U.S. patent number RE29,948 [Application Number 05/801,944] was granted by the patent office on 1979-03-27 for crystalline silicates and catalytic conversion of organic compounds therewith.
This patent grant is currently assigned to Mobil Oil Corporation. Invention is credited to Francis G. Dwyer, Edwin E. Jenkins.
United States Patent |
RE29,948 |
Dwyer , et al. |
March 27, 1979 |
**Please see images for:
( Certificate of Correction ) ** |
Crystalline silicates and catalytic conversion of organic compounds
therewith
Abstract
A crystalline metal organosilicate having the composition, in
its anhydrous state, as follows: where M is a metal, other than a
metal of Group IIIA, n is the valence of said metal, R is an alkyl
ammonium radical and x is a number greater than 0 but not exceeding
1, said organosilicate being characterized by a specified X-ray
diffraction pattern. Said organosilicate is prepared by digesting a
reaction mixture comprising (R.sub.4 N).sub.2 O, sodium oxide, an
oxide of a metal other than a metal of group IIIA, an oxide of
silicon and water. The crystalline organosilicates are useful as
adsorbents and in their catalytically active form as catalysts for
organic compound conversion.
Inventors: |
Dwyer; Francis G. (West
Chester, PA), Jenkins; Edwin E. (Woodstown, NJ) |
Assignee: |
Mobil Oil Corporation (New
York, NY)
|
Family
ID: |
23632788 |
Appl.
No.: |
05/801,944 |
Filed: |
May 31, 1977 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
412393 |
Nov 2, 1973 |
03941871 |
Mar 2, 1976 |
|
|
Current U.S.
Class: |
208/110; 208/119;
208/134; 423/326; 423/332; 423/335; 423/705; 423/713; 423/DIG.22;
502/62; 534/11; 556/10; 556/173; 556/400; 556/9 |
Current CPC
Class: |
B01J
29/405 (20130101); B01J 29/46 (20130101); B01J
31/0254 (20130101); C01B 39/08 (20130101); C01B
39/085 (20130101); C07C 7/13 (20130101); C01B
37/02 (20130101); C07C 7/13 (20130101); C07C
15/067 (20130101); B01J 31/0239 (20130101); B01J
2229/37 (20130101); Y10S 423/22 (20130101) |
Current International
Class: |
B01J
31/02 (20060101); B01J 29/00 (20060101); B01J
29/40 (20060101); B01J 29/46 (20060101); C01B
37/02 (20060101); C01B 37/00 (20060101); C01B
39/00 (20060101); C01B 39/08 (20060101); C07C
7/13 (20060101); C07C 7/00 (20060101); C10G
011/02 (); C10G 035/06 (); C01B 033/20 (); B01J
021/08 () |
Field of
Search: |
;423/326,327,328-333,335
;252/431N,455Z,454
;260/448C,448.2,429R,429BQ,429.3,429.9,429.7,439R,683.65
;208/110,119,134 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Veda et al. "Molecular Sieve Zeolites-I", Copyright A.C.S., pp.
135-139. .
Barrer et al., "Journal of the Chemical Society", 1959, pp.
195-208..
|
Primary Examiner: Meros; Edward J.
Attorney, Agent or Firm: Huggett; Charles A. Barclay;
Raymond W.
Claims
We claim:
1. A crystal metal organosilicate having a composition, in its
anhydrous state, in terms of mole ratios of oxides as follows:
where M is sodium or sodium in combination with tin, calcium,
nickel or zinc, R is a tetraalkylammonium and x is a number greater
than 0 but not exceeding 1, said organosilicate having the X-ray
diffraction lines set forth in Table I of the specification.
2. A crystalline silicate resulting from thermal treatment of the
composition of claim 1 by heating to a temperature in the range of
200.degree. to 600.degree. C. for between 1 and 48 hours.
3. The composition of claim 1 which has been exchanged with
ammonium ions.
4. The composition of claim 1 wherein R is tetrapropylammonium.
5. The composition of claim 1 wherein M comprises tin.
6. The composition of claim 1 wherein M comprises sodium.
7. The composition of claim 1 wherein M comprises calcium.
8. The composition of claim 1 wherein M comprises nickel.
9. The composition of claim 1 wherein M comprises zinc.
10. A method of preparing a crystalline metal organosilicate as
defined in claim 1 which comprises preparing a mixture containing a
tetraalkylammonium compound, sodium oxide, an oxide of tin,
calcium, nickel, or zinc, an oxide of silicon and water and having
a composition in terms of mole ratios of oxides falling within the
following ranges:
wherein R is alkyl radical and M is total metal, maintaining the
mixture at a temperature at about 100.degree. C. to about
175.degree. C. until crystals of said metal organosilicate are
formed and separated and recovering said crystals.
