.46 0.44
D-14642
1329213
-_35-
BeAP0 compositions are generally synthesized
by hydrct~ermal crystalliza~ion 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 Sroup V~ of the Periodic Table, and/or
optionally an alkali or other metal. The reaction
mixture is generally placad 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 pre~erably between about lOO C and
about 200'C until crystals Or the BeAP0 product are
obtained, usually a period of from several hours to
several weeks. Typical effective times of from 2 hours
` to about 30 day-~, genQrally from about 4 hours to about
14 days, and prefarably about 1 to aboùt 7 days, have
been observed. ~he product is recovered ~y any
convenient met~od ~uch as centrifugation or filtration.
2Q In synthesizing tha BeAP0 compositions, it is
prefarred to employ a reaction mixture composition
expressed in terms Or the molar ratios as follows:
( 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
D-14642
- 1329213
-18~-
amount within the range of greater than zero (0) to
about 6, and most praferabl~ not more than a~out 1.5;
"b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300, most
S preforably 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
selectad such that the mole fractions "x", lly~ and "z"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point ` ~ ~ ~
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
X 0.39 0.60 0.01
E~pocially preferred reaction mixtures are
those wherQin the mole fractions "x", "y" and "zl- are
within the limiting compositional values or points as
follows:
D-14642
1329213
-188-
~ole Fraction
Point ` ~ ` y
g o.oi 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 reactan~s are normalized with respect
to the total of ~xn~ ~yN and "zl~ such that
(X + y + 2) ~ 1. 00 mole. Molecular sie~es containing
beryllium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
Pre~arative Reagents
Be~PO compositions may be prepared by using
numerous reagents. Reagents which may be employ~d to
~ prepare BeAPOs include:
-~ (a~ aluminum isopropoxide;
~b) pseudoboehmite or other aluminum oxide;
tc) H3P04: 85 weight percent aqueous
; phosphor~c 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-14642
1329213
- 189 -
(g) Pr2NH: di-n-propylamine, (C3H7~2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(1) Quin: Quinuclidine, (C7H13N);
(j) MQuin: Methyl Quinuclidine hydro~ide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide;
and
~n) DEEA: 2-diethylaminoethanol.
~reParative Procedures
BeAPOs may be prepared by forming a
starting reaction mixture by dissolving the
beryllium sulfate and the H3PO~ in at least part of
the water. To this solution the aluminum oxide or
isoproposide is added. This mixture is then blended
until a homogeneous misture is observed. To this
~isture the templating agent and the resulting
misture 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 of U.S. Patent No.
D-14642-C
1329213
4,759,919 have a framework structure of CrO2n, AlO2-
and PO2+ tetrahedral units (where ~n" is -1, 0 or
+l) 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 (Cr ~ lyPz)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
o~ides. When "n" is -1 or +1, the mole fractions
~", "y~ and "z~ are generally defined as being
within the limiting compositional values or points
as follows:
~ ~ `
` Mole Fraction
Point ~ y ~
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
D-14642-C
~AIqi
1329213
-191--
When "n" is 0, the mola fractions "x'i, "y" and "z" are
generally defined as being within the limiting
compositional values or points as follows:
Mole F~c~on
5 Point x y
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 -1, 0 or ll (i.e. whether the chromium has an
oxidation number of 3, 4 or 5), it being understood that
~ixtures of such are permitted in a given CAPO. When
"n" is -1, the preferred values of x, y and 2 are within
the limiting compositional values or points as follows:
Mole Fraçtion
~ Point ~ ~ ~
; 20 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
In an espQcially preferred subclass of these
CAPSO molecular sieves in which ~'n~' 3 -1~ the values of
x, y and z are as follows:
D-14642
1329213
-192-
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 li~iting compositional values or points as
follows:
. Nole Fraction
-~' Point ~ y
e 0.01 0.60 0.39
: 15 f 0.01 0.47 0.52
g 0.50 0.225 0.275
h 0.50 0.40 0.10
i Q.30 0.60 0.10
Wh~n ~n~ is +1, thQ preferred values of x, y and z are
within the li~iting compositional values or points as
follow~:
D-14642
' - . ~, ~. , '.. ' -
1329213
-193-
Mole Fraction
Point x ~ y z
j o.ol 0.60 0.39
k 0.01 0.40 0.59
1 0.59 0.40 0.01
m 0.39 0.60 o.lo
Sinca the exact nature of the CAP0 molecular
sieves is not clearly understood at present, although
all are believed to contain CrO2 tetrahedra in the
- 10 three-dimensional microporous crystal framework
structure, it is advantageous to characterize the CAPo
molecular sieves by means of their chemical composition.
