This invention relates to a novel synthetic crystalline molecular sieve composition, MCM-37, which may contain framework +3 valence element, e.g. aluminum, and +5 valence element, e.g. phosphorus or with an addition +4 valence element, e.g. silicon, and to use thereof as a support and in catalytic conversion of organic compounds. The crystalline composition of this invention can easily be converted to catalytically active material.

BACKGROUND OF THE INVENTION 
This invention relates to a novel synthetic crystalline molecular sieve 
material, MCM-37, which may contain framework +3 valence element, e.g. 
aluminum and +5 valence element, e.g. phosphorus, or with an additional +4 
valence element, e.g. silicon, and to use thereof in catalytic conversion 
of organic compounds. The crystalline material can easily be converted to 
catalytically active material. It can also be used as a support material. 
DESCRIPTION OF THE PRIOR ART 
Zeolitic materials, both natural and synthetic, have been demonstrated in 
the past to have catalytic properties for various types of hydrocarbon 
conversion. Certain zeolitic materials are ordered, porous crystalline 
aluminosilicates having a definite crystalline structure as determined by 
X-ray diffraction, within which there are a large number of smaller 
cavities which may be interconnected by a number of still smaller channels 
or pores. These cavities and pores are uniform in size within a specific 
zeolitic material. Since the dimensions of these pores are such as to 
accept for adsorption molecules of certain dimensions while rejecting 
those of larger dimensions, these materials have come to be known as 
"molecular sieves" and are utilized in a variety of ways to take advantage 
of these properties. 
Such molecular sieves, both natural and synthetic, include a wide variety 
of positive ion-containing crystalline silicates. These silicates can be 
described as a rigid three-dimensional framework of SiO.sub.4 and Periodic 
Table Group IIIB element oxide, e.g. AlO.sub.4, in which the tetrahedra 
are cross-linked by the sharing of oxygen atoms whereby the ratio of the 
total Group IIIB element, e.g. aluminum, and silicon atoms to oxygen atoms 
is 1:2. The electrovalence of the tetrahedra containing the Group IIIB 
element is balanced by the inclusion in the crystal of a cation, for 
example, an alkali metal or an alkaline earth metal cation. This can be 
expressed wherein the ratio of the Group IIIB element to the number of 
various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One 
type of cation may be exchanged either entirely or partially with another 
type of cation utilizing ion exchange techniques in a conventional manner. 
By means of such cation exchange, it has been possible to vary the 
properties of a given silicate by suitable selection of the cation. The 
spaces between the tetrahedra are occupied by molecules of water prior to 
dehydration. 
Prior art techniques have resulted in the formation of a great variety of 
synthetic zeolites. Many of these zeolites have come to be designated by 
letter or other convenient symbols, as illustrated by zeolite A (U.S. Pat. 
No. 2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (U.S. Pat. 
No. 3,130,007), zeolite ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4 (U.S. 
Pat. No. 3,314,752), zeolite ZSM-5 (U.S. Pat. No. 3,702,886), zeolite 
ZSM-11 (U.S. Pat. No. 3,709,979), zeolite ZSM-12 (U.S. Pat. No. 
3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983), ZSM-35 (U.S. Pat. 
No. 4,016,245), and zeolite ZSM-23 (U.S. Pat. No. 4,076,842), merely to 
name a few. 
The SiO.sub.2 /Al.sub.2 O.sub.3 ratio of a given zeolite is often variable. 
For example, zeolite X can be synthesized with SiO.sub.2 /Al.sub.2 O.sub.3 
ratios of from 2 to 3; zeolite Y, from 3 to about 6. In some zeolites, the 
upper limit of the SiO.sub.2 /Al.sub.2 O.sub.3 ratio is unbounded. ZSM-5 
is one such example wherein the SiO.sub.2 /Al.sub.2 O.sub.3 ratio is at 
least 5 and up to the limits of present analytical measurement techniques. 
U.S. Pat. No. 3,941,871 (Re. 29,948) discloses a porous crystalline 
silicate made from a reaction mixture containing no deliberately added 
alumina in the recipe and exhibiting the X-ray diffraction pattern 
characteristic of ZSM-5. U.S. Pat. Nos. 4,061,724, 4,073,865 and 4,104,294 
describe crystalline silicate of varying alumina and metal content. 
Aluminum phosphates are taught, for example, in U.S. Pat. Nos. 4,310,440 
and 4,385,994. These aluminum phosphate materials have essentially 
electroneutral lattices. U.S. Pat. No. 3,801,704 teaches an aluminum 
phosphate treated in a certain way to impart acidity. Aluminophosphates 
are also described by Wilson, S. T. et al. in the Journal of the American 
Chemical Society 104, 1146-1147 (1982). 
An early reference to a hydrated aluminum phosphate which is crystalline 
until heated at about 110.degree. C., at which point it becomes amorphous, 
is the "H.sub.1 " phase or hydrate of aluminum phosphate of F.d'Yvoire, 
Memoir Presented to the Chemical Society. No. 392, "Study of Aluminum 
Phosphate and Trivalent Iron", July 6, 1961 (received), pp. 1762-1776. 