11. A method of preparing a crystalline metal organosilicate as
defined in claim 1 which comprises preparing a mixture containing a
tetraalkylammonium compound, sodium oxide, an oxide of tin,
calcium, nickel or zinc, an oxide of silicon and water and having a
composition in terms of mole ratios of oxides falling within the
following ranges:
wherein R is an alkyl radical and M is total metal, maintaining the
mixture at a temperature at about 100.degree. C. to about
175.degree. C. until crystals of said metal organosilicate are
formed and thereafter separating and recovering said crystals.
.Iadd. 12. In a process for conducting in the presence of a solid
porous catalyst a hydrocarbon conversion reaction, the improvement
which comprises contacting charge hydrocarbons for said reaction at
conversion conditions with a catalyst comprising the composition of
claim 1. .Iaddend. .Iadd. 13. In a process for conducting in the
presence of a solid porous catalyst an organic compound conversion
reaction, the improvement which comprises contacting an organic
compound charge for said reaction at conversion conditions with a
catalyst comprising the composition of claim 2. .Iaddend..Iadd. 14.
In a process for conducting in the presence of a solid porous
catalyst a hydrocarbon conversion reaction, the improvement which
comprises contacting charge hydrocarbons for said reaction at
conversion conditions with a catalyst comprising the composition of
claim 3. .Iaddend..Iadd. 15. The process of claim 12 wherein said
catalyst comprises the composition of claim 4. .Iaddend..Iadd. 16.
The process of claim 12 wherein said catalyst comprises the
composition of claim 5. .Iaddend..Iadd. 17. The process of claim 12
wherein said catalyst comprises the composition of claim 6.
.Iaddend..Iadd. 18. The process of claim 12 wherein said catalyst
comprises the composition of claim 7. .Iaddend..Iadd. 19. The
process of claim 12 wherein said catalyst comprises the composition
of claim 8. .Iaddend..Iadd. 20. The process of claim 12 wherein
said catalyst comprises the composition of claim 9. .Iaddend.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel crystalline metal organosilicates
and to methods for their preparation and to organic compound
conversion, especially hydrocarbon conversion therewith.
2. Description of the Prior Art
Zeolitic materials, both natural and synthetic, have been known in
the past to have catalytic capability for various types of
hydrocarbon conversion reactions. Certain of these zeolitic
materials comprising ordered porous crystalline aluminosilicates
have a definite crystalline structure, as determined by X-ray
diffraction, within which there are a number of small cavities
which are interconnected by a number of still smaller channels.
These cavities and channels are precisely uniform in size within a
specific zeolitic material. Since the dimensions of these pores are
such as to accept for adsorption purposes molecules of certain
dimensions while rejecting those of larger dimensions, these
materials have commonly been known to be "molecular sieves" and are
utilized in a variety of ways to take advantage of the adsorptive
properties of these compositions.
These molecular sieves include a wide variety of positive ion
containing crystalline aluminosilicates, both natural and
synthetic. These aluminosilicates can be described as a rigid
three-dimensional network of SiO.sub.4 and AlO.sub.4 in which the
tetrahedra are cross linked by the sharing of oxygen atoms whereby
the ratio of the total aluminum and silicon atoms to oxygen is 1:2.
The electrovalence of the tetrahedra containing aluminum is
balanced by the inclusion in the crystal of a cation, for example
an alkali metal or alkaline earth cation. Thus, a univalent
positive sodium cation balances one negatively charged
aluminosilicate tetrahedra where an alkaline earth metal cation is
employed in the crystal structure of an aluminosilicate, it
balances two negatively charged tetrahedra because of its doubly
positive valence. One type of cation may be exchanged either
entirely or partially by 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 size of the pores
in a given aluminosilicate by suitable selection of the particular
cation. The spaces between the tetrahedra are occupied by moles of
water prior to dehydration.