This is due to the low level of chromium presant in
certain of the CAP0 molecular sieves prepared to date
which makes it difficult to ascertain the exact nature
of the interaction botween chromium, aluminum and
phosphorus. As a result, although it is believed that
CrO2 tetrahQdra are substituted isomorphously for A102
or P02 tetrahodra, it is appropriate to characterize
certain CAPO compositions by re~erence 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-14642
.'; '~ .
: :
1329213
-194-
element of Group VA of t~e Periodic Table, and/or
optionally an alXali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
`5 polytetrafluoroethylene and heatQd, preferably under
autogenous pressura at a temperature between about SO-C
and about 250~C, and preferably between about lOO~C and
about 200~C until crystals of the CAP0 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 synthasizing the CAPO compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (CrxAlyPz)o2 bH20
wherein "R" is an organic templating agent; "a" is the
amount of organic t~mplating 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
praferably not greater than about 20; and "x", "y" and
D-14642
.
-1~292~3
-195--
"z" represen~ the mole fractions of chromiu~, aluminum
and phosphorus, respectively, and each has a value of
at least 0.01.
}n 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 ~ y
L 0.01 0.60 0.39
M 0.01 0.39 0.60
N 0.39 0.01 0.60
0 0.98 0.01 0.01
P 0.39 0.60 0.01
Especially preferred reaction mixtures are
those containing from about 0.1 to about 0.4 moles of
chromiuc, and from about 0.75 to about 1.25 moles of
- aluminu~, per mole of phosphorus.
In thQ foregoing expres`sion of the reaction
composition, the reactants are normalized with respect
to th~ total of "x", "y" and n Z n such that
(x + y + z) - 1.00 mole. Molecular sieves containing
chromium, aluminum and phosphorus as framework
tetrahedral oxide unit~ are prapared as follows:
.
~ D-14642
.
1329213
-196-
Pr~parative Reaae~ts
C~PO compositions may be prepared ~y using
numerous reagents. Reagents which may be employed to
prepare CAPOs include:
(a) aluminum isopropoxide, or aluminum
chlorhydrol;
(b) ps~udo~oehmite or other aluminum oxide:
~c) H3P04: 85 weight percent aqueous
phosphoric acid;
(d) chromium(III) orthophosphate,
chromium(III) acatate and chromium
acetate hydroxide,
(Cr3(0H)2(CH3CQo)7);
` (e) TEAOH: 40 weight percent aqueous solution
~ of tetraethylammonium hydroxide;
~f) TBAOH: 40 weight percent aqueous solution
o~ tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
~h) ~r3N: tri-n-propylamine, (C3H~)3N;
~i) Quin: Quinuclidine, (C7Hl3N);
~) MQuin: Nethyl Quinuclidine hydroxide,
CH30H);
~X) C-hex: cyclohexylamine;
; (1) ~MAOH: tetramethylammonium hydroxide;
~m) TPAOH: tetrapropylammonium hydroxide; and
~n) DEEA: 2-diethylaminoethanol.
-
D-14642
.
;;: '' ' ,'' . :
.. . .
'', ,- ' . .
1329213
-197-
Pre~arative Procedures
CAPOs may be prepàred 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 addad to an aqueous solution of
phosphoric acid in an ice bath. The templating agent is
th~n added, and thQ final mixture mixed until
homogeneous.
Whichever techniqu~ is employed to produce the
reaction mixture, this mixture is then placed in a lined
(polytetrafluoroethylene) stainless steel pressure
vossQl and dige~ted at a temp~rature (150'C or 200-C)
for a time or placed in lined screw top bottles for
D-14642
- 198 - 1329213
digestion at 100C. Digestions are typically carried
out under autogenous pressure.
GaAPO MOLECULAR SIE~ES
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 : (Ga~AlyPz)O2
wherein nRn represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the molar amount of "R" present per mole of
(Ga~AlyPz)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 limit;ng compositional values or points as follows:
D-14642-C
' ~
.: - . . : ;
- 132g213
- ~99 -
~ole Fraction
Point ~ y
A 0.01 0.60 0.39
B 0.01 0.34 0.6S
S 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, thQ value of "z" in the GaAP0
molecular sieves is not greatQr than about 0.60.