This material, when crystalline, is identified by the Joint Commission for 
Powder Diffraction Standards (JCPDS), card number 15-274. Once heated at 
about 110.degree. C., however, the d'Yvoire material becomes amorphous or 
transforms to the aluminophosphate form of tridymite. 
A naturally occurring, highly hydrated basic ferric oxyphosphate mineral, 
cacoxenite, is reported by Moore and Shen, Nature, Vol. 306, No. 5941, pp. 
356-358 (1983) to have a framework structure containing very large 
channels with a calculated free pore diameter of 14.2 Angstroms. R. 
Szostak et al., Zeolites: Facts, Figures, Future, Elsevier Science 
Publishers B.V., 1989, present work showing cacoxenite as being very 
hydrophilic, i.e. adsorbing non-polar hydrocarbons only with great 
difficulty. Their work also shows that thermal treatment of cacoxenite 
causes an overall decline in X-ray peak intensity. 
Silicoaluminophosphates of various structures are taught in U.S. Pat. No. 
4,440,871. Aluminosilicates containing phosphorus, i.e. 
silicoaluminophosphates of particular structures are taught in U.S. Pat. 
Nos. 3,355,246 (i.e. ZK-21) and 3,791,964 (i.e. ZK-22). Other teachings of 
silicoaluminophosphates and their synthesis include U.S. Pat. Nos. 
4,673,559 (two-phase synthesis method); 4,880,611 (MCM-9); 4,623,527 
(MCM-10); 4,639,358 (MCM-1); 4,647,442 (MCM-2); 4,664,897 (MCM-4); and 
4,632,811 (MCM-3). 
A method for synthesizing crystalline metalloaluminophosphates is shown in 
U.S. Pat. No. 4,713,227, and an antimonophosphoaluminate and the method 
for its synthesis are taught in U.S. Pat. No. 4,619,818. U.S. Pat. No. 
4,567,029 teaches metalloaluminophosphates, and titaniumaluminophosphate 
and the method for its synthesis are taught in U.S. Pat. No. 4,500,651. 
The phosphorus-substituted zeolites of Canadian Patents 911,416; 911,417; 
and 911,418 are referred to as "aluminosilicophosphate" zeolites. Some of 
the phosphorus therein appears to be occluded, not structural. 
U.S. Pat. No. 4,363,748 describes a combination of silica and 
aluminum-calcium-cerium phosphate as a low acid activity catalyst for 
oxidative dehydrogenation. Great Britain Pat. No. 2,068,253 discloses a 
combination of silica and aluminum-calcium-tungsten phosphate as a low 
acid activity catalyst for oxidative dehydrogenation. U.S. Pat. No. 
4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an 
amorphous body to be mixed with zeolite for use as cracking catalyst. U.S. 
Pat. No. 3,213,035 teaches improving hardness of aluminosilicate catalysts 
by treatment with phosphoric acid. The catalysts are amorphous. 
Other references teaching aluminum phosphates include U.S. Pat. Nos. 
4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,358; 4,158,621; 
4,071,471; 4,014,945; 3,904,550 and 3,697,550. Since their neutral 
framework structure is essentially void of ion-exchange properties, they 
are used as catalyst supports or matrices. 
For a period of time, the largest molecular sieves contained 12-membered 
rings with an associated pore opening of about 7.4 .ANG.. Recently, 
however, the search for larger pore molecular sieves resulted in the 
discovery of molecular sieves with pores larger than that of 12-membered 
rings. It is also well known that each molecular sieve has a distinctive 
X-ray diffraction pattern. 
U.S. Pat. No. No. 4,310,440 describes aluminophosphates including a 
structure designated AlPO.sub.4 -8 which has a distinctive X-ray 
diffraction pattern having a significant interplanar d-spacing at 
13.6-13.3 Angstroms. AlPO.sub.4 -8 is believed to have a 14-membered ring. 
Davis, et al. describe an aluminophosphate-based molecular sieve with an 
18-membered ring designated VPI-5 Nature 331, 362-366 (1988)). 
U.S. Pat. No. No. 4,880,611 discloses a synthetic crystalline molecular 
sieve composition, MCM-9, which may contain framework +3 valence element, 
e.g. aluminum, +4 valence element, e.g. silicon, and +5 valence element, 
e.g. phosphorus. Its crystals have pore windows of about 12-13 Angstroms 
in diameter formed by 18 tetrahedral members and after heating at 
110.degree. C. or higher, display an X-ray diffraction pattern with 
interplanar d-spacings at 16.4.+-.0.2, 8.2.+-.0.1, 6.21.+-.0.05, 
6.17.+-.0.05, 5.48.+-.0.05, and 4.74.+-.0.05 Angstroms without a 
significant interplanar d-spacing at 13.6-13.3 Angstroms. 
SUMMARY OF THE INVENTION 
The present invention is directed to a novel synthetic crystalline 
molecular sieve composition comprising a crystal having a framework 
topology giving a certain X-ray diffraction pattern which may contain one 
or more +3 valence elements, +5 valence elements and which may also 
include +4 valence elements and to its use as a support or as a catalyst 
component in catalytic conversion of organic, e.g. hydrocarbon, compounds. 