One such group of crystalline aluminosilicates, designated as those
of the ZSM-5 type, have been known and are particularly described
in U.S. Pat. No. 3,702,886, the disclosure of which is incorporated
herein by reference. The ZSM-5-type crystalline aluminosilicates
have been prepared, for example, from a solution containing a
tetraalkyl ammonium hydroxide, sodium oxide, an oxide of aluminum
or gallium, an oxide of silicon or germanium and water and have
been found to be characterized by a specific X-ray diffraction
pattern.
The above crystalline aluminosilicates, as previously noted, have
been characterized by the presence of aluminum and silicon, the
total of such atoms to oxygen being 1:2. The amount of alumina
present appears directly related to acidity characteristics of the
resulting product. A low alumina content has been recognized as
being advantageous in attaining a low degree of acidity which in
many catalytic reactions is translated into low coke making
properties and low aging rates.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a
family of crystalline metal organosilicates which are essentially
free of Group IIIA metals, i.e. aluminum and/or gallium. These
organosilicates have surprisingly been found to be characterized by
an X-ray diffraction pattern characteristic of the above-noted
ZSM-5-type crystalline aluminosilicates. In addition to having such
characteristic X-ray diffraction pattern, the crystalline
organosilicates of the present invention can be identified in their
anhydrous state in terms of mole ratios of oxides as follows:
where M is a metal other than a metal of Group IIIA, n is the
valence of said metal, R is an alkyl ammonium radical and x is
greater than 0 but not exceeding 1. Preferably R is a tetraalkyl
ammonium radical, the alkyl groups of which contain 2-5 carbon
atoms.
In the above composition, R.sub.2 O and M.sub.2/n O may be removed
by replacement with or conversion to other desired components which
serve to enhance catalytic activity, stability and/or adsorption
characteristics. It is particularly contemplated that R and/or M
may be at least partially in the ammonium form as a result of ion
exchange.
As above noted, the family of crystalline metal organosilicates
disclosed and claimed herein have a definite X-ray diffraction
pattern. Such X-ray diffraction pattern, similar to that for the
ZSM-5 zeolites, shows the following significant lines:
TABLE I ______________________________________ Interplanar spacing
d(A): Relative intensity ______________________________________
11.1 .+-.0.2 s 10.0 .+-.0.2 s 7.4 .+-.0.15 w 7.1 .+-.0.15 w 6.3
.+-.0.1 w 6.04 .+-.0.1 w 5.97 5.56 .+-.0.1 w 5.01 .+-.0.1 w 4.60
.+-.0.08 w 4.25 .+-.0.08 w 3.85 .+-.0.07 ys 3.71 .+-.0.05 s 3.04
.+-.0.03 w 2.99 .+-.0.02 w 2.94 .+-.0.02 w
______________________________________
These values were determined by standard techniques. The radiation
was the K-alpha doublet of copper and a Geiger Counter Spectrometer
with a strip chart pen recorder was used. The peak heights, I, and
the positions as a function of two times theta, where theta is the
Bragg angle, were read from the spectrometer chart. From these, the
relative intensities, 100 I/I.sub.0, where I.sub.0 is the intensity
of the strongest line or peak and d(obs.), the interplanar spacing
in A, corresponding to the recorded lines were calculated. In Table
I the relative intensities are given in terms of the symbols s =
strong, w = weak and vs = very strong.
The crystalline metal organosilicate of the present invention can
be used either in the alkali metal form, e.g. the sodium form,
other desired metal form, the ammonium form or the hydrogen form.
Preferably, one or other of the last two forms is employed. They
can also be used in intimate combination with a hydrogenation
component such as tungsten, vanadium, molybdenum, rhenium, nickel,
cobalt, chromium, manganese or a noble metal such as platinum or
palladium where a hydrogenation-dehydrogenation function is to be
performed. Such component can suitably be impregnated on or
physically intimately admixed with the crystalline
organosilicate.
The above organosilicates as synthesized or after impregnation can
be beneficially converted to another form by thermal treatment.
This can be done by heating to a temperature in the range of
200.degree. to 600.degree. C. in an atmosphere such as air,
nitrogen, etc. and that atmospheric or subatmosphereic pressures
for between 1 and 48 hours. Dehydration may also be performed at
lower temperatures merely by placing the organosilicate in a
vacuum, but a longer time is required to obtain a sufficient amount
of dehydration.