In a preferred subclass of the GaAP0 molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
lS Point .~ y
a 0.01 O.S9 0.40
b 0.01 0.34 0.65
c 0.34 0.01 0.6S
d 0.59 0.01 0.40
In an espQcially prQferred subclass of the
GaAPO molecular sievQs the values of x, y and z are as
follow~:
D-14642
'.~
13292.13
--, ~o
Mole Fraction
Point x v 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 0~55
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
el~ment of Group VA of the Periodic Table, and/or
optionally an alkali or other mQtal. The reàction
mixture is generally placed in a sealed pressure vessel,
preferably lined wit~ an inert plastic material such as
polytetrafluoroethylene and heated, preferably under
autogenous pressure at a temperatura between about 50~C
and about 250'C, and preferably between about lOO-C and
about 200-C, until crystals of the GaAP0 product are
obtained, usually a period of from several hours to
several weeks. Typical afrective 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-14642
1329213
-201-
been observed. The product is recovered by any
convenient method such as centrifugation or filtration.
In synthesizing the GaAP0 compositions, it is
preferred to employ à reaction mixture composition
expressed in terms of the molar ratios as follows:
aR (GaxAlyPz)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, and most preferably not more than about 1.0;
"b" ~as a value of from zero (0) to about 500,
preferably betwoen about 2 and about 300, most
preferably botween about 2 and about 20; and "x", "y"
and "zn`repr~sent the mole fractions of gallium,
aluminu~ and phosphorus, respectively,~and each has a
value of at least 0.01.
- In one embodiment the reaction mixture is
s~lected such that the mole ~ractions "x", "y" and "z"
are genQrally defined as being within the limiting
compositional values or points as follows:
D-14642
1329213
--L'3'2,--
Mole Fraction
Point ~ ` y
G O.ol 0.60 0.39
H 0.01 0.3g 0.60
S I 0.39 0.01 0.60
J 0.98 o.ol o.o
X 0.39 0.60 o.ol
Especially preferred reaction mixtures are
those containing from 0.2 to O~S mole of Ga203 and from
0.3 to 1 mole of A12O3 for each mole of P2O5.
In the ~oregoing ~xprQssion of t~e reaction
composition, the reactants are normalized with respect
to the total of "x~, "y" and "z" such that
(X + y + 2~ ~ 1. 00 mole. Molecular sieves containing
gallium, aluminum and phosphorus as framework
tetrahedral oxide units are preparQd as follows:
Preparative Reagents
GaaPO co~positions may be prepared by using
num~rous reagents. Reagents which may be employed to
pr~pare GaAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) ~3P04: 85 weight percent aqueous
phosphoric acid:
:- 25 (d) gallium sulfate or gallium(III)
hydroxide;
: D-14642
.
. .
. ~
:. . . . .
`` 1329213
-203-
(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);
Quin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine:
~1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) D~EA: 2-diethylaminoethanol.
PreoarativQ Proc~dures
&aAPOs may be prepared by forming a starting
reaction mixture by mixing the phosphoric acid with at
least part of tho water. To this solution the aluminum
~` oxide or iQopropoxide is added. This mixture is then
blend~d until a homogeneous mixture is observed. To
this mixture the gallium sulfate or gallium hydroxide
and the templating agent are successively added and the
re~ulting mixture blended until a homogeneous mixture is
o~served.
Alternatively, the alum~num oxide may be mixed
with a solution of the gallium sulfate or hydroxide, and
then the phosphoric acid and the templating agent
D-14642
.
,,.,. ~ . .
.,, ~ .
- 204 - 1329213
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 mi~ture is then blended until
a homogeneous mi~ture is observed.
Whichever technique is employed to form
the reaction mi~ture, the mixture is then placed in a
lined (polytetrafluoroethylene) stainless steel
pressure vessel and digested at a temperature tl50C
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 of U.S.
Patent No. 4,888,167 have a framework structure of
GeO2, AlO2- and P02~ tetrahedral units and have an
empirical chemical composition on an anhydrous basis
e~pressed 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-14642-C
1~29213
-205-
(GexAlyPz)O2 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
tetrahedral oxides. The mole fractions "x", "y" and "z"
are generally defined as being within t~e 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 0.94 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 o~ x, y and z are within the limiting
compositional values or points as follows:
Mole Fraction
Poin~ ~ y
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-14642
.
