Note: Descriptions are shown in the official language in which they were submitted.
1 335600
- NEW ZEOLITE SSZ-26
05 BACKGROUND OF THE INVENTION
Natural and synthetic zeolitic crystalline
aluminosilicates are useful as catalysts and adsorbents.
These aluminosilicates have distinct crystal structures
which are demonstrated by X-ray diffraction. The crystal
structure defines cavities and pores which are character-
istic of the different species. The adsorptive and cata-
lytic properties of each crystalline aluminosilicate are
determined in part by the dimensions of its pores and
cavities. Thus, the utility of a particular zeolite in a
particular application depends at least partly on its
crystal structure.
Because of their unique molecular sieving
characteristics, as well as their catalytic properties,
crystalline aluminosilicates are especially useful in such
applications as gas drying and separation and hydrocarbon
conversion. Although many different crystalline alumino-
silicates and silicates have been disclosed, there is a
continuing need for new zeolites and silicates with desir-
able properties for gas separation and drying, hydrocarbon
and chemical conversions, and other applications.
Crystalline aluminosilicates are usually
prepared from aqueous reaction mixtures containing alkali
or alkaline earth metal oxides, silica, and alumina.
"Nitrogenous zeolites" have been prepared from reaction
mixtures containing an organic templating agent, usually a
nitrogen-containing organic cation. By varying the syn-
thesis conditions and the composition of the reaction mix-
ture, different zeolites can be formed using the same
templating agent. Use of N,N,N-trimethyl cyclopentylammo-
nium iodide in the preparation of Zeolite SSZ-15 molecular
sieve is disclosed in U.S. Patent No. 4,610,854; use of
l-azoniaspiro [4.4] nonyl bromide and N,N,N-trimethyl neo-
pentylammonium iodide in the preparation of a molecular
sieve termed "Losod~ is disclosed in Helv. Chim. Acta
(1974), Vol. 57, page 1533 (W. Sieber and W. M. Meier);
_ -2- l3356~o
use of quinuclidinium compounds to prepare a zeolite
termed "NU-3" is disclosed in European Patent Publication
No. 40016; use of 1,4-di(l-azoniabicyclo t2.2.2.]octane)
lower alkyl compounds in the preparation of Zeolite SSZ-
16 molecular sieve is disclosed in U.S. Patent No.
4,508,837; use of N,N,N-trialkyl-l-adamantamine in the
preparation of zeolite SSZ-13 molecular sieve is
disclosed in U.S. Patent No. 4,544,538.
SUMMARY OF THE INVENTION
We have prepared a family of crystalline
aluminosilicate molecular sieves with unique properties,
referred to herein as "Zeolite SSZ-26", or simply "SSZ-
26", and have found a highly effective method for
preparing SSZ-26.
SSZ-26 has a mole ratio of an oxide selected
from silicon oxide, germanium oxide, and mixtures thereof
to an oxide selected from aluminum oxide, gallium oxide,
iron oxide, and mixtures thereof greater than about 10:1
and preferably in the range of 10:1 to 200:1, and having
the X-ray diffraction lines of Table 1 below. The
zeolite further has a composition, as synthesized and in
the anhydrous state, in terms of mole ratios of oxides as
follows: (0.1 to 2.0)Q2O:(O" to 2.0)M2O:W2O3:(10 to 20O)YO2
wherein M is an alkali metal cation, W is selected from
aluminum, gallium, iron, and mixtures thereof, Y is
selected from silicon, germanium and mixtures thereof,
and Q is a hexamethyl [4.3.3.0] propellane-8,11-
diammonium cation. SSZ-26 zeolites can have a YO2:W2O3
mole ratio in the range of 10 to 200. As prepared, the
silica:alumina mole ratio is typically in the range of
12:1 to about 100:1. Higher mole ratios can be obtained
by treating the zeolite with chelating agents or acids to
extract aluminum from the zeolite lattice. This includes
reagents such as (NH4)2SiF6 or acidic ion exchange resins.
The silica:alumina mole ratio can also be increased by
using silicon and carbon halides and other similar
compounds. Preferably, SSZ-26 is an aluminosilicate
wherein W is aluminum and Y is silicon.
3 1 335600
Our invention also involves a method for preparing
SSZ-26 zeolites, comprising preparing an aqueous mixture
containing sources of a hexamethyl [4.3.3Ø]
propellane-8,11-diammonium cation, an oxide selected
S from aluminum oxide, gallium oxide, iron oxide, and
mixtures thereof, and an oxide selected from silicon
oxide, germanium oxide, and mixtures thereof, and having
a composition, in terms of mole rations of oxides,
falling within the following ranges: Y02/W203, 10:1 to
200:1; and Q/Y02 0.05:1 to 0.50:1; wherein Y is selected
from silicon, germanium, and mixtures thereof, W is
selected from aluminum, gallium, iron, and mixtures
thereof, and Q is a hexamethyl ~4.3.3.0] propellane-
8,11-diammonium cation; maintaining the mixture at a
temperature of at least 100C until the crystals of said
zeolite are formed; and recovering said crystals.
Various aspects of this invention are as follows:
A compound which is N,N,N',N'-tetramethyl ~4.3.3.0]
propellane-8,11-diamine.
A compound of the formula
C~N(CH3)3 2A-
N(CH 3 ) 3
wherein A- is an anion.
DETAITFn DESCRIPTION OF T~ I~v~ ON
SSZ-26 zeolites, as synthesized, have a crystalline
structure whose X-ray powder diffraction pattern shows
the following characteristic lines:
Table 1
2 e d/n I/Io x loo
7.78 11.36 100
20.33 4.389 63
21.37 4.158 25
21.99 4.042 53
-- 1 3356~0
3a
22.85 3.890 46 Sh
23.00 3.867 64
26.49 3.365 33
Sh = Shoulder
Typical SSZ-26 aluminosilicate zeolites have the X-
ray diffraction pattern of Tables 3-7.