The crystalline metal organosilicates of the invention can be
suitably synthesized by preparing a solution containing (R.sub.4
N).sub.2 O, sodium oxide, an oxide of a metal other than a metal of
Group IIIA and water and having a composition in terms of mole
ratios of oxides falling within the following ranges:
TABLE II ______________________________________ Broad Preferred
______________________________________ OH.sup.- /SiO.sub.2 .01-5
.05-1.0 R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) .05-1.0 .1-.8
H.sub.2 O/OH.sup.- 50-1000 50-500 SiO.sub.2 /M.sub.2/n O >1
>3 ______________________________________
wherein R is an alkyl radical, preferably between 2 and 5 carbon
atoms and M is total metal. Thereafter, the mixture is maintained
until crystals of the metal organosilicate are formed. Preferably,
crystallization is performed under pressure in an autoclave or
static bomb reactor. The temperature ranges from 100.degree. C. to
200.degree. C. generally, but at lower temperatures, e.g. about
100.degree. C., crystallization time is longer. Thereafter, the
crystals are separated from the liquid and recovered. Typical
reaction conditions consist of heating the foregoing reaction
mixture to a temperature from about 100.degree. C. to 175.degree.
C. for a period of time of from about 6 hours to 60 days. The more
preferred temperature range is from about 100.degree. C. to
175.degree. C. with the amount of time at a temperature in such
range being from about 12 hours to 30 days.
The treatment of the amorphous mixture is carried out until
crystals form. The resulting crystalline product is separated from
the reaction medium, as by cooling to room temperature, filtering
and water washing. The product so obtained is dried, e.g. at
230.degree. F., for from about 8 to 24 hours. If desired, milder
conditions may be employed, e.g. room temperature under vacuum.
The desired crystalline organosilicate can be prepared utilizing
materials which supply the appropriate oxide. Such compositions
include sodium silicate, colloidal silica, silica hydrosol, silica
gel, silicic acid, sodium hydroxide, compounds of the desired
metal, other than a metal of Group IIIA and tetraalkylammonium
compounds, e.g. tetrapropylammonium bromide. In addition to
tetrapropylammonium compounds, it is contemplated that tetramethyl,
tetraethyl or tetrabutyl ammonium compounds may similarly be
employed. It will be understood that each oxide component utilized
in the reaction mixture for preparing the crystalline metal
organosilicates of this invention can be supplied by one or more
initial reactants and they can be mixed together in any order. For
example, sodium oxide can be supplied by an aqueous solution of
sodium hydroxide or by an aqueous solution of sodium silicate;
tetrapropylammonium can be supplied in the form of its hydroxide as
can the other tetraalkylammonium radicals noted hereinabove. The
reaction mixture can be prepared either batchwise or continuously.
Crystal size and crystallization time of the crystalline metal
organosilicate composition will vary with the nature of the
reaction mixture employed.
The crystalline organosilicates described herein are substantially
free of alumina, but may contain very minor amounts of such oxide
attributable primarily to the presence of aluminum impurities in
the reactants and/or equipment employed. Thus, the molar ratio of
alumina to silica will be in the range of 0 to less than 0.005
Al.sub.2 O.sub.3 to more than 1 mole of SiO.sub.2. Generally, the
latter may range from >1 SiO.sub.2 up to 500 or more.
DESCRIPTION OF SPECIFIC EMBODIMENTS
The crystalline metal organosilicates as synthesized can have the
original components thereof replaced by a wide variety of others
according to techniques well known in the art. Typical replacing
components would include hydrogen, ammonium, alkyl ammonium and
aryl ammonium and metals, other than metals of Group IIIA,
including mixtures of the same. The hydrogen form may be prepared,
for example, by substitution of original sodium with ammonium. The
composition is then calcined at a temperature of, say, 1000.degree.
F. causing evolution of ammonia and retention of hydrogen in the
composition. Of the replacing metals, preference is accorded to
metals of Groups II, IV and VIII of the Periodic Table.
The crystalline silicates are then preferably washed with water and
dried at a temperature ranging from 150.degree. F. to about
600.degree. F. and thereafter calcined in air or other inert gas at
temperatures ranging from 500.degree. F. to 1500.degree. F. for
periods of time ranging from 1 to 48 hours or more.
Regardless of the synthesized form of the organosilicate the
spatial arrangement of atoms which form the basic crystal latices
remain essentially unchanged by the described replacement of sodium
or other alkali metal or by the presence in the initial reaction
mixture of metals in addition to sodium, as determined by an X-ray
powder diffraction pattern of the resulting organosilicate. The
X-ray diffraction patterns of such products are essentially the
same as those set forth in Table I above.