13292i3
-206-
An especially preferred subclass of the GeAP0
molecular sieves are those in which the value of "x" is
not greater than about 0.13.
GeAP0 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 o an
element of Group V~ of the Periodic Table, and/or
lo optionally an alXali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
polytetrafluoroethylQnQ and heated, preferably under
autogenous pressure at a temperature between about SO C
lS and about 250'C, and preferably between aboùt lOO C and
about 200'C, until crystals of the GeAP0 product are
obtained, usually a period o~ 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 GeAP0 compositions, it is
pre~erred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
aR : (GexAlyPz)o2 : bH20
D-14642
~ , . - ., , . . . . :
. . '. ' ' ~
1329213
-207-
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 (o) to about 500,
preferably between about 2 and about 300, most
preferably between about 10 and about 60: and "xn, "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 e~bodiment the reaction mixture is
selected such that the mole fractions "x", Ny~l and "z"
are generally defined as being within the limiting
compositional valuès or points as follows: `
~Qle Fraction
~oint ~ y
F 0.01 0.60 0.39
G 0.01 0.39 0.60
20 H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0~01
ESPQCia11Y preferred reaction mixtures are
those containing from 0.2 to 0.4 mole of GeO2 and from
0.75 to 1.25 mole of A12O3 for each mole of P2O5.
D-14642
, .
13292~3
-208-
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to the total of "xn, "y" and "zl- such that
(x I y + z) = 1.00 mole. Molecular sieves containing
germanium, aluminum and phosphorus as framework
tetrahedral oxide units are prepared as follows:
Pre~arative Reagents
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 tetraQthylammonium hydroxide;
tf) TBAOH: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H~)3N:
(i) Quin: Quinuclidine, (C7H13N);
(;) ~Quin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(k) C-hex: cyclohexylamine;
D-14642
''" '' ' '' ' ~, ', ~ .
1329213
-209-
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Preparative Procedures
In some cases, it may be advantageous, when
synthesizing the GeAPO compositions, to first combine
sources of germanium and aluminum, to form a mixed
germanium/aluminum compound (this compound being
typic~lly a mixed oxide) and thereafter to combine this
- 10 mixed compound with a source of phosphorus to form the
c final GeAPO composition. Such mixed oxides may be
prepared for example by hydrolyzing aqueous solutions
containing germanium tetrachloride and aluminum
chlorhydrol, or aluminu~ tri-sec-~utoxide.
` GeAPOs may be prepared by forming a starting
reaction mixture by mixing the phosph~ric acid with at
least part of the water. To this solution is added the
mix~d 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-14642
~.
` - 210 - 13292~3
added successively the phosphoric acid and the
templating agent. The resulting mixture is then
blended until a homogeneous mi~tue is observed.
In a third process, a solution is formed by
dissolving the phosphoric acid in water, adding
aluminum o~ide or isopropoxide and mixing
thoroughly. To the resultant mixture is added a
solution containing the templating agent and
germanium dio~ide. 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. Digestion are
typically carried out under autogenous pressure.
LiAPO MOL~CULAR SIEVES
The LiAPO molecular sieves U.S. Patent No.
4,789,535 have a framework structure of Lio2-3,
A102-, and PO2~ tetrahedral units and have an
empirical chemical composition on an anhydrous basis
e~pressed by the formula:
mR : (Li~AlyP2)O2
D-14642-C
1329213
-211-
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the mol~r 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 ~E~ction
y ,~
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 LiAP0 molecular
sieves the values of x, y and z are within the limiting
compositional values or points as follows:
.
D-14642
1329213
-212-
Moie 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
In an especially preferred subclass of the
LiAPo molecular sieves the values of x, y and z are
within the following limits:
Mole Fraction
Point ~ y Z
e 0.01 0.52 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
0.0~ 0.52 0.41
LiAPo compositions are generally synthesized
~` by hydrothermal crystallization from a reaction mixture
containing reactive sources of lithium, aluminum and
phosphorus, prefQra~ly an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
~lement of Group VA of the Periodic Table, and/or
optionally an alXali or other metal. The reaction
mixture is generally placed in a sealed pressure vessel,
preferably lined with an inert plastic material such as
D-14642
:,
,
. - ' . -
1329213
-~13-
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 LiAP0 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
5-days, have been observed. The product is recovered by
any convenient method such as centrifugation or
filtration.