The anhydrous crystalline composition of this invention has the general 
chemical formula: 
EQU M.sub.x/m.sup.m+ :(XO.sub.2).sub.1-y.sup.- : (YO.sub.2).sub.1-x.sup.+ 
:(ZO.sub.2).sub.x+y :N.sub.y/n.sup.n- 
wherein X is the +3 valence element, Y is the +5 valence element, Z is the 
+4 valence element, M is a cation of valence m, N is an anion of valence 
n, and x and y are numbers of from greater than -1 to less than +1 which 
satisfy the relationships: 
(1) if x is 0, then y is not 0, 
(2) if y is 0, then x is not 0, and 
(3) x+y is greater than 0.001 and less than 1. 
In the composition above, when x is greater than y, the present composition 
is a cation exchanger with potential use as an acidic catalyst. When x is 
less than y, it is an anion exchanger with potential use as a basic 
catalyst. 
In the synthesized form of the present composition, it can also contain 
occluded organic material, D', and water molecules, entrapped during the 
synthesis and filling the microporous voids. It then has the general 
formula: 
EQU vD':M.sub.x/m.sup.m+ :(XO.sub.2).sub.1-y.sup.- :(YO.sub.2).sub.1-x.sup.+ 
:(ZO.sub.2).sub.x+y : N.sub.y/n.sup.n- :w(H.sub.2 O) 
wherein v is the number of moles of D', occluded organic material resulting 
from organic directing agent (D), and/or solvent used in synthesis of and 
filling microporous voids of the composition, which material may be 
removed upon calcination, w is moles of H.sub.2 O, e.g. from 0 to about 5, 
and x and y are the numbers defined above. The MCM-37 crystalline material 
in the as-synthesized form has a characteristic x-ray diffraction pattern 
as set forth in Table 1A. 
The present invention is a unique composition of matter which can be 
adjusted to exhibit a valuable combination of catalytic, sorption and 
ion-exchange properties and is also useful in fulfilling a support 
function.

DETAILED DESCRIPTION OF THE INVENTION 
The composition of the present invention may comprise one or more +3 
valence elements, such as those selected from the group consisting of 
aluminum, iron, chromium, vanadium, molybdenum, arsenic, antimony, 
manganese, gallium and boron; one or more +5 valence elements, such as 
those selected from the group consisting of phosphorus, arsenic, antimony 
and vanadium, and optionally one or more +4 valence elements, such as 
those selected from the group consisting of silicon, germanium and 
titanium in the structure thereof. 
The composition of the present invention will exhibit unique and useful 
catalytic, sorptive and shape selective properties along with the presence 
of a +4 valence element/(+3 valence element plus +5 valence element), e.g. 
silicon/(aluminum+phosphorus), atomic ratio of less than unity, but 
greater than zero, e.g. from about 0.001 to 0.99. It is well recognized 
that aluminum phosphates exhibit a phosphorus/aluminum atomic ratio of 
only 0.8 to 1.2 and contain essentially no structural silicon. Also, the 
phosphorus-substituted zeolite compositions, sometimes referred to as 
"aluminosilicophosphate zeolites", have a silicon/aluminum atomic ratio of 
from 0.66 to 8.0, and a phosphorus/aluminum atomic ratio of from greater 
than 0 to 1.0. 
The original cations of the as-synthesized present composition can be 
replaced in accordance with techniques well known in the art, at least in 
part, by ion exchange with other cations. Preferred replacing cations 
include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions 
and mixtures thereof. Particularly preferred cations are those which 
render the composition catalytically active or control catalytic activity, 
especially for hydrocarbon conversion. These include hydrogen, rare earth 
metal and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and 
VIII of the Periodic Table of the Elements. 
Typical ion exchange technique would be to contact the synthetic present 
composition with a salt of the desired replacing cation or cations. 
Examples of such salts include the halides, e.g. chlorides, nitrates and 
sulfates. 
Framework topologies of the present composition containing +5 valence 
element, e.g. phosphorus, and +3 valence element, e.g. aluminum, in 
tetrahedrally coordinated structural positions along with which +4 valence 
element, e.g. silicon which may be present are not those of layered 
materials, but are rigid 3-dimensional crystals. 
The crystalline composition of the present invention can be beneficially 
thermally treated, either before or after ion exchange. This thermal 
treatment is performed by heating the composition in an atmosphere such as 
air, nitrogen, hydrogen, steam, etc., at a temperature of from about 
300.degree. C. to about 1100.degree. C., preferably from about 350.degree. 
C. to about 750.degree. C., for from about 1 minute to about 20 hours. 
While subatmospheric or superatmospheric pressures may be used for this 
thermal treatment, atmospheric pressure is desired for reasons of 
convenience. 