The crystalline silicates prepared in accordance with the instant
invention are formed in a wide variety of particular sizes.
Generally, the particles can be in the form of powder, a granule,
or a molded product such as an extrudate having a particle size
sufficient to pass through a 2 mesh (Tyler) screen and be
maintained on a 400 mesh (Tyler) screen in cases where the catalyst
is molded such as by extrusion. The aluminosilicate can be extruded
before drying or dried or partially dried and then extruded.
In the case of many catalysts, it is desired to incorporate the new
crystalline silicate with another material resistant to the
temperatures and other conditions employed in organic processes.
Such materials include active and inactive materials and synthetic
and naturally occurring zeolites as well as inorganic materials
such as clays, silica and/or metal oxides. The latter may be either
naturally occurring or in the form of gelatinous precipitates or
gels including mixtures of silica and metal oxides. Use of the
material in conjunction with the new crystalline aluminosilicate,
i.e. combined therewith which is active, tends to improve the
conversion and/or selectivity of the catalyst in certain organic
conversion processes. Inactive materials suitably serve as diluents
to control the amount of conversion in a given process so that
products can be obtained economically and in an orderly manner
without employing other means for controlling the rate of reaction.
Normally, crystalline materials have been incorporated into
naturally occurring clays, e.g. bentonite and kaolin to improve the
crush strength of the catalyst under commercial operating
conditions. These materials, i.e. clays, oxides etc., function as
binders for the catalyst. It is desirable to provide a catalyst
having good crush strength because in a petroleum refinery the
catalyst is often subjected to rough handling which tends to break
the catalyst down into powder-like materials which cause problems
in processing. These clay binders have been employed for the
purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the
crystalline metal organosilicate described herein include the
montmorillonite and kaolin family, which families include the
sub-bentonites and the kaolins known commonly as Dixie, McNamee,
Georgia and Florida or others in which the main constituent is
halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can
be used in the raw state as originally mined or initially subjected
to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the crystalline metal
organosilicate may be composited with a porous matrix material such
as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,
silica-berylia, silica-titania as well as ternary compositins such
as silica-alumina-thoria, silica-alumina-zirconia,
silica-alumina-magnesia and silica-magnesia-zirconia. The matrix
can be in the form of a cogel. The relative proportions of finally
divided crystalline metal organosilicate and inorganic oxide gel
matrix can vary widely with the crystalline organosilicate content
ranging from about 1 to 90 percent by weight and more usually in
the range of about 2 to about 50 percent by weight of the
composite.
Employing the catalyst of this invention, containing a
hydrogenation component, heavy petroleum residual stocks, cycle
stocks, and other hydrocrackable charge stocks can be hydrocracked
at temperatures between 400.degree. F. and 825.degree. F. using
molar ratios of hydrogen to hydrocarbon charge in the range between
2 and 80. The pressure employed will vary between 10 and 2,500 psig
and the liquid hourly spaced velocity between 0.1 and 10.
Employing the catalyst of this invention for catalytic cracking,
hydrocarbon cracking stocks can be cracked at a liquid hourly space
velocity between about 0.5 and 50, a temperature between about
550.degree. F. and 1100.degree. F., a pressure between about
subatmospheric and several hundred atmospheres.
Employing a catalytically active form of a member of the family of
zeolites of this invention containing a hydrogenation component,
reforming stocks can be reformed employing a temperature between
700.degree. F. and 1000.degree. F. The pressure can be between 100
and 1000 psig, but is preferably between 200 and 700 psig. The
liquid hourly space velocity is generally between 0.1 and 10,
preferably between 0.5 and 4 and the hydrogen to hydrocarbon mole
ratio is generally between 1 and 20, preferably between 4 and
12.
The catalyst can also be used for hydroisomerization of normal
paraffins when provided with a hydrogenation component, e.g.
platinum. Hydroisomerization is carried out at a temperature
between 200.degree. and 700.degree. F., preferably 300.degree. to
550.degree. F., with a liquid hourly space velocity between 0.01
and 2, preferably between 0.25 and 0.50 employing hydrogen such
that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1.
Additionally, the catalyst can be used for olefin isomerization
employing temperatures between 30.degree. F. and 500.degree. F.