In synthesizing the LiAP0 compositions, it is
preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
x y z) 2 2
wh~r~in "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 rangQ of greatQr than zero tO) to
about 6, and most preferably not more than about 2: "b"
h~s a value of from zero tO) to about 500, pr~ferably
b~tween 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,
respQctively, and each has a value of at least 0.01.
In one ~mbodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
D-14642
1329~13
. -21~-
are generally defined as being within the limiting
compositional values or poi~ts as follows
Mole Fraction
Point ~ y
S 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 praferred subclass of the
: reaction mixtures, the values of "xn, "y" and "z" are
within the li~iting compositional values or points as
follows:
Mole Fraction
lS Point ~ ~ ~
1 0.03 O.S0 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 O.S0 0.46
In the foregoing expression of the reaction
composition, the reactants are normalized with respect
to th~ total of "x", "y" and n Z 1l such that
(x I y ~ z) - 1.00 mole.
Since the exact nature of the LiAP0 molecular
sieves is not clearly understood at present, although
D-14642
, ' .
: ` . ` ` , ~ ,.
. .
~,. . ' . . ~ .'
. ... ~ ~ . , .
1329213
-215-
all are believed to contain Lio2 tetrahedra in the
three-dimensional microporous crystal framework
structure, it is advantageous to characterize the LiAPo
molecular sieves by means of their chemical co~position
This is due to the low level of lithium present in
certain of the LiAP0 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 A102
or P02 tetrahedra, it is appropriate to characterize
certain LiAP0 compositions by reference to their
chemical composition in terms of the mole ratios of
oxides
Nolecular sieves containing lithium, aluminum
; and phosphorus as framework tetrahedral oxide units are
prepared as follow~
PreDarative Re~aents
LiAPO compositions may be prepared by using
num~rous reagents Reagents which may ~e employed to
pr-pare LiAPOs include
(a) aluminum isopropoxide;
~b) pseudoboehmite or other aluminum oxide
~c) H3PO4 85 weight percent aqueous
phosphoric acid;
D-14642
.2l6 ~3292~3
(d) lithium sulfate or lithium
orthophospha~e:
(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,
(C~H13NCH30H);
(k) C-hex: cyclohexylamine;
(1) TNAOH: tetramethylammonium hydroxide;
~m) TP~OH: tetrapropylammonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Pr~arative PrQcedures
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
ag-nt is add~d. ThQ resultant mixture is then blended~
until a homog~neou-~ mixture is observed. To this
mixture th~ lithium phosphate or sulfate is added and
th~ r~sulting mixture blended until a homogeneous
mixture i~ obsQrved. Alternatively, an initial mixture
may be form~d by mixing aluminum oxide and lithium
phosphate or sulfate. To the resultant mixture are
D-14642
,
. -
,:;, . ~, ~ . ::
- 217 - 1329213
added successively phosphoric acid and an aqueous
solution of the templating agent, and the resulting
mi~ture blended until a homogeneous mixture is
observed.
In a third procedure, the phosphoric acid is
mi~ed 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 mi~ture, the mi~ture 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 U.S. Patent No.
4,917,876 have three-dimensional microporous
framework structures of FeO2n, TiO2, AlO2- and PO2~
tetrahedral o~ide units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (NXAlyPz)o2
D-14642-C
`
132921~
-218-
wherein "~" represents at least one organic templating
agent present in the intracxystalline pore system, "~"
represents iron and titanium; I'm" represents the molar
amount of "R" present per mole o~ (MXAlyPz)O2 and has a
va.ue 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 ~he limiting compositional
values or points as follows:
Mola Fraction
Point ~ y 2
A 0.02 0.60 0.38
B 0.02 0.38 0.60
: 15 C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a pre~erred su~class of the FeTiAP0
~olecular si~ves thQ val~e8 of x, y and 2 are within the
li~iting compositional values or points as follows:
D-14642
1329213
-21~-
- Mole Fraction
Point x ~ - y 2
a 0.02 0.60 0.38
b 0.02 0.38 0.60
`5 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
FeTiAP0 compositions are generally synthesized
by hydrothermal crystallization from a reaction mixture
containing reactive sources of iron, titanium, aluminum
and phosphorus, prefQrably an organic templating, i.e.,
structure-directing, agent, preferably a compound of an
element of Group VA of the`Periodic Table, and/or
optionàlly 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 FeTiAP0 product are
obtained, usually a period of from several hours to
several weeks.` Typical effective ti~es 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
D-14642
.
-
1329213
-220-
any convenient method such as centrifugation or
fi1tration.