The present composition exhibits an X-ray diffraction pattern which 
distinguishes it from other prior crystalline compositions. The X-ray 
diffraction pattern of this composition may have the following 
characteristic values: 
TABLE 1A 
______________________________________ 
Interplanar d-Spacings (A) 
Relative Intensity 
______________________________________ 
16.41 .+-. 0.59 s-vs 
14.12 .+-. 0.45 s-vs 
5.68 .+-. 0.08 vw-w 
______________________________________ 
and more specifically the following characteristic values: 
TABLE 1B 
______________________________________ 
Interplanar d-Spacings (A) 
Relative Intensity 
______________________________________ 
16.41 .+-. 0.59 s-vs 
14.12 .+-. 0.45 s-vs 
8.98 .+-. 0.22 w-m.sup. 
5.68 .+-. 0.08 vw-w 
4.50 .+-. 0.05 vw-w 
4.10 .+-. 0.04 w-m.sup. 
______________________________________ 
and even more specifically the following characteristic values: 
TABLE 1C 
______________________________________ 
Interplanar d-Spacings (A) 
Relative Intensity 
______________________________________ 
16.41 .+-. 0.59 .sup. s-vs 
14.12 .+-. 0.45 .sup. s-vs 
8.98 .+-. 0.22 w-m 
8.88 .+-. 0.22 w-m 
5.68 .+-. 0.08 vw-w .sup. 
5.61 .+-. 0.08 vw-w .sup. 
4.50 .+-. 0.05 vw-w .sup. 
4.45 .+-. 0.05 vw-w .sup. 
4.10 .+-. 0.04 w-m 
______________________________________ 
Intensity scale is vw=0-20, w=20-40, m=40-60, s=60-80, and vs=80-100. 
The X-ray diffraction lines in Tables 1A, 1B and 1C identify a crystal 
framework topology in the composition exhibiting large pore windows of 
approximately 14-membered ring size. The pores are at least about 8.5-9.0 
Angstroms in diameter. These lines distinguish this topology from other 
crystalline aluminosilicate, aluminophosphate and silicoaluminophosphate 
structures. It is noted that the X-ray pattern of the present composition 
is void of a d-spacing value at 13.6-13.3 Angstroms with any significant 
intensity relative the strongest d-spacing value. If a d-spacing value in 
this range appears in a sample of the present composition, it is due to 
impurity and will have a weak relative intensity. The large pore 
"AlPO.sub.4 -8" of U.S. Pat. No. 4,310,440 has a d-spacing value at 
13.6-13.3 Angstroms with medium-very strong relative intensity as reported 
in the patent. 
These X-ray diffraction data were collected with conventional X-ray 
systems, using copper K-alpha radiation. The positions of the peaks, 
expressed in degrees 2 theta, where theta is the Bragg angle, were 
determined by scanning 2 theta. The interplanar spacings, d, measured in 
Angstrom units (A), and the relative intensities of the lines, I/I.sub.o, 
where I.sub.o is one-hundredth of the intensity of the strongest line, 
including subtraction of the background, were derived from the 
experimental X-ray diffraction pattern. It should be understood that this 
X-ray diffraction pattern is characteristic of all the species of the 
present compositions. Ion exchange of cations with other ions results in a 
composition which reveals substantially the same X-ray diffraction pattern 
with some minor shifts in interplanar spacing and variation in relative 
intensity. Relative intensity of individual lines may also vary relative 
the strongest line when the composition is chemically treated, such as by 
dilute acid treatment. Other variations can occur, depending on the +4 
valence element/+3 valence element, e.g. silicon/aluminum, and the +5 
valence element/+3 valence element, e.g. phosphorus/aluminum, ratios of 
the particular sample, as well as its degree of thermal treatment. The 
relative intensities of the lines are also susceptible to changes by 
factors such as sorption of water, hydrocarbons or other components in the 
channel structure. Further, the optics of the X-ray diffraction equipment 
can have significant effects on intensity, particularly in the low angle 
region. Intensities may also be affected by preferred crystallite 
orientation. 
The computed X-ray powder diffraction pattern of MCM-37 based on a 
structural model is shown in Table 1D. This structural model may not be 
correct in all respects but a theoretical X-ray powder pattern computed 
from the model reproduces the d-spacings and intensities observed on the 
experimental X-ray pattern to within the expected limits. 
TABLE 1D 
______________________________________ 
Relative 
Interplanar 
Intensities 
2.THETA. d-Spacing .ANG. 
I/I % .times. 100 
______________________________________ 
5.41 16.33 100.0 
6.25 14.13 53.3 
6.30 14.02 52.6 
9.86 8.97 6.7 
9.95 8.89 7.4 
11.35 7.80 &gt;1.0 
14.65 6.05 1.3 
14.75 6.00 1.3 
15.63 5.67 3.5 
15.79 5.61 3.4 
16.28 5.44 2.4 
17.24 5.14 2.2 
17.30 5.13 2.0 
19.79 4.49 2.9 
19.80 4.48 1.5 
19.91 4.46 1.3 
19.98 4.44 2.9 
20.39 4.36 1.6 
20.43 4.35 1.4 
21.66 4.10 24.0 
21.76 4.08 4.7 
21.89 4.06 4.8 
22.37 3.97 1.8 
22.60 3.93 2.3 
22.60 3.93 5.3 
22.61 3.93 2.1 
22.61 3.93 2.1 
22.71 3.92 1.9 
22.77 3.91 5.3 
22.81 3.90 7.2 
25.12 3.54 4.6 
25.23 3.53 4.5 
25.42 3.50 &gt;1.0 
28.29 3.15 &gt;1.0 
29.52 3.03 &gt;1.0 
29.72 3.01 2.1 
29.89 2.99 2.1 
31.69 2.824 &gt;1.0 
32.88 2.724 2.4 
33.42 2.681 1.0 
33.51 2.674 &gt;1.0 
______________________________________ 
The crystalline composition of this invention may be converted to the dry, 
hydrogen form by thermal treatment of the organic cation-containing form 
or hydrogen ion precursor-containing form resulting from ion exchange. 