In order to more fully illustrate the nature of the invention and a
manner of practicing the same, the following examples are
presented.
In the examples which follow, whenever adsorption data are set
forth, it was determined as follows:
A weighed sample of the material was contacted with the desired
pure adsorbate vapor in an adsorption chamber at a pressure less
than the vapor-liquid equilibrium pressure of the adsorbate at room
temperature. This pressure was kept constant during the adsorption
period which did not exceed about eight hours. Adsorption was
complete when a constant pressure in the adsorption chamber was
reached, i.e. 12 mm. of mercury for water and 20 mm. for n-hexane
and cyclohexane. The increase in weight was calculated as the
adsorption capacity of the sample.
EXAMPLE 1
A crystalline organosilicate containing tin and sodium was
synthesized from tetrapropylammonium bromide, colloidal silica,
stannous chloride and sodium hydroxide. A mixture of 19.1 grams of
colloidal silica (30 weight percent SiO.sub.2), 15.6 grams of
tetrapropylammonium bromide, 1.5 grams of NaOH, 1.0 gram of
SnCl.sub.4.5 H.sub.2 O and 100 grams of water was prepared. This
mixture was placed in an autoclave and maintained for 22 hours at
300.degree. F. and autogenous pressure. The product was removed,
filtered, water washed and dried at 230.degree. F. X-ray
diffraction analysis established the product as being crystalline
and having the X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .095 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0294 H.sub.2 O 6.3 Na.sub.2 O .01875
SnO.sub.2 .0029 R.sub.4 N/R.sub.4 N + Na .610 OH.sup.- /SiO.sub.2
.395 H.sub.2 O/OH.sup.- 168.3 SiO.sub.2 /M.sub.2/n O 4.38
______________________________________
where R is propyl and M is total metal.
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.3
0.06 Na 3.1 SiO.sub.3 91 (approx.) Sn 6.1
______________________________________
EXAMPLE 2
A crystalline organosilicate containing sodium was produced from
tetrapropylammonium bromide, colloidal silica and sodium hydroxide.
A mixture of 19.1 grams of colloidal silica (30 weight percent
SiO.sub.2), 15.6 grams tetrapropylammonium bromide, 1.0 gram NaOH
and 100 grams of water was prepared. This mixture was placed in an
autoclave and maintained for 24 hours at 300.degree. F. and
autogenous pressure. The product was removed, filtered, water
washed and dried at 230.degree. F. X-ray diffraction analysis
established the product as being crystalline and having the X-ray
diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below.
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .095 [(C.sub.3
H.sub.8).sub.4 N]O .0294 H.sub.2 O 6.3 Na.sub.2 O .0125 R.sub.4
N/R.sub.4 N + Na .701 OH.sup.- /SiO.sub.2 .263 H.sub.2 O/OH.sup.-
252.5 SiO.sub.2 /Na.sub.2 O 7.6
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.3
0.13 N 0.69 Na 0.80 SiO.sub.2 98.8 Adsorption Wt. Percent
______________________________________ Cyclohexane 2.4 Water 4.6
______________________________________
EXAMPLE 3
A crystalline organosilicate containing sodium was synthesized from
sodium silicate, sodium hydroxide, sulfuric acid and
tetrapropylammonium bromide. A mixture of 40 grams of sodium
silicate "Q" Brand (Na.sub.2 O/SiO.sub.2 = 0.299), 31.2 grams of
tetrapropylammonium bromide, 0.5 gram NaOH, 4.6 grams H.sub.2
SO.sub.4 and 200 grams of water was prepared. This mixture was
maintained for 6 days at 212.degree. F. and atmospheric pressure.
The product was removed, filtered, water washed and dried at about
250.degree. F. X-ray diffraction analysis established the product
as being crystalline and having the X-ray diffraction pattern set
forth in Table I.
The reaction composition is shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .1896 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0587 H.sub.2 O 12.5 Na.sub.2 O .0943
R.sub.4 N/R.sub.4 N + Na .384 OH.sup.- /SiO.sub.2 .499 H.sub.2 O
/OH.sup.- 132.1 SiO.sub.2 /Na.sub.2 O 2.01
______________________________________
After calcination for 16 hours at 1000.degree. F. in air, the
product was used to effect selective separation of C.sub.8 aromatic
isomers. As will be evident from the data shown below in Table III,
ortho xylene and meta xylene are both very selectively excluded at
200.degree. C., while para xylene and ethylbenzene are both
sorbed.