In synthesizing the FeTiAPO compositions, it
is preferred to employ a reaction mixture composition
expressed in terms of the molar ratios as follows:
~ 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; "b" has a value of from zero (0) to about 500,
preferably between about 2 and about 300; and "x", "y"
and "z" represent the mole fractions of "N" (iron and
titanium, aluminum and phosphorus, respectively, and
each has a value of at least 0.01.
In one embodiment the reaction mixture is
sQlected such that the mole fractions "x", "y" and 1'2"
are generally defined as being within the limiting
compositional values or points as follows:
Mole Fraction
Point ~ y
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.39 0.01 0.60
25 I 0.98 0.01 0.01
J 0.39 0.60 0.01
D-14642
, . .
-221- 1329213
- In the foregoing expression of the reaction
composition, the reactants ~re nor~alized with respect
to the total of "x", "y" and "z" such that
(x I y ~ z) = 1.00 mole.
Molecular sieves containing iron, titanium,
aluminum and phosphorus as framework tetrahedral oxide
units are prèpared as follows:
Preparative Reagents
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) psèudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid;
(d) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
(e) TBAOa: 40 weight percent aqueous solution
of tetrabutylammonium hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3N: tri-n-propylamine, (C3H7)3N;
(h) ~uin: Quinuclidine, (C7H13N):
D-14642
- 222 - 1329213
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(j) C-hex: cyclohexylamine;
(k) TMAOH: tetramethylammonium hydroxide;
(1) TPAOH: tetrapropylammonium hydroxide;
and
(m) DEEA: 2-diethylaminoethanol.
Preparative Procedure~
FeTiAPOs may be prepared by forming a
homogeneous reaction mi~ture containing reactive
sources of iron, titanium, aluminum and phosphorus.
The reaction mi~ture 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 a lined screw top bottles for
digestion at 100C~ Digestions are typically carried
out under autogenous pressure.
~APO MOLECUhAR SIEVES
The XAPO molecular sieves of U.S. Patent No.
4,956,165 have a three-dimensional microporous
framework structures of MO2n, AlO2- and PO2+
tetrahedral o~ide units having an empirical chemical
composition on an anhydrous basis expressed by the
formula:
mR : (MXAlyPz)o2
;'
D-14642-C
. .
1329213
-223-
wherein ~R~ represents at least one organic templating
agent present in t~e intracrystalline pore system; "M"
represents at least one element from each of the classes
of: 1) iron and titanium; and 2) cobalt, magnesium,
`5 manganese and zinc; "n" is 0, -1 or -2; "m" represents a
molar amount of "R" present per mole of (MXAlyPz)02 and
has a value of zero (0~ to about 0.3; 3B~ `'x", "y" and
"z" represent the mole fractions of "M", aluminum and
phosphorus, respectively, present as tetrahedral oxides.
Tha mola fractions "x", "y" and "z" are generally
defined as being within the limiting compositional
values or points as follows:
Mole Fraction
Point ~ y
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 XAPO molecular
siev~s th~ valu~s of x, y and z are within the limiting
compositional values or points as follows:
D-14642
1329213
-224-
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
XAPO 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
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
polytetrafluoroethylane and heated, preferably under
autogenous pressure at a temperature between about 50~c
~20 and about 250'C, and preferably between about lOO-C and
-about 200'C until crystals of the XAPO product are
obtained, usually a period of from several hours to
SeVQr~l WQekS. Typical effective times of from 2 hours
to about 30 days, generally from about 2 hours to about
20 days, have been observed. The product is recovered
., .
D-14642
' - ` " .
1329213
-22s-
by any convenient ~et~od such as centrifugation or
filtration. ~ -
In synthesizing the XAP0 compositions, it is
preferred to employ a reaction mixture composition
`5 expressed in terms of the molar ratios as follows:
aR : (MXAlyP2)02 : 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: "M" represents at laast one element from each
of the classes of: 1) iron and titanium; and 2) cobalt,
magnesium, manganese and zinc; "b" has a value of from
zero (0) to about S00, preferably between about 2 and
15 about 300: and "x", "y" and ~Zll represent the mole
fractions of "M" (iron and/or titanium, and at laast one
of cobalt, magnesium, manganese and zinc), aluminum and
phosphorus, respectively, and each has a value of at
least 0.01, with th~ proviso that "x" has a value of at
20 l~st 0.02~
In one embodiment the reaction mixture is
selected such that the mole fractions "x", "y" and "z"
are generally d~fined as being within the limiting
composition~l v~lue~ or points as follows:
`' .