In general, the composition of the present invention can be prepared by any 
suitable means, such as, for example, from either a one-phase or a 
two-phase reaction mixture. Preparation in a one-phase system may 
comprise: 
(1) providing a reaction mixture comprising sources of X oxide, Y oxide and 
Z oxide, wherein X represents one or more elements of +3 valence selected 
from the group consisting of, for example, aluminum, iron, chromium, 
vanadium, molybdenum, arsenic, antimony, manganese, gallium and boron; Y 
represents one or more elements of +5 valence selected from the group 
consisting of, for example, phosphorus, arsenic, antimony and vanadium; Z 
represents one or more elements of +4 valence selected from the group 
consisting of, for example, silicon, germanium and titanium, an organic 
directing agent D, inorganic ions M, and water, the components of said 
reaction mixture having the following relationship: 
EQU (D).sub.a :(M.sub.2 O).sub.b :(X.sub.2 O.sub.3).sub.c :(ZO.sub.2).sub.d : 
(Y.sub.2 O.sub.5).sub.e :(Solvent).sub.f :(N).sub.g :(H.sub.2 O).sub.h 
where a, b, c, d, f, n/q, and h are numbers satisfying the following 
relationships: 
a/(c+d+e) is less than 4, 
b/(c+d+e) is less than 2, 
d/(c+e) is less than 2, 
f/(c+d+e) is from 0.1 to 15, 
g/(c+d+e) is less than 2, and 
h/(c+d+e) is from 3 to 150. 
wherein upon initial provision of said reaction mixture said oxide source 
unstable in the water is dispersed or dissolved in the water-immiscible 
organic solvent; 
(2) heating said reaction mixture at a rate of from 5.degree. C. to 
200.degree. C. per hour to a temperature of from 80.degree. C. to 
300.degree.; 
(3) agitating said reaction mixture in a manner sufficient to intimately 
admix the water-immiscible organic solvent and the water with each other, 
thereby progressively hydrolyzing the oxide source unstable in water; 
(4) maintaining said agitated reaction mixture at a temperature of from 
80.degree. C. to 300.degree. C. and a pH of from 2 to 9 until crystals of 
oxide material are formed; and 
(5) recovering from said reaction mixture a composition characterized, in 
the anhydrous state, as follows: 
EQU D'.sub.v :M.sub.x/m.sup.m+ :(XO.sub.2).sub.1-y.sup.- 
:(YO.sub.2).sub.1-x.sup.30 :(ZO.sub.2).sub.x+y : N.sub.y/n.sup.n- 
wherein D' represents the total of organic directing agent D plus organic 
solvent, v is the number of moles of D', m is the valence of cation M, n 
is the valence of anion N, and x and y are numbers of from greater than -1 
to less than +1 which satisfy the relationships: 
(1) if x is 0, then y is not 0, 
(2) if y is 0, then x is not 0, and 
(3) x+y is greater than 0.001 and less than 1. 
Reaction conditions may comprise carefully heating the above reaction 
mixture at a rate of from 5.degree. C. to 200.degree. C. per hour to a 
temperature of from about 80.degree. C. to about 300.degree. C. for a 
period of time of from about 5 hours to about 500 hours until crystals of 
the present composition are formed. A more preferred temperature rang is 
from about 100.degree. C. to about 200.degree. C. with the amount of time 
at a temperature in such range being from about 15 hours to about 168 
hours. During heating and maintaining the reaction mixture at the desired 
temperature, the pH must be carefully controlled to be from about 2 to 
about 12. Control of pH can be accomplished by adjusting the concentration 
of the added organic and/or inorganic base(s). 
The reaction is carried out until crystals of the desired composition form. 
The crystalline product is recovered by separating same from the reaction 
medium, as by cooling the whole to room temperature, filtering and washing 
with water before drying. 
A two-phase system may also be used as described in U.S. Pat. No. No. 
4,647,442, which is incorporated herein by reference. In a two-phase 
system, the reaction mixture composition can be prepared utilizing 
materials which supply the appropriate components. In a two-phase system, 
the aqueous phase components may include from the sources of the +3, +4 or 
+5 valence elements, e.g. silicon, phosphorus, or aluminum, those not 
included in the water-immiscible, e.g. organic, phase. The organic phase 
comprises an organic solvent and a source of at least one of the +3, +4 or 
+5 valence elements, e.g. silicon, phosphorus, or aluminum, insoluble in 
the aqueous phase under reaction conditions. The aqueous phase also 
contains the required directing agent. 