TABLE III ______________________________________ A. Pure Components
Retention Time. Sec. ______________________________________
Mesitylene 10 o-Xylene 11 m-Xylene 11 p-Xylene 394 Ethylbenzene 319
B. C.sub.8 -Aromatic Mixture Major Separation No Resolution Minor
Separation OX, MX/PX, EB Number of Peaks 2 Resolution Excellent
Capacity (.mu. l/g) III ______________________________________
EXAMPLE 4
A crystalline organosilicate containing sodium was synthesized from
sodium silicate, sulfuric acid, tetrapropylammonium bromide and
water. A mixture of 80 grams of sodium silicate (Na.sub.2
O/SiO.sub.2 = 0.299), 8 grams of sulfuric acid, 60 grams of
tetrapropylammonium bromide and 200 grams of water was prepared.
This mixture was maintained at 212.degree. F. for 66 hours and
autogenous pressure. The product was removed, filtered, water
washed and dried at about 250.degree. F. X-ray diffraction analysis
established the product as being crystalline and having the X-ray
diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .379 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .113 H.sub.2 O 13.9 Na.sub.2 O .176
R.sub.4 N/R.sub.4 N + Na .391 OH.sup.- /SiO.sub.2 .498 H.sub.2
O/OH.sup.- 73.66 SiO.sub.2 /Na.sub.2 O 2.15 Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub. 3
0.18 N 0.78 Na 1.3 SiO.sub.2 97 (approx.)
______________________________________
EXAMPLE 5
A crystalline organosilicate containing sodium was synthesized from
sodium silicate, sulfuric acid, sodium hydroxide,
tetramethylammonium chloride, tetrapropylammonium bromide and
water. A mixture of 40 grams of sodium silicate (Na.sub.2
O/SiO.sub.2 = 0.299), 1.5 grams of sodium hydroxides, 3 grams of
sulfuric acid, 6 grams of tetramethylammonium chloride, 6 grams of
tetrapropylammonium bromide and 231 grams of water was prepared.
This mixture was maintained for 113 hours at 320.degree. F. and
autogenous pressure. The product was removed, filtered, water
washed and dried at about 250.degree. F. X-ray diffraction analysis
showed the crystalline material to have the X-ray diffraction
pattern set forth in Table I.
The reaction composition is shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .1897 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0113 [(CH.sub.3).sub.4 N].sub.2 O .0274
H.sub.2 O 14.2 Na.sub.2 O .0755 R.sub.4 N/R.sub.4 N + Na .339
OH.sup.- /SiO.sub.2 .473 H.sub.2 O/OH.sup.- 158.1 SiO.sub.2
/Na.sub.2 O 2.513 ______________________________________
where R is propyl + methyl.
EXAMPLE 6
A crystalline organosilicate containing sodium was synthesized from
sodium silicate, sodium hydroxide, sulfuric acid,
tetrapropylammonium bromide and water. A mixture of 160 grams of
sodium silicate (Na.sub.2 O/SiO.sub.2 = 0.299), 2 grams of sodium
hydroxide, 18.4 grams of sulfuric acid. 124.8 grams of
tetrapropylammonium bromide and 800 grams of water was prepared.
This mixture was maintained for 40 hours at 212.degree. F. and
autogenous pressure. The product was removed, filtered, water
washed and dried at about 250.degree. F. X-ray diffraction analysis
showed the crystalline material to have the X-ray diffraction
analysis set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .759 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .2347 H.sub.2 O 50.02 Na.sub.2 O .2521
R.sub.4 N/R.sub.4 N + Na .482 OH.sup.- /SiO.sub.2 .1696 H.sub.2
O/OH.sup.- 388.7 SiO.sub.2 /Na.sub.2 O 3.01
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.2
0.202 Na 1.5 SiO.sub.2 96.5
______________________________________
EXAMPLE 7
A crystalline organosilicate containing zirconium and sodium was
synthesized from colloidal silica, sodium hydroxide, zirconium
oxide (25 percent solution), tetrapropylammonium bromide and water.
A mixture of 50 grams of colloidal silica (30 weight percent
SiO.sub.2), 1 gram of sodium hydroxide, 25 grams of zirconium oxide
(25 percent solution), 20 grams of tetrapropylammonium bromide and
50 grams of water was prepared. This mixture was maintained for 25
days at 300.degree. F. and autogeneous pressure. The product was
removed, filtered, water washed and dried at about 250.degree. F.
