Foam reduction during synthesis of MCM-41

A method for synthesizing an ultra-large pore crystalline material which can be used as a sorbent or catalyst component for the conversion of organic and inorganic compounds is improved through the addition of an antifoaming agent. The addition of antifoaming agents reduces foaming without interfering with material synthesis. Elimination of foam allows for easier charging of autoclaves and processing of synthesis mixtures.

FIELD OF THE INVENTION 
The process of the present invention relates to the synthesis of M41S 
materials using antifoaming agents. 
BACKGROUND OF THE INVENTION 
Porous inorganic solids have great utility as catalysts and separation 
media for industrial applications. Catalytic and sorptive activity are 
enhanced by the extensive surface area provided by a readily accessible 
microstructure characteristic of these solids. 
The porous materials in use today can be sorted into three broad categories 
using the details of their microstructure as a basis for classification. 
These categories are 1) amorphous and paracrystalline supports, 2) 
crystalline molecular sieves and 3) modified layered materials. 
Variations in the microstructures of these materials manifest themselves as 
important differences in the catalytic and sorptive behavior of the 
materials, as well as differences in various observable properties used to 
characterize them. For example, surface area, pore size and variability in 
pore sizes, the presence or absence of X-ray diffraction patterns, as well 
as the details in such patterns, and the appearance of the materials when 
their microstructure is studied by transmission electron microscopy and 
electron diffraction methods can be used to characterize porous inorganic 
solids. 
Amorphous and paracrystalline materials represent an important class of 
porous inorganic solids which have been used for many years in industrial 
applications. Typical examples of these materials are the amorphous 
silicas commonly used in catalyst formulations and the paracrystalline 
transitional aluminas used as solid acid catalysts and petroleum reforming 
catalyst supports. 
The amorphous materials are generally characterized as "amorphous" since 
they are substances having no long range order. Unfortunately, this can be 
somewhat misleading since almost all materials are ordered to some degree, 
at least on the local scale. An alternate term which has been used to 
describe these materials is "X-ray indifferent". The microstructure of the 
silicas consists of 100-250 .ANG. particles of dense amorphous silica 
(Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Vol. 20, 
John Wiley & Sons, New York, p. 766-781, 1982), with the porosity 
resulting from voids between the particles. Since there is no long range 
order in these materials, the pore sizes tend to be distributed over a 
rather large range. This lack of order also manifests itself in the X-ray 
diffraction pattern, which is usually featureless. 
Paracrystalline materials such as the transitional aluminas also have a 
wide distribution of pore sizes, but exhibit better defined X-ray 
diffraction patterns usually consisting of a few broad peaks. The 
microstructure of these materials consists of tiny crystalline regions of 
condensed alumina phases and the porosity of the materials results from 
irregular voids between these regions (K. Wefers and Chanakya Misra, 
"Oxides and Hydroxides of Aluminum", Technical Paper No. 19 Revised, Alcoa 
Research Laboratories, p. 54-59, 1987). 
Despite any differences arising between these paracrystalline or amorphous 
materials, neither substance has long range order controlling the sizes of 
pores in the material. Consequently, variability in pore size is typically 
quite high. The sizes of pores in these materials fall into what is known 
in the art as the "mesoporous range", which, for the purposes of this 
Application, is from about 13 to 200 .ANG.. 
In sharp contrast to these structurally ill-defined solids are materials 
whose pore size distribution is narrow because it is controlled by the 
precisely repeating crystalline nature of the materials' microstructure. 
These materials are referred to as "molecular sieves", the most important 
examples of which are zeolites. 
Zeolites, 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. These crystalline structures contain a large number of 
small 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 provide 
access to molecules of certain dimensions while rejecting those of larger 
dimensions, these materials are known as "molecular sieves". These 
molecular sieves have been utilized in a variety of ways in order to take 
advantage of their properties. 
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 Group 
IIIB element oxides, e.g. AlO.sub.4, in which the tetrahedra are 
cross-linked by the sharing of oxygen atoms. The ratio of the total Group 
IIIB element, e.g. aluminum, and Group IVB element, e.g. silicon, atoms to 
oxygen atoms is 1:2. The electrovalence of the tetrahedra containing the 
Group IIIB element, e.g. aluminum, is balanced by the inclusion of a 
cation in the crystal. Examples of such cations include alkali metal or 
alkaline earth metal cations. This can be expressed wherein the ratio of 
the Group IIIB element, e.g. aluminum, 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, with ratios 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, as measured within the limits of 
present analytical measurement techniques. U.S. Pat. No. 3,941,871 (U.S. 
Pat. No. Re. 29,948) discloses a porous crystalline silicate made from a 
reaction mixture containing no deliberately added aluminum 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 
silicates of varying alumina and metal content. 
Additionally, aluminum phosphates are taught in the U.S. Pat. Nos. 
4,310,440 and 4,385,994, for example. 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. 
An early reference to a hydrated aluminum phosphate which is crystalline 
until heated at about 110.degree. C., at which point it becomes amorphous 
or transforms, 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", Jul. 6, 1961 (received), pp 
1762-1776. This material, when crystalline, is identified by the JCPDS 
International Center for Diffraction Data 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. 
Compositions comprising crystals having a framework topology after heating 
at 110.degree. C. or higher and exhibiting an X-ray diffraction pattern 
consistent with a material having pore windows formed by 18 tetrahedral 
members of about 12-13 .ANG. in diameter are taught in U.S. Pat. No. 
4,880,611. 
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 .ANG.. 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); 4,623,527 (MCM-10); 4,639,358 
(MCM-1); 4,647,442 (MCM-2); 4,664,897 (MCM-4); 4,638,357 (MCM-5); and 
4,632,811 (MCM-3). 
A method for synthesizing crystalline metalloaluminophosphates is shown in 
U.S. Pat. No. 4,713,227. 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 Patent 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 patents 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. 
