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0277A
United States Patent (19) 11 Patent Number: 5,300,277
Kresge et al. 45) Date of Patent: k Apr. 5, 1994
(54) SYNTHESIS OF MESOPOROUS 4,791,088 12/1988 Chu et al............................. 502/232
CRYSTALLINE MATERAL 4,793,333 12/1988 Lok et al. ................................ 55/33
4,803,060 2/1989 Occelli........ ... 423/326
(75) Inventors: Charles T. Kresge, West Chester, Pa.; 4,826,667 5/1989 Zones et al. ........................ 423/277
Wielsaw J. Roth, Sewell, N.J. 4,831,006 5/1989 Aufidenbrink ...................... 502/242
(73) Assignee: Mobil Oil Corporation, Fairfax, Va. 4,859,648 8/1989 Landis et al. ....................... 502/242
4,880,611 11/1989 von Ballmoos et al. ... 423/306
* Notice: The portion of the term of this patent 4,954,325 9/1990 Rubin et al. ........... ... 423/328
subsequent to Oct. 15, 2008 has been 5,057,296 10/1991 Beck ............... ... 423/277
disclaimed. 5,102,643 4/1992 Kresge et al. ....................... 423/328
5,108,725 4/1992 Beck et al. .......................... 423/705
(21) Appl. No.: 964,235 5,112,589 5/1992 Johnson et al. ..................... 423/705
5,156,828 10/1992 Pegnen et al. . ... 42.3/709
22) Filed: Oct. 21, 1992 5,211,934 5/1993 Kresge et al... ... 42.3/706
5,215,737 6/1993 Chu et al. ............................ 423/712
Related U.S. Application Data OTHER PUBLICATIONS
(63) Continuation-in-part of Ser. No. 734,825, Jul. 24, 1991,
Pat. No. 5, 198,203, which is a continuation-in-part of Eugster, H. P., "Hydrous Sodium Silicates from Lake
Ser. No. 470,008, Jan. 25, 1990, Pat. No. 5,102,643. Magadi, Kenya: Precursors of Bedded Chert,' Science,
(51) Int. Cl. ....................... C01B33/20; C01B33/26 vol. 157, pp. 1177-1180 (1967).
(52) U.S. Cl. ......... . . . . . . . . . . . . . . . . . . . . . . . 423/703; 423/328.2;
d'Yvoire, F., "Memoir: Study of Aluminum Phosphate
423/329.1; 42.3/705; 502/64 and Trivalent Iron,' pp. 1762-1776.
(58) Field of Search ............... 423/700, 705, 709, 706, Moore, P. B. et al., "An X-ray Structural Study of
423/712; 502/60, 62 Cacoxenite, a Mineral Phosphate,” Nature, v. 306, No.
5941, pp. 356-358 (1983).
(56) References Cited Kirk-Othmer Encyclopedia of Chemical Technology,
U.S. PATENT DOCUMENTS 3rd ed., v. 20, pp. 766–781.
3,414,602 12/1968 Acara .................................. 260/448 Szostak, R., et al., "Ultralarge Pore Molecular Sieves:
3,567,372 3/1971 Duecker et al. ...................... 23/11 Characterization of the 14 Angstrons Pore Mineral,
3,884,835 5/1975 Vaughan ....... ... 252/451 Cacoxenite," Zeolites: Facts, Figures and Future, El
4,091,079 5/1978 Vaughan ............................. 423/328 seview Sc. Pub., BV. (1989).
4,176,090 1 1/1979 Vaughan et al. . ... 252/455 Z Primary Examiner-Anthony McFarlane
4,216,188 8/1980 Shabria et al. ...................... 423/18
4,248,739 2/1981 Vaughan et al. . ... 252/455 R Attorney, Agent, or Firm-Alexander J. McKillop;
4,310,440 l/1982 Wilson et al. ....................... 252/.435 Malcolm D. Keen; Dennis P. Santini
4,367,163 1/1983 Pinnavaia et al. ... 252/455 R 57 ABSTRACT
4,385,994 5/1983 Wilson et al. ....................... 210/689
4,440,871 4/1984 Lok et al. ...... ... SO2/214 This invention relates to an improvement in the method
4,481,177 11/1984 Valyocsik . ... 423/329 for synthesis of a new synthetic composition of porous
4,578.258 3/1986 Rieck ................ ... 423/325 crystalline material. The new crystalline material exhib
4,582,693 4/986 Desmond et al. ... 423/329 its a large sorption capacity demonstrated by its ben
4,626,421 2/1986 Zones ................ ... 423/326 zene adsorption capacity of greater than about 10 grams
4,632,815 12/1986 Valyocsik. ... 423/328
4,640,829 2/1987 Rubin ........ ... 423/328 benzene/100 grams at 50 torr and 25 C. and a particu
4,650,655 3/1987 Chu et al. ...... ... 423/328 lar, unique X-ray diffraction pattern.
