Molecular sieve abstract
Molecular sieve compositions having three-dimensional microporous
framework structures of BO.sub.2 AlO.sub.2 PO.sub.2 and SiO.sub.2
tetrahedral oxide units are disclosed. These molecular sieves have
an empirical chemical composition on an anhydrous basis expressed
by the formula: wherein "R" represents at least one organic
templating agent present in the intracrystalline port system; "m"
represents the molar amount of "R" present per mole of
(B.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 ; and "w",
"x", "y" and "z" represent the mole
fraction of boron, aluminum, phosphorus and silicon, respectively,
present as tetrahedral oxides. Their use as adsorbents, catalysts,
etc. is also disclosed.
Molecular sieve claims
We claim:
1. Crystalline molecular sieves comprising three-dimensional microporous
framework structures of BO.sub.2 AlO.sub.2 PO.sub.2 and SiO.sub.2
tetrahedral units having an empirical chemical composition on an
anhydrous basis expressed by the formula:
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.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero
to about 0.3; and "w", "x", "y" and
"z" represent the mole fractions of boron, aluminum, phosphorus
and silicon, 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 FIG. 1 said crystalline
molecular sieves having a characteristic X-ray powder diffraction
pattern which contains at least the d-spacings set forth in one
of the following Tables C, F, J, N, P, T, V, W and X:
2. Crystalline molecular sieves according to claim 1 wherein the
mole fractions of boron, aluminum, phosphorus and silicon present
as tetrahedral oxides are within the hexagonal compositional area
defined by points a, b, c, d, e and f of FIG. 2.
3. Crystalline molecular sieves according to claim 2 wherein the
mole fractions of boron, aluminum, phosphorus and silicon present
as tetrahedral oxides are within the hexagonal compositional area
defined by points g, h, i, j, k and l of FIG. 2.
4. The crystalline molecular sieves of claim 1 wherein "m"
is not greater than about 0.15.
5. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table C given in claim 1.
6. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table F given in claim 1.
7. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table J given in claim 1.
8. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table P given in claim 1.
9. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table T given in claim 1.
10. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table V given in claim 1.
11. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table W given in claim 1.
12. The crystalline molecular sieves of claim 1 or 2 having a characteristic
X-ray powder diffraction pattern which contains at least the d-spacings
set forth in Table X given in claim 1.
13. The crystalline molecular sieves of claim 12 wherein the X-ray
powder diffraction pattern set forth in Table X contains at least
the d-spacings set forth in one of the following Tables XA XB, SC
and XD:
14. Process for preparing crystalline molecular sieves having three-dimensional
microporous framework structures of BO.sub.2 AlO.sub.2 PO.sub.2
and SiO.sub.2 tetrahedral units having an empirical chemical composition
on an anhydrous basis expressed by the formula:
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.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero
to about 0.3; and "w", "x", "y" and
"z" represent the mole fractions of boron, aluminum, phosphorus
and silicon, 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 FIG. 1 said crystalline
molecular sieves having a characteristic X-ray powder diffraction
pattern which contains at least the d-spacings set forth in one
of the following Tables C, F, J, N, P, T, V, W and X:
which process comprises providing a reaction mixture composition
at an effective temperature and for an effective time sufficient
to produce said molecular sieves, said reaction mixture composition
being expressed in terms of molar oxide ratios as follows:
wherein "R" is an organic templating agent; "a"
is the amount of "R" and is an effective amount greater
than zero to about 6; "b" has a value of from zero to
about 500; and "s", "t", "u" and "v"
represent the mole fractions, respectively, of boron, aluminum,
phosphorus and silicon in the (B.sub.s Al.sub.t P.sub.u Si.sub.v)O.sub.2
constituent, and each has a value of at least 0.01.
15. Process according to claim 14 wherein "s", "t",
"u" and "v" are within the area defined by points
F, G, H, I and J of FIG. 3.
16. Process according to claim 14 wherein "a" is not
greater than about 0.5.
17. Process according to claim 14 wherein "b" is not
greater than about 20.
18. Process according to claim 14 wherein the source of phosphorus
in the reaction mixture is orthophosphoric acid.
19. Process according to claim 18 wherein the source of phosphorus
in the reaction mixture is orthophosphoric acid and the source of
aluminum is at least one compound selected from the group consisting
of pseudo-boehmite and aluminum alkoxides.
20. Process according to claim 19 wherein the aluminum alkoxide
is selected from the group consisting of aluminum isopropoxide,
tri-sec-butoxide and hexadecoxide.
21. Process according to claim 14 wherein the silicon source is
silica or a tetraalkyl orthosilicate.