The precise crystalline microstructure of most zeolites manifests itself in 
a well-defined X-ray diffraction pattern that usually contains many sharp 
maxima and that serves to uniquely define the material. Similarly, the 
dimensions of pores in these materials are very regular, due to the 
precise repetition of the crystalline microstructure. All molecular sieves 
discovered to date have pore sizes in the microporous range, which is 
usually quoted as 2 to 20 .ANG., with the largest reported being about 12 
.ANG.. 
Certain layered materials, which contain layers capable of being spaced 
apart with a swelling agent, may be pillared to provide materials having a 
large degree of porosity. Examples of such layered materials include 
clays. Such clays may be swollen with water, whereby the layers of the 
clay are spaced apart by water molecules. Other layered materials are not 
swellable with water, but may be swollen with certain organic swelling 
agents such as amines and quaternary ammonium compounds. Examples of such 
non-water swellable layered materials are described in U.S. Pat. No. 
4,859,648 and include layered silicates, magadiite, kenyaite, trititanates 
and perovskites. Another example of a non-water swellable layered 
material, which can be swollen with certain organic swelling agents, is a 
vacancy-containing titanometallate material, as described in U.S. Pat. No. 
4,831,006. 
Once a layered material is swollen, the material may be pillared by 
interposing a thermally stable substance, such as silica, between the 
spaced apart layers. The aforementioned U.S. Pat. Nos. 4,831,006 and 
4,859,648 describe methods for pillaring the non-water swellable layered 
materials described therein and are incorporated herein by reference for 
definition of pillaring and pillared materials. 
Other patents teaching pillaring of layered materials and the pillared 
products include U.S. Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and 
4,367,163; and European Patent Application 205,711. 
The X-ray diffraction patterns of pillared layered materials can vary 
considerably, depending on the degree that swelling and pillaring disrupt 
the otherwise usually well-ordered layered microstructure. The regularity 
of the microstructure in some pillared layered materials is so badly 
disrupted that only one peak in the low angle region on the X-ray 
diffraction pattern is observed, at a d-spacing corresponding to the 
interlayer repeat in the pillared material. Less disrupted materials may 
show several peaks in this region that are generally orders of this 
fundamental repeat. X-ray reflections from the crystalline structure of 
the layers are also sometimes observed. The pore size distribution in 
these pillared layered materials is narrower than those in amorphous and 
paracrystalline materials but broader than that in crystalline framework 
materials. 
Indeed, X-ray diffraction patterns have come to play an important role in 
identification of various crystalline materials, especially pillared 
layered materials. Nevertheless, it is the physical properties of these 
materials which render them valuable assets to the scientific and 
industrial communities. These materials are not only valuable when 
employed in the petroleum industry, but they have also been found to 
exhibit properties useful for a variety of applications including such 
fields as nonlinear optics and the biological and chemical sciences. 
The use of surfactants generates foam in the synthesis of crystalline 
materials. The presence of foam poses problems in the syntheses, 
inhibition of raw material conversion and difficulties in movement of the 
product slurry, purification and filtration, and in the commercial 
manufacture of the above materials. Therefore, it is an object of the 
present invention to provide an M41S synthesis method which reduces the 
problem of foaming. 
SUMMARY OF THE INVENTION 
The method of the present invention involves the use of an antifoaming 
agent to reduce the foam produced by surfactants in M41S synthesis. By 
eliminating the foam, the synthesis and processing of these materials is 
enhanced. Crystallizer charging is generally inhibited by the presence of 
foam created by the large amount of surfactants used. By removing the 
foam, charging and transporting of the synthesis mixture is simplified. 
The invention therefore includes a method for synthesizing a composition of 
matter comprising an inorganic, porous, non-layered crystalline phase 
material exhibiting, after calcination, an X-ray diffraction pattern with 
at least one peak at a d-spacing greater than about 18 Angstrom Units with 
a relative intensity of 100 and a benzene adsorption capacity of greater 
than 15 grams benzene per 100 grams of said material at 50 torr and 
25.degree. C., said method comprising the steps of: 
(a) preparing a mixture capable of forming said composition, said mixture 
comprising a source of silica, a source of alumina, an organic (R') agent 
and a solvent or solvent mixture, wherein R' comprises an ion of the 
formula R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q.sup.+, wherein Q is nitrogen or 
phosphorus and wherein at least one of R.sub.1, R.sub.2, R.sub.3 and 
R.sub.4 is aryl or alkyl of from 6 to about 36 carbon atoms or 
combinations thereof, the remainder of R.sub.1, R.sub.2, R.sub.3 and 
R.sub.4 being selected from the group consisting of hydrogen, alkyl of 
from 1 to 5 carbon atoms and combinations thereof; 
(b) maintaining said mixture under sufficient conditions of pH, temperature 
and time for formation of said composition of matter; and 
(c) recovering said composition of matter, wherein said mixture of step (a) 
comprises antifoaming agent. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is directed to a method for improving the synthesis 
of the crystalline material of the invention such that the tendency of the 
synthesis mixture to generate foam is reduced. Addition of antifoaming 
agent reduces foaming without interfering with material synthesis. 
Antifoaming agents are substances that reduce the surface tension of a 
liquid, thus inhibiting the formation of bubbles in the liquid when it is 
agitated. Suitable antifoaming agents for use in the method of the present 
invention include organic phosphates, polyoxyalkylene polymers, silicone 
fluids, such as organosiloxane polymers and siloxane glycol copolymers, 
and mixtures thereof. Any material which lowers the surface tension in the 
reaction mixture may serve as an antifoaming agent in the method of the 
present invention. 
Generally, the amount of antifoaming agent used in the synthesis mixture is 
at least about 50 ppm, based on organic directing agent, and preferably at 
least about 100 ppm, based on organic directing agent. 
Generally the addition of antifoaming agents is at a temperature in the 
range of from about 25.degree. C. to about 302.degree. C. The order of 
addition of the antifoaming agent to the synthesis mixture is not 
critical. 