4,661,332 4/1987 Vaughan et al. . ... 423/326
4,673,559 6/1987 Derouane et al. .................. 423/306 21 Claims, No Drawings
1.
5,300,277
2
Wefers and Chanakya Misra, “Oxides and Hydroxides
SYNTHESIS OF MESOPOROUS CRYSTALLINE of Aluminum", Technical Paper No. 19 Revised, Alcoa
MATERAL Research Laboratories, 54-59 (1987)). Since, in the case
CROSS-REFERENCE TO RELATED
of either material, there is no long range order control
APPLICATIONS
ling the sizes of pores in the material, the variability in
pore size is typically quite high. The sizes of pores in
This application is a continuation-in-part of U.S. pa these materials fall into a regime called the mesoporous
tent application Ser. No. 07/734,825, filed Jul. 24, 1991, range, which, for the purposes of this application, is
now U.S. Pat. No. 5, 198,203, which is a continuation-in
10
from about 13 to 200 Angstroms.
part of U.S. patent application Ser. No. 07/470,008, In sharp contrast to these structurally ill-defined
filed Jan. 25, 1990, now U.S. Pat. No. 5,102,643. solids are materials whose pore size distribution is very
BACKGROUND OF THE INVENTION narrow because it is controlled by the precisely repeat
1. Field of the Invention
ing crystalline nature of the materials' microstructure.
15 These materials are called "molecular sieves', the most
This invention relates to an improved synthesis important examples of which are zeolites.
method for preparing a novel composition of synthetic Zeolites, both natural and synthetic, have been dem
ultra-large pore crystalline material which can be used onstrated in the past to have catalytic properties for
as a sorbent or a catalyst component. various types of hydrocarbon conversion. Certain zeo
2. Description of the Prior Art litic materials are ordered, porous crystalline alumino
Porous inorganic solids have found great utility as 20
catalysts and separations media for industrial applica silicates having a definite crystalline structure as deter
tion. The openness of their microstructure allows mole mined by X-ray diffraction, within which there are a
cules access to the relatively large surface areas of these large number of smaller cavities which may be intercon
materials that enhance their catalytic and sorptive activ nected by a number of still smaller channels or pores.
ity. The porous materials in use today can be sorted into 25 These cavities and pores are uniform in size within a
three broad categories using the details of their micro specific zeolitic material. Since the dimensions of these
structure as a basis for classification. These categories pores are such as to accept for adsorption molecules of
are the amorphous and paracrystalline supports, the certain dimensions while rejecting those of larger di
crystalline molecular sieves and modified layered mate mensions, these materials are known as "molecular
rials. The detailed differences in the microstructures of 30 sieves' and are utilized in a variety of ways to take
these materials manifest themselves as important differ advantage of these properties.
ences in the catalytic and sorptive behavior of the mate Such molecular sieves, both natural and synthetic,
rials, as well as in differences in various observable include a wide variety of positive ion-containing crys
properties used to characterize them, such as their sur talline silicates. These silicates can be described as a
face area, the sizes of pores and the variability in those 35 rigid three-dimensional framework of SiO4 and Periodic
sizes, the presence or absence of X-ray diffraction pat Table Group IIIB element oxide, e.g., AlO4, in which
terns and the details in such patterns, and the appear the tetrahedra are cross-linked by the sharing of oxygen
ance of the materials when their microstructure is stud atoms whereby the ratio of the total Group IIIB ele
ied by transmission electron microscopy and electron ment, e.g., aluminum, and Group IVB element, e.g.,
diffraction methods. silicon, atoms to oxygen atoms is 1:2. The electrova
Amorphous and paracrystalline materials represent lence of the tetrahedra containing the Group IIIB ele
an important class of porous inorganic solids that have ment, e.g., aluminum, is balanced by the inclusion in the
been used for many years in industrial applications. crystal of a cation, for example, an alkali metal or an
Typical examples of these materials are the amorphous alkaline earth metal cation. This can be expressed
silicas commonly used in catalyst formulations and the 45
wherein the ratio of the Group IIIB element, e.g., alu
paracrystalline transitional aluminas used as solid acid minum, to the number of various cations, such as Ca/2,
catalysts and petroleum reforming catalyst supports. Sr/2, Na, K or Li, is equal to unity. One type of cation
The term "amorphous" is used here to indicate a mate may be exchanged either entirely or partially with an
rial with no long range order and can be somewhat other type of cation utilizing ion exchange techniques in
misleading, since almost all materials are ordered to 50
a conventional manner. By means of such cation ex
some degree, at least on the local scale. An alternate change, it has been possible to vary the properties of a
term that has been used to describe these materials is
"X-ray indifferent'. The microstructure of the silicas given silicate by suitable selection of the cation. The
consists of 100-250 Angstrom particles of dense amor spaces between the tetrahedra are occupied by mole
phous silica (Kirk-Othmer Encyclopedia of Chemical 55 cules of water prior to dehydration.