:~ D-14642
; '` ` '.
1329213
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Mole Fraction
Point x ~ y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
K 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 O.ol
- In the foregoing expression of the reaction
composition, the reactants are normali~ed with respect
to the total of ~xn, "y" and "z" such that
(X I y + Z) 3 1-00 mole.
XAPO molecular sieves are prepared as follows:
Preparative ~ç~a,~ents
XAPO compositions may be prepared by using
~ 15 numerous reagents. The preferrQd sources of elements
`` nMn for preparing XAFOs 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 XA N ~ include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide:
(c) H3 N 4: 85 weight percent aqueous
phosphoric acid;
-~ (d) TEAOH: 40 weight percent aqueous solution
of tetraethylammonium hydroxide;
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(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);
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH);
(j) C-hex: cyclohexylamine;
(k) TMAOH: tetramethylammonium hydro~ide;
(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 mi~ture 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 MQLECULAR SIEVES
The mi~ed element APO molecular sieves have
a framework structure of MO2n, AlO2- and PO2+
tetrahedral units,
i
.
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~"
.~'
.
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wherein ~o2n represents at least two different~elements
- present as tetrahedral units "MO2n" 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, chromiu~, gallium, germanium,
lithium and vanadium, while a second one of the elements
l'N" is selected from the group consisting of cobalt,
iron, magnesium, mànganese, titanium and zinc.
Preferably, "~" is a mixture of lithium and magnesium.
The mixed-element molecular sieves have an empirical
chemical co~position on an anhydrous basis expressed by
the formula:
mR : (MxAlyPz)O2
wherein "R" represants 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 greatQr than 0.15: and "x", "y" and
"z~ represent the mole fractions of the elements "M"
(i.e. "x" is the total of th~ mole fractions of the two
or mor~ elements "Nn), aluminum and phosphorus,
respectively, present as tetrahedral oxides. The mole
fractions "x", lly~ and "z" ara generally defined as
being within the limiting compositional values or points
as follows:
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Mole Fraction
Point ~ v
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 ~, y and z are
within the limiting compositional values or points as
follows:
Mole Fraction
Point ~ y ~
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 0.69 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 ~ 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, have a framework structure of MO2n, AlO2-
and PO2~ tetrahedral units, wherein MO2n
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represents at least tJo difCerent elements which are
present as tetrahedral unit~ "~02nn with charge "n",
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 ~asis
expressed by the formula:
mR : (~xAlyPz)O2
wherein "R" represents at least one organic templating
agent present in the intracrystalline pore system; "m"
~epresents the molar amount of "R" present per mole of
(MXAlyPz)O2 and has a value of zero to about 0.3; and
nxn, "yn 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 ~ole fractions "x", "y" and "z-- are generally
defined as being within the limiting compositional
values or points as follows:
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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 ~ 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
The mixed-element APO compositions are
~. 20 generally synthesized by hydrothermal crystallization
`` from a reaction mixture containing reactive sources of
the element~`nMI', aluminum and phosphorus, preferably an
organic te~plating, 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
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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
praferably 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
effectiv~ times of from 2 hours to about 30 days,
generally from about 2 hours to about 20 days, and
preferably about 12 ~ours to about 5 days, have been
observed~ The product is recovered by any convenient
met~od such as centrifugation or filtration.
In synthesizing the mixed-element AP0
compositions, it is preferred to employ a reaction
lS mixture composition expressed in terms of the molar
. ratios as follows:
- aR : ~M Al P )0 : bH 0
wherein "R" is an organic templating agent; "a" is the
amount of organic t mplating agent "R" and has a value
of from zero to about 6 and is preferably an effecti~e
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 more than about 10; and "x", "y" and "z" represent
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the mole fractions of "M", aluminum and phosphorus,
respectively, "y" and "z" each having a valùe o~ 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
-5 o.Ol.
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 ~ y
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
- containing not more than about 0.2 moles of the metals
nM" 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 I y + z) ~ 1.00 mole.
Since the exact nature of the mixed-element
2S APO molecular sieves is not clearly understood at
present, although all are believed to contain M02
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~ 234-
tetrahedra in the three-dimensional microporous crystal
framework structure, it is advantageous to characterize
the mixed-element APO molecular sieves by means of their
che~ical composition. This is due to the low level of
`5 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
10 M02 tetrahedra are substituted isomorphously for A102 or
PO2 te~rahedra, it is appropriate to characterize
certain mixed-element APO compositions by reference to
their ch~;cal composition in terms of the mole ratios
of oxides.