The material of this invention may be characterized as a novel synthetic 
composition of matter comprising an ultra-large pore size crystalline 
phase. This material may be an inorganic, porous, non-layered, crystalline 
phase material which can be characterized (in its calcined form) by an 
X-ray diffraction pattern with at least one peak at a d-spacing greater 
than about 18 Angstrom with a relative intensity of 100 and a benzene 
sorption capacity of greater than 15 grams of benzene per 100 grams of the 
material at 50 torr and 25.degree. C. This material and its preparation 
and properties are described in further detail in U.S. Pat. No. 5,102,643, 
incorporated herein by reference. 
The preferred form of the crystalline material is an inorganic, porous 
material having a hexagonal arrangement of uniformly sized pores with a 
maximum perpendicular cross-section pore diameter of at least about 13 
.ANG. Units, and typically within the range of from about 13 .ANG. Units 
to about 200 .ANG. Units, identified as MCM-41. This material exhibits a 
hexagonal electron diffraction pattern that can be indexed with a 
d.sub.100 value greater than about 18 Angstrom which corresponds to at 
least one peak in the X-ray diffraction pattern. This material and its 
preparation and properties are described in further detail in U.S. Pat. 
No. 5,098,684, incorporated herein by reference. 
The inorganic mesoporous crystalline material of this invention may have 
the following composition: 
EQU M.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h) 
wherein W is a divalent element, such as magnesium, and/or a divalent first 
row transition metal, e.g., manganese, cobalt and iron, preferably cobalt; 
X is a trivalent element, such as aluminum, boron, iron and/or gallium, 
preferably aluminum; Y is a tetravalent element such as silicon and/or 
germanium, preferably silicon; Z is a pentavalent element, such as 
phosphorus; M is one or more ions, such as, for example, ammonium, Group 
IA, IIA and VIIB ions, usually hydrogen, sodium and/or fluoride ions; n is 
the charge of the composition excluding M expressed as oxides; q is the 
weighted molar average valence of M; n/q is the number of moles or mole 
fraction of M; a, b, c, and d are mole fractions of W, X, Y and Z, 
respectively; h is a number of from 1 to 2.5; and (a+b+c+d)=1. 
A preferred embodiment of the above crystalline material is when (a+b+c) is 
greater than d, and h=2. A further embodiment is when a and d=0, and h=2. 
In the as-synthesized form, the material may have a composition, on an 
anhydrous basis, expressed empirically as follows: 
EQU rPM.sub.n/q (W.sub.a X.sub.b Y.sub.c Z.sub.d O.sub.h) 
where R is the total organic material not included in M as an ion, and r is 
the coefficient for R, i.e., the number of moles or mole fraction of R. 
The M and R components are associated with the material as a result of 
their presence during crystallization, and are easily removed or, in the 
case of M, replaced by post-crystallization methods described below. 
To the extent desired, the original M, e.g., sodium, ions of the 
as-synthesized support material can be replaced in accordance with 
conventional ion-exchange techniques. Preferred replacing ions include 
metal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions and 
mixtures of these ions. Replacing ions include hydrogen, rare earth metals 
and metals of Groups VIIA (e.g., Mn), VIIIA (e.g., Ni),IB (e.g., Cu), IVB 
(e.g., Sn) of the Periodic Table of the Elements and mixtures of these 
ions. 
The crystalline (i.e., having sufficient order to provide a diffraction 
pattern such as, for example, by X-ray, electron or neutron diffraction, 
following calcination, with at least one peak) mesoporous material may be 
characterized by its structure, which includes extremely large pore 
windows as well as by its high sorption capacity. The term "mesoporous" is 
used here to indicate crystals having uniform pores within the range of 
from about 13 Angstrom to about 200 Angstrom. The mesoporous materials 
have uniform pores within the range of from about 13 Angstrom to about 200 
Angstrom, more usually from about 15 Angstrom to about 100 Angstrom. Since 
these pores are significantly larger than those of other crystalline 
materials, it is appropriate to refer to them as ultra-large pore size 
materials. For the purposes of this application, a working definition of 
"porous" is a material that adsorbs at least 1 gram of a small molecule, 
such as Ar, N.sub.2, n-hexane or cyclohexane, per 100 grams of the solid, 
at appropriate temperature and atmospheric pressure. 
The synthesis of the material is described in U.S. Pat. Nos. 5,108,725 and 
5,057,296, incorporated herein by reference. 
The material can be distinguished from other porous inorganic solids by the 
regularity of its large open pores, whose pore size more nearly resembles 
that of amorphous or paracrystalline materials, but whose regular 
arrangement and uniformity of size (pore size distribution within a single 
phase of, for example, .+-.25%, usually .+-.15% or less of the average 
pore size of that phase) resemble more those of crystalline framework 
materials such as zeolites. The preferred MCM-41 materials have a 
hexagonal arrangement of large open channels that can be synthesized with 
open internal diameters from about 13 Angstrom to about 200 Angstrom. The 
term "hexagonal" is intended to encompass not only materials that exhibit 
mathematically perfect hexagonal symmetry within the limits of 
experimental measurement, but also those with significant observable 
deviations from that ideal state. A working definition as applied to the 
microstructure of MCM-41 would be that most channels in the material would 
be surrounded by six nearest neighbor channels at roughly the same 
distance. Defects and imperfections will cause significant numbers of 
channels to violate this criterion to varying degrees, depending on the 
quality of the material's preparation. Samples which exhibit as much as 
.+-.25% random deviation from the average repeat distance between adjacent 
channels still clearly give recognizable images of the present ultra-large 
pore materials. Comparable variations are also observed in the d.sub.100 
values from the electron diffraction patterns. 
The size of the pores in the present mesoporous materials is large enough 
that the spatiospecific selectivity with respect to transition state 
species in reactions such as cracking is minimized (Chen et al., "Shape 
Selective Catalysis in Industrial Applications", Chemical Industries, 36, 
41-61 (1989) to which reference is made for a discussion of the factors 
affecting shape selectivity). Diffusional limitations are also minimized 
as a result of the very large pores. 