In either system, useful sources of +3 valence element, e.g. aluminum, as 
non-limiting examples, include any known form of oxide or hydroxide, 
organic or inorganic salt or compound. Useful sources of +4 valence 
element, e.g. silicon, include, as non-limiting examples, any known form 
of dioxide or silicic acid, alkoxy- or other compounds of such element. 
Useful sources of +5 valence element, e.g. phosphorus, include, as 
non-limiting examples, any known form of phosphorus acids or phosphorus 
oxides, phosphates and phosphites, and organic derivatives of such 
element. 
The organic solvent is a C.sub.5 -C.sub.10 alcohol or any other liquid 
compound substantially immiscible with water, as nonlimiting examples. 
An organic directing agent can be selected from the group consisting of 
organic mono- or dialkylamines, alkyl being of 3 or 4 carbon atoms, and 
onium compounds having the following formula: 
EQU R.sub.4 M.sup.+ X.sup.- or (R.sub.3 M.sup.+ R'M.sup.+ R.sub.3)X.sub.2 
wherein R or R' is alkyl of from 1 to 20 carbon atoms, or combinations 
thereof; M is a tetracoordinate element (e.g. nitrogen, phosphorus, 
arsenic, antimony or bismuth); and X is an anion (e.g. fluoride, chloride, 
bromide, iodide, hydroxide, acetate, sulfate, carboxylate, etc.). 
Particularly preferred directing agents for synthesis of the present 
composition include onium compounds, above defined, wherein R is alkyl of 
1 to 4 carbon atoms, M is nitrogen and X is halide or hydroxide. 
Non-limiting examples of these include tetrapropylammonium hydroxide, 
tetrabutylammonium hydroxide, tetraethylammonium hydroxide and 
tetrapropylammonium bromide; and dialkylamines wherein alkyl is propyl or 
butyl, also tetrabutylammonium bromide, 2-hydroxyethyl derivatives of 
morpholine, piperidine, and piperazine. Particularly preferred are 
n-dipropylamine, tetra(2-hydroxyethyl)ammonium hydroxide and 
tetrabutylammonium hydroxide. 
The composition prepared by the instant invention can be shaped into a wide 
variety of particle sizes. Generally speaking, the particles can be in the 
form of a powder, a granule, or a molded product, such as an extrudate 
having particle size sufficient to pass through a 2 mesh (Tyler) screen 
and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst 
is molded, such as by extrusion, the crystals can be extruded before 
drying or partially dried and then extruded. 
It may be desired to incorporate the new composition with another material, 
i.e. a matrix, resistant to the temperatures and other conditions employed 
in various organic conversion processes. Such materials include active and 
inactive material and synthetic or naturally occurring zeolites as well as 
inorganic materials such as clays, silica and/or metal oxides, e.g. 
alumina. The latter may be either naturally occurring or in the form of 
gelatinous precipitates or gels including mixtures of silica and metal 
oxides. Catalyst compositions containing the present composition will 
generally comprise from about 1% to 90% by weight of the present 
composition and from about 10% to 99% by weight of the matrix material. 
More preferably, such catalyst compositions will comprise from about 2% to 
80% by weight of the present composition and from about 20% to 98% by 
weight of the matrix. 
Use of a material in conjunction with the new composition, i.e. combined 
therewith, which is active, tends to alter the conversion and/or 
selectivity of the overall catalyst in certain organic conversion 
processes. Inactive materials suitably serve as diluents to control the 
amount of conversion in a given process so that products can be obtained 
economically and orderly without employing other means for controlling the 
rate of reaction. These materials may be incorporated into naturally 
occurring clays, e.g. bentonite and kaolin, to improve the crush strength 
of the catalyst under commercial operating conditions. Said materials, 
i.e. clays, oxides, etc., function as binders for the catalyst. It may be 
desirable to provide a catalyst having good crush strength because in 
commercial use it is desirable to prevent the catalyst from breaking down 
into powder-like materials. These clay binders have been employed normally 
only for the purpose of improving the crush strength of the overall 
catalyst. 
Naturally occurring clays which can be composited with the new crystal 
include the montmorillonite and kaolin families which include the 
subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia 
and Florida clays or others in which the main mineral constituent is 
halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be 
used in the raw state as originally mined or initially subjected to 
calcination, acid treatment or chemical modification. 
In addition to the foregoing materials, the present composition can be 
composited with a porous matrix material such as aluminum phosphate, 
silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, 
silica-beryllia, silica-titania as well as ternary compositions such as 
silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia 
and silica-magnesia-zirconia. The relative proportions of finely divided 
crystalline material and inorganic oxide gel matrix vary widely, with the 
crystal content ranging from about 1 to about 90 percent by weight and 
more usually, particularly when the composite is prepared in the form of 
beads, in the range of about 2 to about 80 weight percent of the 
composite. 