Technology, 3rd ed., 20, 766-781 (1982)), with the poros Prior art techniques have resulted in the formation of
ity resulting from voids between the particles. Since a great variety of synthetic zeolites. Many of these zeo
there is no long range order in these materials, the pores lites have come to be designated by letter or other con
tend to be distributed over a rather large range. This venient symbols, as illustrated by zeolite A (U.S. Pat.
lack of order also manifests itself in the X-ray diffrac No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244);
tion pattern, which is usually featureless. zeolite Y (U.S. Pat. No. 3,130,007); zeolite ZK-5 (U.S.
Paracrystalline materials such as the transitional alu Pat. No. 3,247,195); zeolite ZK-4 (U.S. Pat. No.
minas also have a wide distribution of pore sizes, but 3,314,752); zeolite ZSM-5 (U.S. Pat. No. 3,702,886);
better defined X-ray diffraction patterns usually consist zeolite ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM
ing of a few broad peaks. The microstructure of these 65 12 (U.S. Pat. No. 3,832,449); zeolite ZSM-20 (U.S. Pat.
materials consists of tiny crystalline regions of con No. 3,972,983); ZSM-35 (U.S. Pat. No. 4,016,245); and
densed alumina phases and the porosity of the materials zeolite ZSM-23 (U.S. Pat. No. 4,076,842), merely to
results from irregular voids between these regions (K. name a few.
3
5,300,277
4.
The SiO2/Al2O3 ratio of a given zeolite is often vari and the method for its synthesis are taught in U.S. Pat.
able. For example, zeolite X can be synthesized with No. 4,500,651.
SiO2/Al2O3 ratios of from 2 to 3; zeolite Y, from 3 to The phosphorus-substituted zeolites of Canadian Pa
about 6. In some zeolites, the upper limit of the SiO2. tents 911,416; 911,417; and 91,418 are referred to as
/Al2O3 ratio is unbounded. ZSM-5 is one such example "aluminosilicophosphate' zeolites. Some of the phos
wherein the SiO2/Al2O3 ratio is at least 5 and up to the phorus therein appears to be occluded, not structural.
limits of present analytical measurement techniques. U.S. Pat. No. 4,363,748 describes a combination of
U.S. Pat. No. 3,941,871 (Re. 29,948) discloses a porous silica and aluminum-calcium-cerium phosphate as a low
crystalline silicate Inade from a reaction mixture con acid activity catalyst for oxidative dehydrogenation.
taining no deliberately added alumina in the recipe and 10 Great Britain Patent 2,068,253 discloses a combination
exhibiting the X-ray diffraction tern characteristic of of silica and aluminum-calcium-tungsten phosphate as a
ZSM-5. U.S. Pat. Nos. 4,061,724; 4,073,865 and low acid activity catalyst for oxidative dehydrogena
4,104,294 describe crystalline silicate of varying alu tion. U.S. Pat. No. 4,228,036 teaches an alumina
mina and metal content. aluminum phosphate-silica matrix as an amorphous
Aluminum phosphates are taught in U.S. Pat. Nos. 15 body to be mixed with zeolite for use as cracking cata
4,310,440 and 4,385,994, for example. These aluminum lyst. U.S. Pat. No. 3,213,035 teaches improving hard
phosphate materials have essentially electroneutral lat ness of aluminosilicate catalysts by treatment with phos
tices. U.S. Pat. No. 3,801,704 teaches an aluminum phoric acid. The catalysts are amorphous.
phosphate treated in a certain way to impart acidity. 20 Other patents teaching aluminum phosphates include
An early reference to a hydrated aluminum phos U.S. Pat. Nos. 4,365,095; 4,361,705; 4,222,896;
phate which is crystalline until heated at about 110' C., 4,210,560; 4,179,358; 4,158,621; 4,071,471; 4,014,945;
at which point it becomes amorphous or transforms, is 3,904,550; and 3,697,550.
the "H1' phase or hydrate of aluminum phosphate of F. The precise crystalline microstructure of most zeo
d'Yvoire, Memoir Presented to the Chemical Society, No. 25 lites manifests itself in a well-defined X-ray diffraction
392, "Study of Aluminum Phosphate and Trivalent pattern that usually contains many sharp maxima and
Iron', Jul. 6, 1961 (received), 1762-1776. This material, that serves to uniquely define the material. Similarly,
when crystalline, is identified by the JCPDS Interna the dimensions of pores in these materials are very regu
tional Center for Diffraction Data card number 15-274. lar, due to the precise repetition of the crystalline mi
Once heated at about 110° C., however, the d'Yvoire 30 crostructure. All molecular sieves discovered to date
material becomes amorphous or transforms to the have pore sizes in the microporous range, which is
aluminophosphate form of tridymite. usually quoted as 2 to 20 Angstroms.