The most regular preparations of the present support material give an X-ray 
diffraction pattern with a few distinct maxima in the extreme low angle 
region. The positions of these peaks approximately fit the positions of 
the hkO reflections from a hexagonal lattice. The X-ray diffraction 
pattern, however, is not always a sufficient indicator of the presence of 
these materials, as the degree of regularity in the microstructure and the 
extent of repetition of the structure within individual particles affect 
the number of peaks that will be observed. Indeed, preparations with only 
one distinct peak in the low angle region of the X-ray diffraction pattern 
have been found to contain substantial amounts of MCM-41 in them. Other 
techniques to illustrate the microstructure of this material are 
transmission electron microscopy and electron diffraction. Properly 
oriented specimens of the MCM-41 material show a hexagonal arrangement of 
large channels and the corresponding electron diffraction pattern gives an 
approximately hexagonal arrangement of diffraction maxima. The d.sub.100 
spacing of the electron diffraction patterns is the distance between 
adjacent spots on the hkO projection of the hexagonal lattice and is 
related to the repeat distance a.sub.0 between channels observed in the 
electron micrographs through the formula d.sub.100 =a.sub.0 .sqroot.3/2. 
This d.sub.100 spacing observed in the electron diffraction patterns 
corresponds to the d-spacing of a low angle peak in the X-ray diffraction 
pattern of the material. The most highly ordered preparations of the 
MCM-41 material obtained so far have 20-40 distinct spots observable in 
the electron diffraction patterns. These patterns can be indexed with the 
hexagonal hkO subset of unique reflections of 100, 110, 200, 210, etc., 
and their symmetry-related reflections. 
In its calcined form, the crystalline material may be further characterized 
by an X-ray diffraction pattern with at least one peak at a position 
greater than about 18 Angstrom d-spacing (4.909.degree. 2.theta. for Cu 
K-alpha radiation) which corresponds to the d.sub.100 value of the 
electron diffraction pattern of the material, and an equilibrium benzene 
adsorption capacity of greater than about 15 grams benzene/100 grams 
crystal at 50 torr and 25.degree. C. (basis: crystal material having been 
treated in an attempt to insure no pore blockage by incidental 
contaminants, if necessary). 
The equilibrium benzene adsorption capacity characteristic of this material 
is measured on the basis of no pore blockage by incidental contaminants. 
For instance, the sorption test will be conducted on the crystalline 
material phase having any pore blockage contaminants and water removed by 
ordinary methods. Water may be removed by dehydration techniques, e.g., 
thermal treatment. Pore blocking inorganic amorphous materials, e.g., 
silica, and organics may be removed by contact with acid or base or other 
chemical agents such that the detrital material will be removed without 
detrimental effect on the crystal. 
More particularly, the calcined crystalline material may be characterized 
by an X-ray diffraction pattern with at least two peaks at positions 
greater than about 10 Angstrom d-spacing (8.842.degree..theta. for Cu 
K-alpha radiation), at least one of which is at a position greater than 
about 18 Angstrom d-spacing, and no peaks at positions less than about 10 
Angstrom d-spacing with relative intensity greater than about 20% of the 
strongest peak. Still more particularly, the X-ray diffraction pattern of 
the calcined support material will have no peaks at positions less than 
about 10 Angstrom d-spacing with relative intensity greater than about 10% 
of the strongest peak. In any event, at least one peak in the X-ray 
diffraction pattern will have a d-spacing that corresponds to the 
d.sub.100 value of the electron diffraction pattern of the material. 
The calcined inorganic crystalline material may also be characterized as 
having a pore size of about 13 Angstrom or greater as measured by 
physisorption measurements, described below. Pore size is defined by the 
maximum perpendicular pore diameter of the crystal. 
X-ray diffraction data were collected on a Scintag PAD X automated 
diffraction system employing theta-theta geometry, Cu K-alpha radiation, 
and an energy dispersive X-ray detector. Use of the energy dispersive 
X-ray detector eliminated the need for incident or diffracted beam 
monochromators. Both the incident and diffracted X-ray beams were 
collimated by double slit incident and diffracted collimation systems. The 
slit sizes used, starting from the X-ray tube source, were 0.5, 1.0, 0.3 
and 0.2 mm, respectively. Different slit systems may produce differing 
intensities for the peaks. The support materials that have the largest 
pore sizes may require more highly collimated incident X-ray beams in 
order to resolve the low angle peak from the transmitted incident X-ray 
beam. 
The diffraction data were recorded by step-scanning at 0.04 degrees of 
2.theta., where .theta. is the Bragg angle, and a counting time of 10 
seconds for each step. The interplanar spacings, d's, were calculated in 
Angstrom, 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, above 
background, were derived with the use of a profile fitting routine. The 
intensities were uncorrected for Lorentz and polarization effects. The 
relative intensities are given in terms of the symbols vs=very strong 
(75-100), s=strong (50-74), m=medium (25-49) and w=weak (0-24). The 
diffraction data listed as single lines may consist of multiple 
overlapping lines which under certain conditions, such as very high 
experimental resolution or crystallographic changes, may appear as 
resolved or partially resolved lines. Typically, crystallographic changes 
can include minor changes in unit cell parameters and/or a change in 
crystal symmetry, without a substantial change in structure. These minor 
effects, including changes in relative intensities, can also occur as a 
result of differences in cation content, framework composition, nature and 
degree of pore filling, thermal and/or hydrothermal history, and peak 
width/shape variations due to particle size/shape effects, structural 
disorder or other factors known to those skilled in the art of X-ray 
diffraction. 
The equilibrium benzene adsorption capacity is determined by contacting the 
support material, after dehydration or calcination at, for example, about 
540.degree. C. for at least about one hour and other treatment, if 
necessary, in an attempt to remove any pore blocking contaminants, at 
25.degree. C. and 50 torr benzene until equilibrium is reached. The weight 
of benzene sorbed is then determined as described below. 