X-ray diffraction analysis showed the crystalline material to have
the X-ray diffraction pattern in Table I.
The reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .2496 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0376 H.sub.2 O 5.76 Na.sub.2 O .0125
ZrO.sub.2 .0507 R.sub.4 N/R.sub.4 N + Na .750 H.sub.2 O/OH.sup.-
230.4 SiO.sub.2 /M.sub.2/n O 3.94 Product Composition Wt. Percent
______________________________________ Al.sub.2 O.sub.3 <0.04 N
0.52 Na 0.24 ______________________________________
EXAMPLE 8
A crystalline organosilicate containing calcium and sodium was
synthesized from colloidal silica, sodium hydroxide, calcium
hydroxide, tetrapropylammonium bromide and water. A mixture of 50
grams of colloidal silica (30 weight percent of SiO.sub.2), 1 gram
NaOH, 1 gram Ca(OH).sub.2, 20 grams of tetrapropylammonium bromide
and 100 grams of water was prepared. The mixture was maintained for
16 days at 212.degree. F. and autogenous pressure. The product was
removed, filtered, water washed and dried at about 250.degree. F.
X-ray analysis showed the crystalline material to have the X-ray
diffraction pattern set forth in Table I.
Reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .2496 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0376 H.sub.2 O 7.50 Na.sub.2 O .0125 CaO
.0135 R.sub.4 N/R.sub.4 N + Na .750 OH.sup.- /SiO.sub.2 .l00
H.sub.2 O/OH.sup.- 300 SiO.sub.2 /M.sub.2/n O 9.6
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.3
<0.04 N 0.63 Na 0.66 SiO.sub.2 96 (approx.) Ca 2.9
______________________________________
EXAMPLE 9
A crystalline organoslicate containing nickel and sodium was
synthesized from colloidal silica, sodium hydroxide, nickel
nitrate, tetrapropylammonium bromide and water. A mixture of 50
grams of colloidal silica (30 weight percent SiO.sub.2), 1.5 grams
of NaOH, 4 grams of Ni(NO.sub.3).sub.2.6 H.sub.2 O, 20 grams of
tetrapropylammonium bromide and 60 grams of water was prepared.
This mixture was maintained for 19 days at 212.degree. F. and
autogenous pressure. The product was removed, filtered, water
washed and dried at about 250.degree. F. X-ray diffraction analysis
showed the crystalline material to have the X-ray diffraction
pattern set forth in Table I. The reaction composition and product
analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .2496 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .0376 H.sub.2 O 5.36 Na.sub.2 O .0188 NiO
.01376 R.sub.4 N/R.sub.4 N + Na .667 OH.sup.- /SiO.sub.2 .150
H.sub.2 O/OH.sup.- 142.9 SiO.sub.2 /M.sub.2/n O 7.68
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.3
<0.04 N 0.65 Na 0.71 SiO.sub.2 92 (approx.) Ni 7.0
______________________________________
EXAMPLE 10
A crystalline organosilicate containing zinc and sodium was
synthesized from colloidal silica, sodium hydroxide, zinc nitrate,
tetrapropylammonium bromide and water. A mixture of 100 grams of
colloidal silica, 4 grams NaOH, 4 grams of Zn(NO.sub.3).sub.2.6
H.sub.2 O, 25 grams of tetrapropylammonium bromide and 100 grams of
water was prepared. This mixture was maintained for 14 days at
212.degree. F. and autogenous pressure. The product was removed,
filtered, water washed, and dried at about 250.degree. F. X-ray
diffraction analysis showed the crystalline material to have the
X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________ Reaction Composition Moles
______________________________________ SiO.sub.2 .4992 [(C.sub.3
H.sub.8).sub.4 N].sub.2 O .047 H.sub.2 O 9.53 Na.sub.2 O .05 ZnO
.0059 R.sub.4 N/R.sub.4 N + Na .485 OH.sup.- /SiO.sub.2 .200
H.sub.2 O/OH.sup.- 95.3 SiO.sub.2 /M.sub.2/n O 8.93
______________________________________ Product Composition Wt.
Percent ______________________________________ Al.sub.2 O.sub.3
<0.04 N 0.69 Na 1.3 SiO.sub.2 95 (approx.) ZnO 2.63
______________________________________
* * * * *