Compositions comprising crystals having a frame In layered materials, the interatomic bonding in two
work topology after heating at 110° C. or higher giving directions of the crystalline lattice is substantially differ
an X-ray diffraction pattern consistent with a material 35 ent from that in the third direction, resulting in a struc
having pore windows formed by 18 tetrahedral mem ture that contains cohesive units resembling sheets.
bers of about 12-13 Angstrons in diameter are taught in Usually, the bonding between the atoms within these
U.S. Pat. No. 4,880,611. sheets is highly covalent, while adjacent layers are held
A naturally occurring, highly hydrated basic ferric together by ionic forces or van der Waals interactions.
oxyphosphate mineral, cacoxenite, is reported by These latter forces can frequently be neutralized by
Moore and Shen, Nature, 306, No. 5941, 356-358 (1983) relatively modest chemical means, while the bonding
to have a framework structure containing very large between atoms within the layers remains intact and
channels with a calculated free pore diameter of 14.2 unaffected.
Angstroms. R. Szostak et al., Zeolites: Facts, Figures, Certain layered materials, which contain layers capa
Future, Elsevier Science Publishers B. V. (1989), pres 45 ble of being spaced apart with a swelling agent, may be
ent work showing cacoxenite as being very hydrophilic, pillared to provide materials having a large degree of .
i.e., adsorbing non-polar hydrocarbons only with great porosity. Examples of such layered materials include
difficulty. Their work also shows that thermal treat clays. Such clays may be swollen with water, whereby
ment of cacoxenite causes an overall decline in X-ray the layers of the clay are spaced apart by water mole
peak intensity. 50 cules. Other layered materials are not swellable with
Silicoaluminophosphates of various structures are water, but may be swollen with certain organic swelling
taught in U.S. Pat. No. 4,440,871. Aluminosilicates con agents such as amines and quaternary ammonium com
taining phosphorous, i.e., silicoaluminophosphates of pounds. Examples of such non-water swellable layered
particular structures are taught in U.S. Pat. No. materials are described in U.S. Pat. No. 4,859,648 and
3,355,246 (i.e., ZK-21) and U.S. Pat. No. 3,791,964 (i.e., 55 include layered silicates, magadiite, kenyaite, tritita
ZK-22) Other teachings of silicoaluminophosphates and nates and perovskites. Another example of a non-water
their synthesis include U.S. Pat. No. 4,673,559 (two swellable layered material, which can be swollen with
phase synthesis method); U.S. Pat. No. 4,623,527 certain organic swelling agents, is a vacancy-containing
(MCM-10); U.S. Pat. No. 4,639,358 (MCM-1); U.S. Pat. titanometallate material, as described in U.S. Pat. No.
No. 4,647,442 (MCM-2); U.S. Pat. No. 4,664,897 4,831,006.
(MCM-4); U.S. Pat. No. 4,638,357 (MCM-5); and U.S. Once a layered material is swollen, the material may
Pat. No. 4,632,811 (MCM-3). be pillared by interposing a thermally stable substance,
A method for synthesizing crystalline metal such as silica, between the spaced apart layers. The
loaluminophosphates is shown in U.S. Pat. No. aforementioned U.S. Pat. Nos. 4,831,006 and 4,859,648
4,713,227, and an antimonophosphoaluminate and the 65 describe methods for pillaring the non-water swellable
method for its synthesis are taught in U.S. Pat. No. layered materials described therein and are incorpo
4,619,818. U.S. Pat. No. 4,567,029 teaches metal rated herein by reference for definition of pillaring and
loaluminophosphates, and titaniumaluminophosphate pillared materials.
5
5,300,277
6
Other patents teaching pillaring of layered materials A preferred embodiment of the above crystalline
and the pillared products include U.S. Pat. Nos. material is when (a+b+c) is greater than d, and h-2.
4,216, 188; 4,248,739; 4,176,090; and 4,367,163; and Eu A further embodiment is when a and d = 0, and h =2.
ropean Patent Application 205,711. In the as-synthesized form, the material of this inven
The X-ray diffraction patterns of pillared layered tion has a composition, on an anhydrous basis, ex
materials can vary considerably, depending on the de pressed empirically as follows:
gree that swelling and pillaring disrupt the otherwise
usually well-ordered layered microstructure. The regu rRM/(WXYZaO)
larity of the microstructure in some pillared layered
materials is so badly disrupted that only one peak in the 10
low angle region on the X-ray diffraction pattern is wherein R is the total organic material not included in
observed, as a d-spacing corresponding to the interlayer M as an ion, and r is the coefficient for R, i.e., the num
repeat in the pillared material. Less disrupted materials ber of moles or mole fraction of R.