The above crystalline material, especially in its metal, hydrogen and 
ammonium forms, may be readily converted to another form by thermal 
treatment (calcination). This thermal treatment is generally performed by 
heating one of these forms at a temperature of at least 400.degree. C. for 
at least 1 minute and generally not longer than 20 hours, preferably from 
about 1 to about 10 hours. While subatmospheric pressure can be employed 
for the thermal treatment, atmospheric pressure is desired for reasons of 
convenience, such as in air, nitrogen, ammonia, etc. The thermal treatment 
can be performed at a temperature up to about 750.degree. C. The thermally 
treated product is particularly useful in the catalysis of certain 
hydrocarbon conversion reactions. 
MCM-41 can be prepared by one of several methods, each with particular 
limitations. 
A first method involves a reaction mixture having an X.sub.2 O.sub.3 
/YO.sub.2 mole ratio of from 0 to about 0.5, but an Al.sub.2 O.sub.3 
/SiO.sub.2 mole ratio of from 0 to 0.01, a crystallization temperature of 
from about 25.degree. C. to about 250.degree. C., preferably from about 
50.degree. C. to about 175.degree. C., and an organic directing agent, 
hereinafter more particularly described, or, preferably a combination of 
that organic directing agent plus an additional organic directing agent, 
described below. This first method comprises preparing a reaction mixture 
containing sources of, for example, alkali or alkaline earth metal (M), 
e.g., sodium or potassium, cation if desired, one or a combination of 
oxides selected from the group consisting of divalent element W, e.g., 
cobalt, trivalent element X, e.g., aluminum, tetravalent element Y, e.g., 
silicon, and pentavalent element Z, e.g., phosphorus, an organic (R) 
directing agent, described below, and a solvent or solvent mixture, such 
as, for example, C.sub.1 -C.sub.6 alcohols, C.sub.1 -C.sub.6 diols and/or 
water, especially water. The reaction mixture has a composition, in terms 
of mole ratios of oxides, within the following ranges: 
______________________________________ 
Reactants Useful Preferred 
______________________________________ 
X.sub.2 O.sub.3 /YO.sub.2 
0 to 0.5 0.001 to 0.5 
Al O.sub.3 /SiO.sub.2 
0 to 0.01 0.001 to 0.01 
X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5) 
0.1 to 100 
0.1 to 20 
X.sub.2 O.sub.2 + O.sub.3 /(YO2 + WO + Z2O5) 
0.1 to 100 
0.1 to 20 
Solvent/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
1 to 1500 5 to 1000 
OH.sup.- /YO.sub.2 0 to 10 0 to 5 
(M.sub.2/e O + R.sub.2/f O)/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0.01 to 20 
0.05 to 5 
M.sub.2/e O/ 
YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0 to 10 0 to 5 
R.sub.2/f O/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0.01 to 2.0 
0.03 to 1.0 
______________________________________ 
where e and f are the weighted average valences of M and R, respectively. 
In this first method, when no Z and/or W oxides are added to the reaction 
mixture, the pH is important and must be maintained at from about 9 to 
about 14. When Z and/or W oxides are present in the reaction mixture, the 
pH is not narrowly important for synthesis of MCM-41. In this, as well as 
the following methods for synthesis of MCM-41, the R.sub.2/f O/(YO.sub.2 
+WO+Z.sub.2 O.sub.5 +X.sub.2 O.sub.3) ratio is important. When this ratio 
is less than 0.01 or greater than 2.0, impurity products tend to be 
synthesized at the expense of the desired crystalline material. 
A second method for synthesis of MCM-41 involves a reaction mixture having 
an X.sub.2 O.sub.3 /YO.sub.2 mole ratio of from about 0 to about 0.5, a 
crystallization temperature of from about 25.degree. C. to about 
250.degree. C., preferably from about 50.degree. C. to about 175.degree. 
C., and two separate organic directing agents, i.e., the organic and 
additional organic directing agents, described below. This second method 
comprises preparing a reaction mixture containing sources of, for example, 
alkali or alkaline earth metal (M), e.g., sodium or potassium, cation if 
desired, one or a combination of oxides selected from the group consisting 
of divalent element W, e.g., cobalt, trivalent element X, e.g., aluminum, 
tetravalent element Y, e.g., silicon, and pentavalent element Z, e.g., 
phosphorus, a combination of organic directing agent and additional 
organic directing agent (R), each described below, and a solvent or 
solvent mixture, such as, for example, C.sub.1 -C.sub.6 alcohols, C.sub.1 
-C.sub.6 diols and/or water, especially water. The reaction mixture has a 
composition, in terms of mole ratios of oxides, within the following 
ranges: 
______________________________________ 
Reactants Useful Preferred 
______________________________________ 
X.sub.2 O.sub.3 /YO.sub.2 
0 to 0.5 0.001 to 0.5 
X.sub.2 O.sub.3 /(YO.sub.2 + Z.sub.2 O.sub.5) 
0.1 to 100 
0.1 to 20 
X.sub.2 O.sub.3 /(YO.sub.2 + WO + Z.sub.2 O.sub.5) 
0.1 to 100 
0.1 to 20 
Solvent/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3 
1 to 1500 5 to 1000 
OH.sup.- /YO.sub.2 0 to 10 0 to 5 
(M.sub.2/e O + R.sub.2/f O)/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0.01 to 20 
0.05 to 5 
M.sub.2/e O/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0 to 10 0 to 5 
R.sub.2/f O/ 
(YO.sub.2 + WO + Z.sub.2 O.sub.5 + X.sub.2 O.sub.3) 
0.1 to 2.0 
0.12 to 1.0 
______________________________________ 
where e and f are the weighted average valences of M and R, respectively. 
In this second method, when no Z and/or W oxides are added to the reaction 
mixture, the pH is important and must be maintained at from about 9 to 
about 14. When Z and/or W oxides are present in the reaction mixture, the 
precise value of the pH is not important for crystallization. 