Employing a catalytically active form of the present composition as a 
catalyst component, said catalyst possibly containing additional 
hydrogenation components, reforming stocks can be reformed employing a 
temperature of from about 370.degree. C. to about 540.degree. C., a 
pressure of from about 100 psig to about 1000 psig (791 to 6996 kPa), 
preferably from about 200 psig to about 700 psig (1480 to 4928 kPa), a 
liquid hourly space velocity is from about 0.1 to about 10, preferably 
from about 0.5 to about 4, and a hydrogen to hydrocarbon mole ratio of 
from about 1 to about 20, preferably from about 4 to about 12. 
A catalyst comprising the present composition can also be used for 
hydroisomerization of normal paraffins, when provided with a hydrogenation 
component, e.g. platinum. Such hydroisomerization is carried out at a 
temperature of from about 90.degree. C. to about 375.degree. C., 
preferably from about 145.degree. C. to about 290.degree. C., with a 
liquid hourly space velocity of from about 0.01 to about 2, preferably 
from about 0.25 to about 0.50, and with a hydrogen to hydrocarbon mole 
ratio of from about 1:1 to about 5:1. Additionally, such a catalyst can be 
used for olefin or aromatic isomerization, employing a temperature of from 
about 200.degree. C. to about 480.degree. C. 
Such a catalyst can also be used for reducing the pour point of gas oils. 
This reaction is carried out at a liquid hourly space velocity of from 
about 10 to about 30 and at a temperature of from about 425.degree. C. to 
about 595.degree. C. 
Other reactions which can be accomplished employing a catalyst comprising 
the composition of this invention containing a metal, e.g. platinum, 
include hydrogenation-dehydrogenation reactions and desulfurization 
reactions, olefin polymerization (oligomerization) and other organic 
compound conversions, such as the conversion of alcohols (e.g. methanol) 
or ethers (e.g. dimethylether) to hydrocarbons, and the alkylation of 
aromatics (e.g. benzene) in the presence of an alkylating agent (e.g. 
ethylene). 
Sorption capacities may be determined as follows: 
A weighed sample of the calcined adsorbant is contacted with a flowing 
stream of the equilibrium vapor of the adsorbate at 25.degree. C., admixed 
with dry nitrogen. Adsorbates are water vapor and benzene, n-hexane, 
2-methylpentane, xylene or cyclohexane vapors. The sample temperature is 
maintained at 25.degree. C. to 90.degree. C. for adsorbates other than 
ortho-xylene which can be 120.degree. C. and water for which it was 
60.degree. C. The increase in weight is measured gravimetrically and 
converted to the adsorption capacity of the sample in weight percent of 
calcined adsorbant. 
Alpha Value may also be determined. When Alpha Value is examined, it is 
noted that the Alpha Value is an approximate indication of the catalytic 
cracking activity of the catalyst compared to a standard catalyst and it 
gives the relative rate constant (rate of normal hexane conversion per 
volume of catalyst per unit time). It is based on the activity of the 
highly active silica-alumina cracking catalyst taken as an Alpha of 1 
(Rate Constant=0.016 sec.sup.-1). The Alpha Test is described in U.S. Pat. 
No. 3,354,078, in The Journal of Catalysis, 6, pp. 522-529 (Aug. 1965), 
and in The Journal of Catalysis, 61, p. 395 (1980), each incorporated 
herein by reference as to that description. 
When ion-exchange capacity is examined, it is determined by titrating with 
a solution of sulfamic acid the gaseous ammonia evolved during the 
temperature programmed decomposition of the ammonium-form of the present 
composition. The method is described in Thermochimica Acta, Vol. III, pp. 
113-124, 1971 by G. T. Kerr and A. W. Chester, incorporated herein by 
reference as to that description. 
In order to more fully illustrate the nature of the invention and the 
manner of practicing same, the following examples are presented. 
EXAMPLE 1 
A solution containing 23 g of 85% H.sub.3 PO.sub.4 and 50 g water was mixed 
with 10.31 g of Al.sub.2 O.sub.3 .multidot.nH.sub.2 O (Catapal SB 
alumina). To the mixture, 3 g of silica gel and 50.83 g of 
tetrapropylammonium hydroxide (TPAOH) (40 wt %) were added. The mixture 
was crystallized in a 300 cc. autoclave at 150.degree. C. for 64 hours. 
The product was filtered, washed and calcined under air to 538.degree. C. 
for 2 hours. Table 1 shows the X-ray powder diffraction data and FIG. 1 
shows the X-ray diffraction pattern of the calcined material. 
TABLE 1 
______________________________________ 
D-values and relative intensities MCM-37 Preparation* 
Lambda for this run: 1.54178 Angstroms 
Relative 
Peak No. 2 theta(.degree.) 
d-value(A) 
Intensity 
______________________________________ 
1 5.372 16.452 23.9 
(Peak at 5.372 2.THETA. enhanced by impurity phase.) 
2 6.238 14.169 20.5 
(Peak at 6.238 2.THETA. is unresolved doublet.) 