may show several peaks in this region that are generally The M and R components are associated with the
orders of this fundamental repeat. X-ray reflections 15 material as a result of their presence during crystalliza
from the crystalline structure of the layers are also tion, and are easily removed or, in the case of M, re
sometimes observed. The pore size distribution in these placed by post-crystallization methods hereinafter more
pillared layered materials is narrower than those in particularly described.
amorphous and paracrystalline materials but broader To the extent desired, the original M, e.g., sodium or
than that in crystalline framework materials. 20 chloride, ions of the as-synthesized material prepared
Applicants know of no prior art teaching the pres hereby can be replaced in accordance with techniques
ently claimed improved method for synthesizing the well known in the art, at least in part, by ion exchange
synthetic ultra-large pore non-layered crystalline mate with other ions. Preferred replacing ions include metal
rial herein described. ions, hydrogen ions, hydrogen precursor, e.g., ammo
25 nium, ions and mixtures thereof. Particularly preferred
SUMMARY OF THE INVENTION ions are those which tailor the catalytic activity for
The present invention is directed to an improved certain hydrocarbon conversion reactions. These in
method for synthesizing a novel synthetic composition clude hydrogen, rare earth metals and metals of Groups
of matter comprising an ultra-large pore crystalline IA (e.g., K), IIA (e.g., Ca), VIIA (e.g., Mn), VIIIA
material. The method provides a high purity, reproduc 30 (e.g., Ni),IB (e.g., Cu), IIB (e.g., Zn), IIIB (e.g., In),
ible product in a low-cost procedure compatible with IVB (e.g., Sn), and VIIB (e.g., F) of the Periodic Table
normally used crystal synthesis equipment. The crystal of the Elements (Sargent-Welch Scientific Co. Cat. No.
line material prepared hereby is an inorganic, porous, S-18806, 1979) and mixtures thereof.
non-layered phase which may have uniformly sized The crystalline (i.e., meant here as having sufficient
pores with a pore dimension of at least about 13 Ang
35 order to provide a diffraction pattern such as, for exam
stroms, and within the range of from about 13, e.g., 15,
ple, by X-ray, electron or neutron diffraction, following
Angstroms to about 200 Angstroms as measured by calcination with at least one peak) mesoporous material
argon physisorption. This novel crystalline composition prepared hereby may be characterized by its novel
structure, including extremely large pore windows, and
exhibits an X-ray diffraction pattern and a benzene ad high sorption capacity. The term "mesoporous" is used
sorption capacity usually greater than about 10 grams here to indicate crystals having pores within the range
benzene/100 grams crystal at 50 torr and 25 C. of from about 13, e.g., from about 15, Angstroms to
DESCRIPTION OF SPECIFIC EMBODIMENTS about 200 Angstroms in diameter. The materials of this
invention may have uniform pores within the range of
U.S. patent application Ser. No. 07/734,825 is en 45 from about 13 Angstrons to about 200 Angstrons,
tirely incorporated herein by reference. more usually from about 15 Angstroms to about 100
As demonstrated hereinafter, the inorganic, non-lay Angstrons in diameter. For the purposes of this appli
ered mesoporous crystalline material prepared in accor cation, a working definition of "porous" is a material
dance with this invention has the following composi that adsorbs at least 1 gram of a small molecule, such as
tlOn: 50 Air, N2, n-hexane, benzene or cyclohexane, per 100
grams of the solid.
Mn/(WaxY-ZOh) The material synthesized by the present invention can
be distinguished from other porous inorganic solids by
wherein W is a divalent element, such as a divalent first the regularity of its large open pores, whose pore size
row transition metal, e.g., manganese, cobalt and iron, 55 more nearly resembles that of amorphous or paracrys
and/or magnesium, preferably cobalt; X is a trivalent talline materials, but whose regular arrangement and
element, such as aluminum, boron, iron and/or gallium, uniformity of size (pore size distribution within a single
preferably aluminum; Y is a tetravalent element or mix phase of, for example, +25%, usually --15% or less of
ture of elements comprising silicon; Z is a pentavalent the average pore size of that phase) resemble more those
element, such as phosphorus; M is one or more ions, of crystalline framework materials such as zeolites. The
such as, for example, ammonium, Group IA, IIA and material appears to have a regular arrangement of large
VIIB ions, usually hydrogen, sodium and/or fluoride open pores that can be synthesized with open internal
ions; n is the charge of the composition excluding M dimensions from about 13 Angstroms to about 200 Ang
expressed as oxides; q is the weighted molar average Strons.
valence of M: n/q is the number of moles or mole frac 65 The most regular preparations of the materials syn
tion of M: a, b, c, and d are mole fractions of W, X, Y thesized by the present invention following removal of
and Z, respectively; his a number of from 1 to 2.5; and organic, e.g., by calcination at 540 C. in air for at least
(a-b-c-d)=l. about 1 hour, give an X-ray diffraction pattern with
7
5,300,277
8
distinct maxima in the extreme low angle region. The TABLE 5-continued
positions of these peaks will vary somewhat with 7.2 1.2
changes in the pore diameters of the materials but the
ratios of d-spacings of those peaks will remain fixed.