A third method for synthesis of MCM-41 is where X comprises aluminum and Y 
comprises silicon, the crystallization temperature must be from about 
25.degree. C. to about 175.degree. C., preferably from about 50.degree. C. 
to about 150.degree. C., and an organic directing agent, described below, 
or, preferably a combination of that organic directing agent plus an 
additional organic agent, described below, is used. This third method 
comprises preparing a reaction mixture containing sources of, for example, 
alkali or alkaline earth metal (M), e.g., sodium or potassium, cation if 
desired, one or more sources of aluminum and/or silicon, an organic (R) 
directing agent, hereinafter more particularly described, and a solvent or 
solvent mixture, such as, for example C.sub.1 -C.sub.6 alcohols, C.sub.1 
-C.sub.6 diols and/or water, especially water. The reaction mixture has a 
composition, in terms of mole ratios of oxides, within the following 
ranges: 
______________________________________ 
Reactants Useful Preferred 
______________________________________ 
Al.sub.2 O.sub.3 /SiO.sub.2 
0 to 0.5 0.001 to 0.5 
Solvent/SiO.sub.2 
1 to 1500 5 to 1000 
OH.sup.- /SiO.sub.2 
0 to 10 0 to 5 
(M.sub.2/e O + R.sub.2/f O)/ 
(SiO.sub.2 + Al.sub.2 O.sub.3) 
0.01 to 20 0.05 to 5 
M.sub.2/e O/ 
(SiO.sub.2 + Al.sub.2 O.sub.3) 
0 to 5 0 to 3 
R.sub.2/f O/ 
(SiO.sub.2 + Al.sub.2 O.sub.3) 
0.01 to 2 0.03 to 1 
______________________________________ 
where e and f are the weighted average valences of M and R, respectively. 
In this third method, the pH is important and must be maintained at from 
about 9 to about 14. This method involves the following steps: 
(1) Mix the organic (R) directing agent with the solvent or solvent mixture 
such that the mole ratio of solvent/R.sub.2/f O is within the range of 
from about 50 to about 800, preferably from about 50 to 500. This mixture 
constitutes the "primary template" for the synthesis method. 
(2) To the primary template mixture of step (1) add the sources of oxides, 
e.g., silica and/or alumina such that the ratio of R.sub.2/f O/(SiO.sub.2 
+Al.sub.2 O.sub.3) is within the range of from about 0.01 to about 2.0. 
(3) Agitate the mixture resulting from step (2) at a temperature of from 
about 20.degree. C. to about 40.degree. C., preferably for from about 5 
minutes to about 3 hours. 
(4) Allow the mixture to stand with or without agitation, preferably at a 
temperature of from about 20.degree. C. to about 100.degree. C., and 
preferably for from about 10 minutes to about 24 hours. 
(5) Crystallize the product from step (4) at a temperature of from about 
50.degree. C. to about 175.degree. C., preferably for from about 1 hour to 
about 72 hours. Crystallization temperatures higher in the given ranges 
are most preferred. 
A fourth method for the synthesis of MCM-41 involves the reaction mixture 
used for the third method, but the following specific procedure with 
tetraethylorthosilicate the source of silicon oxide: 
(1) Mix the organic (R) directing agent with the solvent or solvent mixture 
such that the mole ratio of solvent/R.sub.2/f O is within the range of 
from about 50 to about 800, preferably from about 50 to 500. This mixture 
constitutes the "primary template" for the synthesis method. 
(2) Mix the primary template mixture of step (1) with 
tetraethylorthosilicate and a source of aluminum oxide, if desired, such 
that the R.sub.2/f O/SiO.sub.2 mole ratio is in the range of from about 
0.5 to about 2.0. 
(3) Agitate the mixture resulting from step (2) for from about 10 minutes 
to about 6 hours, preferably from about 30 minutes to about 2 hours, at a 
temperature of from about 0.degree. C. to about 25.degree. C., and a pH of 
less than 12. This step permits hydrolysis/polymerization to take place 
and the resultant mixture will appear cloudy. 
(4) Crystallize the product from step (3) at a temperature of from about 
25.degree. C. to about 150.degree. C., preferably from about 95.degree. C. 
to about 110.degree. C., for from about 4 to about 72 hours, preferably 
from about 16 to about 48 hours. 
In each of the above methods, batch crystallization of the crystalline 
material can be carried out under either static or agitated, e.g., 
stirred, conditions in a suitable reactor vessel, such as for example, 
polypropylene jars or teflon lined or stainless steel autoclaves. 
Crystallization may also be conducted continuously in suitable equipment. 
The total useful range of temperatures for crystallization is noted above 
for each method for a time sufficient for crystallization to occur at the 
temperature used, e.g., from about 5 minutes to about 14 days. The 
crystals are then separated from the liquid and recovered. Following the 
synthesis, the crystalline material should be subjected to treatment to 
remove part or all of any organic constituent. 
By adjusting conditions of the synthesis reaction for each method, like 
temperature, pH and time of reaction, etc., within the above limits, 
various embodiments of the MCM-41 crystalline material with a desired 
average pore size may be prepared. In particular, changing the pH, the 
temperature or the reaction time may promote formation of product crystals 
with different average pore size. 
Non-limiting examples of various combinations of W, X, Y and Z contemplated 
for the first and second synthesis methods include: 
______________________________________ 
W X Y Z 
______________________________________ 
-- Al Si -- 
-- Al -- P 
-- Al Si P 
Co Al -- P 
Co Al Si P 
-- -- Si -- 
______________________________________ 
including the combinations of W being Mg, or an element selected from the 
divalent first row transition metals, e.g., Mn, Co and Fe; X being B, Ga 
or Fe; and Y being Ge. 