. 15 Molecular sieves containing the metals "M",
`~ aluminum and phosphorus as framework tetrahedral oxide
uni~s are pr~par~d as follows:
Preparative Reagents
MixQd-Ql~mant APO compositions may be prepared
by using num~rous reagQnts. Reagents which may be
amployed to pr~pare mixed-elament APOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous
phosphoric acid:
(d) lithium phosphate or magnesium hydroxide
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or appropriate salts of the other
elements "M", as described above;
(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,
(C7H13NCH30H);
~X) C-hex: cyclohexylamine;
(1) TMAOH: tetramethylammonium hydroxide;
(m) TPAOH: tetrapropylammonium hydroxide; and
" 15 (n) 9EEA: 2-diethylaminoethanol.
PreDarative Procedures
Mixed elem~nt APOs may be prepared by forming
a s~artin~ reaction mixture by mixing aluminum oxide,
magnsQium hydroxid~, lithium phosphate (or the
corresponding salts o~ 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.
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The reaction mi~ture 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.
SILICOALUMINOPHOSPATE MOLECVLA~ SIEVES
The preferred NZMSs, to date, are the
silicoaluminophosphate molecular sieves described in
U.S. Patent No. 4,440,871. The use of such catalysts
in reforming catalysts or as components in heretofore
employed reforming~dehydrocyclization catalysts
provides improved catalysts and provides products
characterized by an improved selectivity to
iso-products and provides improved activity in
reformating~dehydrocyclization reactions.
The silicoaluminophosphate molecular sieves
of U.S. Patent No. 4,440,871 are disclosed as
microporous crystalline silicoaluminophosphates, the
pores of which are uniform and have nominal diameters
of greater than about 3 Angstroms and whose essential
empirical chemical composition in the as-synthesized
and anhydrous form is: -
mR : (Si~AlyPz)O2
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.
` 1329213
-~37-
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
(SiXAlyPz)02 and has a value of from 0.02 to 0.3; "x",
"y" and "z" represent the mole fractions of silicon,
aluminum and phosphoru~, respectively, present as
tetrahedral oxides, said mole fractions being such that
they are within the pentagonal compositional area
defined by points A, B, C, D and E of the ternary
diagram of FIG. 5 of the aforementioned U.S. Patent No.
4,440,871, and are preferably within the pentagonal
compositional area defined by points a, b, c, d and e of
FIG. 6 of this patent. The SAP0 molecular sieves of
U.S. Patent No. 4,440,871 and the aforementioned
application Serial No. 575,745 are also described as
silicoaluminophosphates having a three-dimensional
microporous frameworX structure of P02 , A102 and SiO2
tetrahedral units, and whose essential empirical
chemical composition on an anhydrous basis is:
~R : (SixAlyPz)02
wherQin "R" repr~sents at least one organic templating
agent present in the intracrystalline pore system; "m"
represents the moles of "~" present per mole of
(SiXAlyPz)02 and has a value of from zero to 0.3; "x",
"y" and "z" represQnt, respectively, the mole ~ractions
of silicon, aluminum and phosphorus present in the oxide
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,:
- 238 - 1329213
moiety, said Mole fractions being within the
compositional area bounded by points A, B, C, D and E
on the ternary diagram which is FIG. 5 of the
aforementioned patent, said silicoaluminophosphate
having a characteristic X-ray powder diffraction
pattern which contains at least the d-spacings set
forth below in any one of Tables I, III, V, VII, IX,
XIII, XVII, XXI, XXIII or XXV of U.S. Patent No.
4,440,871~ Further, the as-synthesized crystalline
silicoaluminophosphates of U.S. Patent No. 4,440,871
may be calcined at a temperature sufficiently high to
remove at least some of any organic templating agent
present in the intracrystalline pore system as a
result of such synthesis~ The
silicoaluminophosphates of U.S. Patent No. 4,440,871
are general referred to therein as "SAPO", as a
class, or as "SAPO-n" wherein "n" is an integer
denoting a particular SAPO as its preparation is
reported in U.S. Patent No. 4,440,871. The
preparation of the SAPOs is disclosed in U.S. Patent
No. 4,440,871.
D-14642-C