Using d1 to indicate the d-spacings of the strongest peak 5 Still more particularly, the X-ray diffraction patterns
in the X-ray diffraction pattern (relative inten of some calcined products of examples presented herein
sity = 100), the X-ray diffraction pattern of the calcined can be characterized, as including at least five peaks at
material of the present invention exhibits d1 at a position positions corresponding to the ranges given in Table 6.
greater than about 18 Angstrons d-spacing and at least
one additional weaker peak with d-spacing d2 such that 10 TABLE 6
the ratios of these d-spacings relative to d1 (i.e., d/dl) d-Spacing, Angstroms Relative Intensity
correspond to the ranges give in Table 1.
33.0 - 2.0 100
TABLE 1 28.7 1.5 W
d-Spacing, dAngstroms d/d Relative Intensity 15 18.2 : 0.5 W
7.2 - 0.4 W
d, 2 - 18 1.0 100 16.5 - 0.3 W
d2 0.87 0.06 W
EXAMPLE 6
EXAMPLE 4 60
Thirty-five grams of Ludox HS-40, a colloidal disper
One hundred grams of cetyltrimethylammonium sion of wt.% SiO2 having an SiO2/Na2O mole ratio of
(CTMA) hydroxide solution prepared as in Example 1 100, was added to 300 grams of cetyltrimethylam
was combined with 30 grams of tetraethylorthosilicate monium (CTMA) hydroxide solution prepared as in
(TEOS) with stirring. The stirring was continued for 65 Example 1. After stirring for 0.5 hour, 20 grams of
one hour. An 11.2 gram quantity of 1N NaOH solution ethanol was added to the mixture. The mixture was then
was then added. This mixture was placed in a polypro placed in an autoclave and maintained at 120° C. with
pylene bottle and put into a steam box -100° C.) for 48 stirring for 24 hours. The mixture had a composition in
19
5,300,277
20
terms of moles per mole SiO2 assuming complete ex
change of the surfactant: EXAMPLE 8(A)
058 moles of (CTMA)2O Argon Physisorption For Pore Systems Up to About 60
0.01 moles of Na2O Angstrons Diameter
55.8 moles of H2O To determine the pore diameters of the products of
8.03 moles of ethanol
The mixture had a Solvent/(R'2O+M2O) ratio of this invention with pores up to about 60 Angstroms in
108.
diameter, 0.2 gram samples of the products of Examples
1 through 6 were placed in glass sample tubes and at
The resultant product was filtered, washed, air-dried tached to a physisorption apparatus as described in U.S.
at 100° C. and calcined (6 hours at 540 C. in air). A 10 Pat. No. 4,762,010, which is incorporated herein by
tabulation of the X-ray diffraction peak positions ob reference.
tained by deconvolution of the X-ray diffraction pattern The samples were heated to 300° C. for 3 hours in
for this high purity preparation follows: vacuo to remove adsorbed water. Thereafter, the sam
5 ples were cooled to 87 K. by immersion of the sample
Interplanar d-Spacing Relative intensity d/d tubes in liquid argon. Metered amounts of gaseous
34.9 100 1.00
argon were then admitted to the samples in stepwise
30.5 11 0.87 manner as described in U.S. Pat. No. 4,762,010, column
22.6 0.5 0.64 20. From the amount of argon admitted to the samples
20.9 0.5 0.60 20 and the amount of argon left in the gas space above the
18.8
17.9
5.0
2.8
0.54
0.5
samples, the amount of argon adsorbed can be calcu
17.2 2.6 0.50
lated. For this calculation, the ideal gas law and the
calibrated sample volumes were used. (See also S. J.
Gregg et al., Adsorption, Surface Area and Porosity, 2nd
The benzene sorption capacity of the product mate 25 ed. (1982)). In each instance, a graph of the amount
rial was measured to be approximately 62 wt.%. The adsorbed versus the relative pressure above the sample,
product had a BET of about 1600 m2/g. at equilibrium, constitutes the adsorption isotherm. It is
EXAMPLE 7
common to use relative pressures which are obtained by
forming the ratio of the equilibrium pressure and the
Fourteen and seven-tenths grams of HiSil 233, a pre 30 vapor pressure Po of the adsorbate at the temperature
cipitated SiO2 which contains approximately 0.55 wt.%. where the isotherm is measured. Sufficiently small
Al2O3, were added to 300 grams of cetyltrimethylam amounts of argon were admitted in each step to gener
monium (CTMA) hydroxide solution prepared as in ate 168 data points in the relative pressure range from 0
Example 1. After stirring for 0.5 hour, 36 grams of solid to 0.6. At least about 100 points are required to define
cetyltrimethylammonium bromide were added to the 35 the isotherm with sufficient detail.