An organic directing agent for use in each of the above methods for 
synthesizing MCM-41 from the respective reaction mixtures is an ammonium 
or phosphonium ion of the formula R.sub.1 R.sub.2 R.sub.3 R.sub.4 Q.sup.+, 
i.e., 
##STR1## 
where Q is nitrogen or phosphorus and wherein at least one of R.sub.1, 
R.sub.2, R.sub.3 and R.sub.4 is aryl or alkyl of from 6 to about 36 carbon 
atoms, e.g., --C.sub.6 H.sub.13, --C.sub.10 H.sub.21, --C.sub.16 H.sub.33 
and --C.sub.18 H.sub.37, or combinations thereof, the remainder of 
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being selected from hydrogen, alkyl 
of from 1 to 5 carbon atoms and combinations of these. The compound from 
which the above ammonium or phosphonium ion is derived may be, for 
example, the hydroxide, halide, silicate, or mixtures of these. 
In the first and third methods above it is preferred to have an additional 
organic directing agent and in the second method it is required to have a 
combination of the above organic directing agent and an additional organic 
directing agent. That additional organic directing agent is the ammonium 
or phosphonium ion of the above directing agent formula wherein R.sub.1, 
R.sub.2, R.sub.3 and R.sub.4 together or separately are selected from the 
group consisting of hydrogen and alkyl of 1 to 5 carbon atoms and 
combinations thereof. Any such combination of organic directing agents go 
to make up "R" and will be in molar ratio of about 100/1 to about 0.01/1, 
first above listed organic directing agent/additional organic directing 
agent. 
The particular effectiveness of the required directing agent, when compared 
with other such agents known to direct synthesis of one or more other 
crystal structures, is believed due to its ability to form micelles which 
function as a template in the above reaction mixture in the nucleation and 
growth of the desired ultra-large pore crystals with the limitations 
discussed above. Non-limiting examples of these directing agents include 
cetyltrimethylammonium, cetyltrimethylphosphonium, cetylpyridinium, 
myristyltrimethylammonium, decyltrimethylammonium, 
dodecyltrimethylammonium and dimethyldidodecylammonium. 
Cetyltrimethylammonium chloride is particularly useful. 
The reaction mixture components can be supplied by more than one source. 
The reaction mixture can be prepared either batchwise or continuously. 
Crystal size and crystallization time of M41S will vary with the nature of 
the reaction mixture employed and the crystallization conditions. 
The crystals prepared by the synthesis procedure 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 sorbent 
is molded, such as by extrusion, the crystals can be extruded before 
drying or partially dried and then extruded. The crystals of the 
mesoporous material may be composited with a matrix material to form the 
finished sorbent and for this purpose conventional matrix materials such 
as alumina, silica-alumina and silica are suitable with preference given 
to silica as a non-acidic binder. Other binder materials may be used, for 
example, titania, zirconia and other metal oxides or clays. The mesoporous 
material is usually composited with the matrix in amounts from 80:20 to 
20:80 by weight, typically from 80:20 to 50:50 mesoporous material:matrix. 
Compositing may be done by conventional means including mulling the 
materials together followed by extrusion of pelletizing into the desired 
finished catalyst particles. A preferred method for extrusion with silica 
as a binder is disclosed in U.S. Pat. No. 4,582,815. 
The following examples illustrate the process of the present invention. 
A series of tests are conducted using a 29 wt. % solution of 
cetyltrimethylammonium chloride (CTMA-Cl), a main surfactant in many M41S 
synthesis methods, with three antifoaming agents, Antifoaming Agent A, 
Antifoaming Agent B and Antifoaming Agent C, manufactured by Ultra 
Additives, Inc. The properties of Antifoaming Agents A, B, and C are set 
forth in Tables 1, 2 and 3, respectively. After conducting the tests, 
autoclave synthesis is performed using Antifoaming Agent A to demonstrate 
that the antifoaming agent would reduce foaming and not interfere in the 
formation of M41S. 
TABLE 1 
______________________________________ 
ANTIFOAMING AGENT A 
FOAM BAM MS-455 (manufactured by Ultra Additives, Inc.) 
Specifications and Properties: 
Translucent, off-white 
Appearance liquid 
______________________________________ 
Viscosity (Brookfield RVF, 
2000 to 4000 
Spindle #3, 20 RPM, 25.degree. C.) cps 
Weight per Gallon, pounds 
8.55 to 8.95 
pH (50% solution) 7.0 TO 8.5 
% Non-volatile by Weight 
52 to 56 
Specific Gravity @ 25.degree. C. 
1.026 to 1.074 
(Theoretical) 
Flash Point, PMCC/.degree.C. 
204 
______________________________________ 
TABLE 2 
______________________________________ 
ANTIFOAMING AGENT B 
FOAM BAN MS-525 (manufactured by Ultra Additives, Inc.) 
Specifications and Properties: 
Translucent, off-white 
Appearance liquid 
______________________________________ 
Viscosity (Brookfield RVF, 
2500 to 5500 
Spindle #3, 20 RPM, 25.degree. C.) cps 
Weight per Gallon, pounds 
8.40 to 8.80 
pH (50% solution) 7.0 to 8.5 
% Non-volatile by Weight 
56 to 60 
Specific Gravity @ 25.degree. C. 
1.008 to 1.056 
(Theoretical) 
Flash Point, PMCC/.degree.C. 
204 
______________________________________ 
TABLE 3 
______________________________________ 
ANTIFOAMING AGENT C 
FOAM BAN MS-575 (manufactured by Ultra Additives, Inc.) 
Specifications and Properties: 
Opaque, off-white 
Appearance liquid 
______________________________________ 
Viscosity (Brookfield RVF, 
2000 to 4000 
Spindle #3, 20 RPM, 25.degree. C.) cps 
Weight per Gallon, pounds 
8.55 to 8.95 
pH (50% solution) 7.0 to 8.5 
% Non-volatile by Weight 
71 to 75 
Specific Gravity @ 25.degree. C. 
1.026 to 1.074 
(Theoretical) 
Flash Point, PMCC/.degree.C. 
204 
______________________________________

EXAMPLE 1 
An amount of 145.4 grams of 29 wt. % CTMA-Cl (150 ml.) is placed in a 600 
ml. beaker. The contents are then agitated at 158 rpm with a stirrer for 
30 seconds. After agitation, the total volume increased to 350 ml., with 
the liquid volume being 90 ml. Thus, 260 ml. of foam is generated without 
the presence of an anti-foam agent. The foam does not dissipate after 7 
minutes. 