22. Process according to claim 14 wherein the source of boron is
selected from the group consisting of oxides, hydroxides, alkoxides,
chlorides, bromides, iodides, sulfates, nitrates, carboxylates and
mixtures thereof.
23. Process according to claim 14 wherein the source of boron is
selected from the group consisting of boric acid and trialkyl borates.
24. Process according to claim 14 wherein the reaction mixture
composition contains from about 1.0 to about 1.5 total moles of
boron and silicon per mole of phosphorus.
25. Process according to claim 14 wherein the reaction mixture
composition contains from about 0.75 to about 1.25 moles of aluminum
per mole of phosphorus.
26. Process according to claim 14 wherein the organic templating
agent is a quaternary ammonium or quaternary phosphonium compound
having the formula:
wherein X is nitrogen or phosphorus and each R is an alkyl or aryl
group containing from 1 to 8 carbon atoms.
27. Process according to claim 14 wherein the organic templating
agent is an amine.
28. Process according to claim 14 wherein the templating agent
is selected from the group consisting of tetrapropylammonium ion;
tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine;
piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine;
N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 14-diaziabicyclo-(222)octane;
N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine;
3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;
quinuclidine; N,N'-dimethyl-14-diazabicyclo (222) octane ion;
tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium
ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine;
and a polymeric quaternary ammonium salt .sub.x wherein x is a value
of at least 2.
29. Molecular sieve prepared by calcining, at a temperature sufficiently
high to remove at least some of any organic templating agent present
in the intracrystalline pore system, a crystalline molecular sieve
having three-dimensional microporous framework structures of BO.sub.2
AlO.sub.2 PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical
chemical composition on an anhydrous basis expressed by the formula:
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.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero
to about 0.3; and "w", "x", "y" and
"z" represent the mole fractions of boron, aluminum, phosphorus
and silicon, 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 FIG. 1 said crystalline
molecular sieves having a characteristic X-ray powder diffraction
pattern which contains at least the d-spacings set forth in one
of the following Tables C, F, J, N, P, T, V, W and X
Molecular sieve description
Field of the Invention
The instant invention relates to a novel class of crystalline microporous
molecular sieves and to the method of their preparation. The invention
relates to novel boron-aluminum-phosphorus-silicon-oxide molecular
sieves containing framework tetrahedral oxide units of boron, aluminum,
phosphorus and silicon. These compositions may be prepared hydrothermally
from gels containing reactive compounds of boron, aluminum, phosphorus
and silicon capable of forming framework tetrahedral oxides, and
preferably at least one organic templating agent which functions
in part to determine the course of the crystallization mechanism
and the structure of the crystalline product.
Background of the Invention
Molecular sieves of the crystalline alumino-silicate zeolite type
are well known in the art and now comprise over 150 species of both
naturally occurring and synthetic compositions. In general the crystalline
zeolites are formed from corner-sharing AlO.sub.2 and SiO.sub.2
tetrahedra and are characterized by having pore openings of uniform
dimensions, having a significant ion-exchange capacity and being
capable of reversibly desorbing an adsorbed phase which is dispersed
throughout the internal voids of the crystal without displacing
any atoms which make up the permanent crystal structure.
Other crystalline microporous compositions which are not zeolitic,
i.e. do not contain AlO.sub.2 tetrahedra as essential framework
constituents, but which exhibit the ion-exchange and/or adsorption
characteristics of the zeolites are also known. Metal organosilicates
which are said to possess ion-exchange properties, have uniform
pores and are capable of reversibly adsorbing molecules having molecular
diameters of about 6.ANG. or less, are reported in U.S. Pat. No.
3941871 issued Mar. 2 1976 to Dwyer et al. A pure silica polymorph,
silicalite, having molecular sieving properties and a neutral framework
containing neither cations nor cation sites is disclosed in U.S.
Pat. No. 4061724 issued Dec. 6 1977 to R. W. Grose et al.
A recently reported class of microporous compositions and the first
framework oxide molecular sieves synthesized without silica, are
the crystalline aluminophosphate compositions disclosed in U.S.
Pat. No. 4310440 issued Jan. 12 1982 to Wilson et al. These materials
are formed from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently
neutral frameworks as in the case of silica polymorphs. Unlike the
silica molecular sieve, silicalite, which is hydrophobic due to
the absence of extra-structural cations, the alumino-phosphate molecular
sieves are moderately hydrophilic, apparently due to the difference
in electronegativity between aluminum and phosphorus. Their intracrystalline
pore volumes and pore diameters are comparable to those known for
zeolites and silica molecular sieves.