mixture. After additional stirring for 0.25 hour, 20 The step (inflection) in the isotherm indicates filling
grams of ethanol were added to the mixture. The mix of a pore system. The size of the step indicates the
ture was then placed in an autoclave and maintained at amount adsorbed, whereas the position of the step in
120° C. with stirring for 24 hours. The mixture had a terms of P/Po reflects the size of the pores in which the
composition in terms of moles per SiO2 assuming con adsorption takes place. Larger pores are filled at higher
plete exchange of the surfactant: P/Po. In order to better locate the position of the step in
the isotherm, the derivative with respect to log (P/P) is
formed. This conversion was obtained by using the
0.003 moles of Al2O3 following formula:
0.79 moles of (CTMA)2O 45
50.77 moles of H2O
8.03 moles of C2H5OH K
log(P/P) = is (or S4Das
a
The mixture had a Solvent/(R'2O+M2O) ratio of 74.
The resultant product was filtered, washed, air-dried 50 S10 S4 -- Slo
at 100° C., and calcined (6 hours at 540 C. in air). A 9(L - D/2)9 3(D/2) 9(D/2)9
tabulation of the X-ray diffraction peak positions ob
tained by deconvolution of X-ray diffraction pattern for wherein d=pore diameter in nanometers, K=32.17,
this preparation follows: S=0.2446, L=d-0.19, and D =0.57. .
55 This formula is derived from the method of Horvath
Interplanar d-Spacing Relative intensity d/d and Kawazoe (G. Horvath et al., J. Chem. Eng. Japan,
35.5 100 1.00 16 (6), 470 (1983)). The constants required for the imple
3.5 28 0.88 mentation of this formula were determined from a mea
23.2 0.65 sured isotherm of AlPO4-5 and its known pore size.
21.7 1 0.61 This method is particularly useful for microporous ma
9.4
18.5
10
8
0.55
0.52
terials having pores of up to about 60 Angstroms in
17.7 5 0.50
diameter.
17.0 2 0.48 The results of this procedure for the samples from
65
Examples 1 through 6 are tabulated below.
The benzene sorption capacity of the product mate
rial was measured to be approximately 68 wt.%. The Example Pore Diameter, Angstroms
product had a BET surface area of 966 m2/g. 28
21
5,300,277
22
-continued ions, and a solvent or solvent mixture such that the
mole ratio
Example Pore Diameter, Angstrons
2 29 Solvent/(R'2O--M2O)
3 30
4. 29
5 27 is from about 45 to less than about 100,
6 3. (2) adding one or a combination of oxides of tetrava
lent element Y, and optionally one or a combina
tion of oxides of elements selected from the group
EXAMPLE 8(B) 10 consisting of divalent element W, trivalent element
Argon Physisorption For Pore Systems Over About X and pentavalent element Z to the mixture of step
60 Angstroms Diameter (1), such that the mole ratio
The above method of Horvath and Kawazoe for
determining pore size from physisorption isotherms was 15
intended to be applied to pore systems of up to 20 Ang is from about 0.3 to about 1, where R is the total of
strons diameter; but with some care as above detailed, R'--R",
its use can be extended to pores of up to 60 Angstroms (3) agitating the mixture resulting from step (2) at a
diameter.
In the pore regime above 60 Angstroms diameter, temperature of from about O' C. to about 50 C. and
however, the Kelvin equation can be applied. It is usu 20 a pH of from about 7 to about 14, and
ally given as: (4) crystallizing the product from step (3) at a temper
ature of from about 50 C. to about 200 C.,
the improvement wherein Y comprises silicon and the
-2AV oxide of Y is added as a colloidal dispersion of SiO2 or
in(P/P) = rRT cos 8
25 a precipitated SiO2, ethanol is added to the mixture
where:
prior to crystallizing step (4), and wherein the Sol
A = surface tension of sorbate
vent/(R'2O--M2O) mole ratio of step (1) is from about
45 to less than about 110.
Vre molar volume of sorbate 2. The method of claim 1 wherein the mole ratio
e = contact angle (usually taken for practical reasons 30 R2O/CYO2--X2O3-Z2O5 -- WO) is from about 0.3 to
to be 0) about 0.6.