Impurity Phase 
7.426 11.904 38.1 
3 9.828 8.999 9.1 
4 9.928 8.909 4.8 
Impurity Phase 
10.749 8.230 1.7 
5 11.296 7.833 &gt;1.0 
Impurity Phase 
12.482 7.091 38.9 
Impurity Phase 
12.893 6.866 7.2 
6 17.314 5.122 3.6 
7 15.557 5.696 1.2 
8 15.752 5.626 1.4 
Impurity Phase 
18.049 4.915 4.4 
Impurity Phase 
18.717 4.741 1.0 
Impurity Phase 
18.999 4.671 3.0 
9 19.767 4.491 10.9 
(Peak at 19.767 2.THETA. enhanced by impurity phase.) 
10 20.300 4.374 100.0 
(Peak at 20.300 2.THETA. enhanced by impurity phase.) 
Impurity Phase 
20.954 4.239 45.8 
Impurity Phase 
21.189 4.193 22.1 
Impurity Phase 
21.447 4.143 65.6 
11 (shoulder) 
21.662 4.102 8.1 
12 22.483 3.954 20.5 
(Peak at 22.483 2.THETA. enhanced by impurity phase.) 
Impurity Phase 
22.737 3.911 11.5 
Impurity Phase 
22.992 3.868 45.0 
Impurity Phase 
24.470 3.638 6.7 
Impurity Phase 
24.653 3.611 2.3 
13 25.060 3.553 3.5 
14 25.216 3.532 1.9 
______________________________________ 
*This preparation is a mixture of several phases. Peaks due to the MCM37 
component are numbered consecutively. 
EXAMPLE 2 
A mixture containing 130.0 g of distilled water, 39.7 g of Al.sub.2 O.sub.3 
.multidot.nH.sub.2 O (Catapal alumina (74.5%)) and 70.7 g orthophosporic 
acid (H.sub.3 PO.sub.4 =85.7%) were mixed together and aged without 
stirring for 3 hours at 25.degree. C.. 194.6 g of 40 wt % 
tetrabutylammonium hydroxide in H.sub.2 O were then added and stirred for 
an additional 30 minutes at 25.degree. C. The final gel (pH=5.5) was 
charged to a 300 cc autoclave equipped with a stainless steel liner, 
pressurized with 300 psig nitrogen and heated without stirring to 
143.degree. C. for 20 hours. 
After cooling, product was removed, washed and decanted using distilled 
H.sub.2 O until a reasonably clear liquid wash was obtained. Some of the 
washed as-synthesized product was collected using a filter funnel assembly 
and dried in air at 130.degree. C./3 hours. In addition, some of the still 
wet washed product was soxhlet extracted overnight using distilled water 
and dried again in air at 130.degree. C./3 hours. Some of the extracted 
product was then calcined in air at 1.degree. C./minute from 25.degree. C. 
to 538.degree. C. and held for 6 hours. Table 2 shows the X-ray powder 
diffraction data and FIG. 2 shows the X-ray diffraction pattern of this 
material. 
TABLE 2 
______________________________________ 
Tabulation of X-Ray Powder Diffraction Data for MCM-37 
Preparation. 
Lambda for this run = 1.54178 A. 
Relative 
Peak 2 theta d-value Intensity 
______________________________________ 
01 5.394 16.383 78.4 
02 6.264 14.110 100.0 
(unresolved 
doublet) 
03 9.847 8.982 65.5 
04 9.958 8.882 44.9 
Impurity Phase 
10.815 8.180 2.6 
05 11.329 7.810 5.3 
Impurity Phase 
12.502 7.080 7.6 
06 14.623 6.057 5.1 
07 14.740 6.010 3.9 
08 15.600 5.680 13.7 
09 15.784 5.614 15.3 
10 16.248 5.455 11.4 
11 17.258 5.138 11.3 
Impurity Phase 
18.183 4.879 2.1 
Impurity Phase 
18.803 4.719 1.7 
Impurity Phase 
18.983 4.675 0.8 
12 19.745 4.496 25.7 
13 19.956 4.449 17.8 
14 20.344 4.365 13.1 
Impurity Phase 
21.015 4.227 5.0 
Impurity Phase 
21.429 4.146 5.2 
15 21.682 4.099 35.9 
16 21.871 4.064 6.7 
17 22.351 3.977 3.1 
18 22.563 3.941 22.0 
(Peak at 22.563 2.THETA. enhanced by impurity phase.) 
19 22.766 3.906 52.6 
(Peak at 20.766 2.THETA. enhanced by impurity phase.) 
Impurity Phase 
23.369 3.808 1.9 
Impurity Phase 
24.476 3.637 3.4 
20 25.075 3.551 33.5 
21 25.214 3.532 21.1 
______________________________________ 
EXAMPLE 3 
A solution containing 115.25 g of 85% H.sub.3 PO.sub.4 and 150.00 g water 
was mixed with 68.75 g Al.sub.2 O.sub.3 .multidot.nH.sub.2 O (Catapal 
alumina) and aged for two hours at 80.degree.-90.degree. C. 6.0 g 
di-n-butylamine in 15 g water were then added. 40 g of the final gel (pH 
5.0) were heated at 150.degree. C. for 64 hours and calcined. FIG. 3 shows 
the X-ray diffraction pattern of the product material.