In U.S. Pat. No. 4440871 there is described a novel class of
silicon-substituted alumino-phosphates which are both microporous
and crystalline. The materials have a three dimensional crystal
framework of PO.sub.2.sup.+, AlO.sub.2.sup.- and SiO.sub.2 tetrahedral
units and, exclusive of any alkali metal or calcium which may optionally
be present, an as-synthesized empirical chemical composition on
an anhydrous basis of:
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 (Si.sub.x
Al.sub.y P.sub.z)O.sub.2 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 silicoaluminophosphate species involved;
and "x", "y", and "z" represent the
mole fractions of silicon, aluminum and phosphorus, respectively,
present as tetrahedral oxides. The minimum value for each of "x",
"y", and "z" is 0.01 and preferably 0.02. The
maximum value for "x" is 0.98; for "y" is 0.60;
and for "z" is 0.52. These silicoaluminophosphates exhibit
several physical and chemical properties which are characteristic
of aluminosilicate zeolites and aluminophosphates.
In U.S. Pat. No. 4500651 there is described a novel class of
titanium-containing molecular sieves whose chemical composition
in the as-synthesized and anhydrous form is represented by the unit
empirical formula:
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 (Ti.sub.x
Al.sub.y P.sub.z)O.sub.2 and has a value of between zero and about
5.0; and "x", "y" and "z" represent
the mole fractions of titanium, aluminum and phosphorus, respectively,
present as tetrahedral oxides.
In U.S. Pat. No. 4567029 there is described a novel class of
crystalline metal alumino-phosphates having three-dimensional microporous
framework structures of MO.sub.2 AlO.sub.2 and PO.sub.2 tetrahedral
units and having an empirical chemical composition on an anhydrous
basis expressed by the formula:
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 (M.sub.x
Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; "M"
represents at least one metal of the group magnesium, manganese,
zinc and cobalt; "x", "y", and "z"
represent the mole fractions of the metal "M", aluminum
and phosphorus, respectively, present as tetrahedral oxides.
In U.S. Pat. No. 4544143there is described a novel class of crystalline
ferroaluminophosphates having a three-dimensional microporous framework
structure of FeO.sub.2 AlO.sub.2 and PO.sub.2 tetrahedral units
and having an empirical chemical composition on an anhydrous basis
expressed by the formula
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 (Fe.sub.x
Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; and
"x", "y" and "z" represent the mole
fractions of the iron, aluminum and phosphorus, respectively, present
as tetrahedral oxides.
The instant invention relates to new molecular sieve compositions
comprising framework tetrahedral units of BO.sub.2.sup.-, AlO.sub.2.sup.-,
PO.sub.2.sup.+ and SiO.sub.2.
DESCRIPTION OF THE FIGURES
FIG. 1 is a ternary diagram wherein parameters relating to the
instant compositions are set forth as mole fractions.
FIG. 2 is a ternary diagram wherein parameters relating to preferred
compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the
reaction mixtures employed in the preparation of the compositions
of this invention are set forth as mole fractions.
SUMMARY OF THE INVENTION
The instant invention relates to a new class of boron-aluminum-phosphorus-silicon-oxide
molecular sieves having a crystal framework structure of BO.sub.2.sup.-,
AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide
units. These new molecular sieves exhibit ion-exchange, adsorption
and catalytic properties and, accordingly, find wide use as adsorbents
and catalysts. The members of this novel class of compositions have
crystal framework structures of BO.sub.2.sup.-, AlO.sub.2.sup.-,
PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units and have an empirical
chemical composition on an anhydrous basis expressed by the formula:
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.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero
to about 0.3; and "w", "x", "y" and
"z" represent the mole fractions of boron, aluminum, phosphorus
and silicon, respectively, present as tetrahedral oxides. These
molecular sieve compositions comprise crystalline molecular sieves
having a three-dimensional microporous framework structure of BO.sub.2.sup.-,
AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units.
The instant molecular sieve compositions are characterized in several
ways as distinct from heretofore known molecular sieves, including
the aforementioned ternary compositions. The instant molecular sieves
are characterized by the enhanced thermal stability of certain species
and by the existence of species heretofore unknown for binary and
ternary molecular sieves.
The molecular sieves of the instant invention will be generally
referred to by the acronym "BAPSO" to designate the framework
of BO.sub.2.sup.-, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2
tetrahedral units. Actual class members will be identified by denominating
the various structural species which make up the BAPSO class by
assigning a number and, accordingly, are identified as "BAPSO-i"
wherein "i" is an integer. 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.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention relates to a new class of boron-aluminum-phosphorus-silicon-oxide
molecular sieves comprising a crystal framework structure of BO.sub.2.sup.-,
AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide
units. These new molecular sieves exhibit ion-exchange, adsorption
and catalytic properties and, accordingly, find wide use as adsorbents
and catalysts. |