EXAMPLE 2 
An amount of 0.48 grams of a 5 wt. % solution of Antifoaming Agent A (570 
ppm based on CTMA-Cl), as described in Table 1, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are than agitated at 158 rpm with a stirrer for 30 seconds. After 
agitation, the total volume increased to 200 ml., with the liquid volume 
being approximately 125 ml. Thus, 75 ml. of foam is generated. After 30 
seconds at rest, all foam is eliminated. 
EXAMPLE 3 
An amount of 0.084 grams of a 5 wt. % solution of Anitifoaming Agent A (100 
ppm based on CTMA-Cl), as described in Table 1, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are then agitated at 158 rpm with a STIRRER for 30 seconds. After 
agitation, the total volume increased to 225 ml., with the liquid volume 
being approximately 110 ml. Thus, 115. ml of foam is generated. After 2 
minutes at rest, all foam is eliminated. 
EXAMPLE 4 
An amount of 0.48 grams of a 5 wt. % solution of Antifoaming Agent B (570 
ppm based on CTMA-Cl), as described in Table 2, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are then agitated at 158 rpm with a stirrer for 30 seconds. After 
agitation, the total volume increased to 225 ml., with the liquid volume 
being approximately 125 ml. Thus, 100 ml. of foam is generated. After 2 
minutes at rest, all foam is eliminated. 
EXAMPLE 5 
An amount of 0.15 grams of a 5 wt. % solution of Antifoaming Agent B (180 
ppm based on CTMA-Cl), as described in Table 2, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are then agitated at 158 rpm with a stirrer for 30 seconds. After 
agitation, the total volume increased to 225 ml., with the liquid volume 
being approximately 125 ml. Thus, 100 ml. of foam is generated. After 7 
minutes at rest, all foam is eliminated. 
EXAMPLE 6 
An amount of 0.043 grams of a 5 wt. % solution of Antifoaming Agent C (51 
ppm based on CTMA-Cl), as described in Table 3, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are then agitated at 158 rpm with a stirrer for 30 seconds. After 
agitation, the total volume increased to 210 ml., with the liquid volume 
being approximately 125 ml. Thus, 85 ml. of foam is generated. After 5 
minutes at rest, all foam is eliminated. 
EXAMPLE 7 
An amount of 0.48 grams of a 5 wt. % solution of Antifoaming Agent C (570 
ppm based on CTMA-Cl), as described in Table 3, is added to 145.4 grams of 
29 wt. % CTMA-Cl (150 ml.) and is placed in a 600 ml. beaker. The contents 
are then agitated at 158 rpm with a stirrer for 30 seconds. After 
agitation, the total volume increased to 175 ml., with the liquid volume 
being approximately 140 ml. Thus, 35 ml. of foam is generated. After 30 
seconds at rest, all foam is eliminated. 
Example 1 shows a large amount of foam produced in the absence of 
antifoaming agent. In comparison, the use of antifoaming agent in Examples 
2 to 7 results in a reduction in the amount of foam produced. 
EXAMPLE 8 
A 0.87 gram amount of a 5 wt. % solution of Antifoaming Agent A (100 ppm) 
is added to 1500 grams of 29 wt. % CTMA-Cl. Upon the addition of 
Antifoaming Agent A, all foam from the CTMA-Cl is eliminated. The 
resulting solution is charged to an autoclave and heated with 250 rpm 
agitation to 302.degree. F. The mixture is held at 302.degree. F. for 24 
hours and then cooled to room temperature. Agitation of the final solution 
induced foam formation, but the foam disappeared over several hours 
showing that the antifoamant functioned after exposure to M41S synthesis 
conditions. 
EXAMPLE 9 
One part of a 45 wt. % sodium aluminate solution is added to 10.9 parts of 
a 25 wt. % tetramethylammonium hydroxide (TMA-OH) solution. 0.02 parts of 
a 5 wt. % solution of Antifoaming Agent A (100 ppm based on CTMA-Cl), as 
described in Table 1, is added to 31.9 parts of 29 wt. % CTMA-Cl, 
completely eliminating foam from the surfactant and the resulting CTMA-Cl 
solution is charged to an autoclave. The sodium aluminate/TMA-OH mixture 
is then added to the autoclave and mixed for 15 minutes at 60 rpm. No foam 
is observed inside the autoclave. 7.3 parts of precipitated silica (HiSil) 
is added to the autoclave and after mixing for 15 minutes, the synthesis 
mixture is heated to 257.degree. F. at 90 rpm. The mixture is held at this 
temperature for 48 hours and then cooled to room temperature. The product 
drycake from the synthesis is identified as MCM-41 by x-ray diffraction. 
EXAMPLE 10 
0.003 parts of a 5 wt. % solution of Antifoaming Agent A (100 ppm based on 
CTMA-Cl), as described in Table 1, is added to 5.4 parts of 29 wt. % 
CTMA-Cl, completely eliminating foam from the surfactant and the resulting 
CTMA-Cl solution is charged to an autoclave. 1.0 part of a 25 wt. % TMA-OH 
solution is then added to the autoclave and mixed for 15 minutes at 60 
rpm. No foam is observed inside the autoclave. 1.0 part of precipitated 
silica (HiSil) is added to the autoclave and after mixing for 15 minutes, 
the synthesis mixture is heated to 212.degree. F. at 90 rpm. The mixture 
is held at this temperature for 28 hours. The temperature is then raised 
to 302.degree. F. for an additional 27.5 hours and cooled to room 
temperature. The product drycake from the synthesis is identified as 
MCM-41 by x-ray diffraction. 
Examples 9 and 10 show that the use of antifoaming agent has no effect on 
the M41S product. 
Changes and modifications in the specifically described embodiments can be 
carried out without departing from the scope of the invention which is 
intended to be limited only by the scope of the appended claims.