R = gas constant 3. The method of claim 1 wherein R' comprises an ion
T= absolute temperature of the formula RR2R3R4Q+, wherein Q is nitrogen or
rk= capillary condensate (pore) radius phosphorus and wherein at least one of R1, R2, R3 and
P/Po= relative pressure (taken from the physisorp 35 R4 is aryl or alkyl of from 8 to about 36 carbon atoms or
tion isotherm) combinations thereof, the remainder of R1, R2, R3 and
The Kelvin equation treats adsorption in pore sys R4 being selected from the group consisting of hydro
tens as a capillary condensation phenomenon and re gen, alkyl of from 1 to 7 carbon atoms and combinations
lates the pressure at which adsorption takes place to the thereof.
pore diameter through the surface tension and contact 4. The method of claim 1 wherein R" comprises an
angle of the adsorbate (in this case, argon). The princi ion of the formula RR2R3R4Q, wherein Q is nitrogen
ples upon which the Kelvin equation are based are valid or phosphorus and wherein at least one of R1, R2, R3
for pores in the size range 50 to 1000 Angstrom diame and R4 are selected from the group consisting of hydro
ter. Below this range the equation no longer reflects gen, alkyl of 1 to 7 carbon atoms and combinations
physical reality, since true capillary condensation can 45 thereof.
not occur in smaller pores; above this range the loga 5. The method of claim 1 wherein R' is cetyltrime
rithmic nature of the equation precludes obtaining suffi thylammonium, octadecyltrimethylammonium, cetyl
cient accuracy for pore size determination. pyridinium, myristyltrimethylammonium, decyltrime
The particular implementation of the Kelvin equation thylammonium, dodecyltrimethylammonium or dime
often chosen for measurement of pore size is that re 50 thylididodecylammonium.
ported by Dollimore and Heal (D. Dollimore and G. R. 6. The method of claim 5 wherein R' is cetyltrime
Heal, J. Applied Chem, 14, 108 (1964)). This method thylammonium or octadecyltrimethylammonium.
corrects for the effects of the surface layer of adsorbate 7. The method of claim 1 wherein said solvent is
on the pore wall, of which the Kelvin equation proper C-C6 alcohol, C1-C6 diol, water or mixture thereof.
does not take account, and thus provides a more accu 55 8. The method of claim 1 wherein said porous crystal
rate measurement of pore diameter. While the method line phase material has, after calcination, an X-ray dif
of Dollinore and Heal was derived for use on desorp fraction pattern including values substantially as shown
tion isotherms, it can be applied equally well to adsorp in Table 2 of the specification.
tion isotherms by simply inverting the data set. 9. The method of claim 1 wherein said porous crystal
What is claimed is: 60 line phase material has, after calcination, an X-ray dif
1. In a method for synthesizing a composition of fraction pattern including values substantially as shown
matter comprising an inorganic, porous crystalline in Table 3 of the specification.
phase material having, after calcination, an X-ray dif 10. The method of claim 1 wherein said porous crys
fraction pattern including values substantially as shown talline phase material has, after calcination, an X-ray
in Table 1 which comprises the steps of 65 diffraction pattern including values substantially as
(1) combining a primary organic directing agent (R'), shown in Table 4 of the specification.
optional additional organic directing agent (R'), 11. The method of claim 1 wherein said porous crys
optional source of alkali or alkaline earth metal (M) talline phase material has, after calcination, an X-ray
23
5,300,277
24
diffraction pattern including values substantially as 14. The method of claim 13 wherein the sun
shown in Table 5 of the specification. (a-b-c) is greater than d, and h =2.
12. The method of claim 1 wherein said porous crys 15. The method of claim 13 wherein W is a divalent
talline phase material has, after calcination, an X-ray first row transition metal or magnesium; X is aluminum,
diffraction pattern including values substantially as boron, gallium or iron; and Z is phosphorus.
16. The method of claim 13 wherein W comprises
shown in Table 6 of the specification. cobalt, X comprises aluminum, and Z comprises phos
13. The method of claim 1 wherein said crystalline phorus.
phase has a composition expressed as follows: 17. The method of claim 14 wherein W is a divalent
10 first row transition metal or magnesium; X is aluminum,
boron, gallium or iron; and Z is phosphorus.
18. The method of claim 14 wherein W comprises
wherein M is one or more ions; n is the charge of the cobalt, X comprises aluminum, and Z comprises phos
phorus.
composition excluding M expressed as oxides; q is the 15 19. The method of claim 13 wherein a and d are 0 and
weighted molar average valence of M; n/q is the num h=2.
ber of moles or mole fraction of M; W is one or more 20. The method of claim 19 wherein X comprises
divalent elements; X is one or more trivalent elements; aluminum, boron, gallium or iron.
21. The method of claim 1 wherein said crystalline
Y comprises silicon; Z is one or more pentavalent ele 0 phase
ments; a,b,c, and d are mole fractions of W,X,Y and Z, pores ofhas a regular arrangement of uniformly sized
respectively; h is a number of from 1 to 2.5; and by argonatphysisorption.
least about 13 Angstrom Units as measured
(a+b+c+d)= 1. t k . . .
25
30
35
45
SO
55
65