The X-ray powder diffraction patterns were
determined by st~ndard technique~. The radiation was the
0-~1 ~4~ 1 3 3 5 6 0 0
K-alpha/doublet of copper and a scintillation counter
spectrometer with a strip-chart pen recorder was used.
S The peak heights I and the positions, as a function of 2 e
where e is the Bragg angle, were read from the spectro-
meter chart. From these measured values, the relative
intensities, lOOI/Io, where Io is the intensity of the
strongest line or peak, and d, the interplanar spacing in
Angstroms corresponding to the recorded lines, can be
calculated. The X-ray diffraction pattern of Table 1 is
characteristic of SSZ-26 zeolites. The zeolite produced
by exchanging the metal or other cations present in the
zeolite with various other cations yields substantially
the same diffraction pattern although there can be minor
shifts in interplanar spacing and minor variations in
relative intensity. Minor variations in the diffraction
pattern can also result from variations in the organic
compound used in the preparation and from variations in
the silica-to-alumina mole ratio from sample to sample.
Calcination can also cause minor shifts in the X-ray
diffraction pattern. Notwithstanding these minor per-
turbations, the basic crystal lattice structure remains
unchanged.
After calcination the SS2-26 zeolites have a
crystalline structure whose X-ray powder diffraction
pattern shows the following characteristic lines as
indicated in Table 2 below:
Table 2
2 e d/nI/Io x 100
7.78 11.36 100
20.22 4.392 18
21.34 4.164 5
21.98 4.044 15
22.93 3.878 13 Sh
23.08 3.853 19
26.48 3.366 12
Sh = Shoulder
ol s 13356GO
SSZ-26 zeolites can be suitably prepared from an
aqueous solution containing sources of an alkali metal
05 oxide, a hexamethyl [4.3.3.0] propellane-8,11-diammonium
cation, an oxide of aluminum, gallium, iron, or mixtures
thereof, and an oxide of silicon or germanium, or mixture
of the two. The reaction mixture should have a composi-
tion in terms of mole ratios falling within the following
ranges:
Broad Preferred
YO2/W2O3 10-200 20-100
OH /YO2 0.10-1.0 0.20-0.50
Q/YO2 0.05-0.50 0.05-0.20
M+/YO2 0.05-0.50 0.15-0.30
H2/YO2 15-300 25-60
Q/Q+M+ 0.20-0.70 0.30-0.67
wherein Q is a hexamethyl [4.3.3.0] propellane-8,11-
diammonium cation, Y is silicon, germanium or both, and W
is aluminum, gallium, iron, or mixtures thereof. M is an
alkali metal ion, preferably sodium. The organic propel-
lane compound which acts as a source of the propellanequaternary ammonium ion employed can provide hydroxide
ion. Anions which are associated with the organic cation
are those which are not detrimental to the formation of
the zeolite.
The hexamethyl [4.3.3.0] propellane-8,11-
diammonium cation component Q, of the crystallization
mixture, is preferably derived from a compound of the
formula:
~ 3 2Ae
including syn,syn; syn,anti; and anti,anti
orientations and wherein Ae is an anion which is not
1 335600
0~ -6-
-
detrimental to the formation of the zeolite. Representative
of the anions include halogen, e.g., fluoride, chloride,
05 bromide and iodide, hydroxide, acetate, sulfate, tetra-
fluoroborate, carboxylate, and the like. Hydroxide is themost preferred anion.
The reaction mixture is prepared using standard
zeolitic preparation techniques. Typical sources of
aluminum oxide for the reaction mixture include alumi-
nates, alumina, and aluminum compounds such as AlC13,A12(SO4)3, kaolin clays, and other zeolites. Typical
sources of silicon oxide include silicates, silica
hydrogel, silicic acid, colloidal silica, fumed silicas,
tetraalkyl orthosilicates, and silica hydroxides.
Gallium, iron, and germanium can be added in forms
corresponding to their aluminum and silicon counterparts.
Salts, particularly alkali metal halides such as sodium
chloride, can be added to or formed in the reaction
mixture. They are disclosed in the literature as aiding
the crystallization of zeolites while preventing silica
occlusion in the lattice.
The reaction mixture is maintained at an
elevated temperature until the crystals of the zeolite are
formed. The temperatures during the hydrothermal crystal-
lization step are typically maintained from about 140C to
about 200C, preferably from about 150C to about 180C
and most preferably from about 150C to about 170C. The
crystallization period is typically greater than 1 day and
3 preferably from about 5 days to about 10 days.
Preferably the zeolite is prepared using mild
stirring or aqitation. High speed stirring may lead to
co-crystallization of at least one other zeolite.
Stirring at less than 100 RPM is preferred.
The hydrothermal crystallization is conducted
under pressure and usually in an autoclave so that the
reaction mixture is subject to autogenous pressure. The
reaction mixture can be stirred during crystallization.
Once the zeolite crystals have formed, the solid
product is separated from the reaction mixture by standard
-7- 1 3 3 5 6 0 0
mechanical separation techniques such as filtration. The
crystals are water-washed and then dried, e.g., at 90C to
05 150C for from 8 to 24 hours, to obtain the as synthesized,
SSZ-26 zeolite crystals. The drying step can be performed
at atmospheric or subatmospheric pressures.
During the hydrothermal crystallization step,
the SSZ-26 crystals can be allowed to nucleate spontane-
ously from the reaction mixture. The reaction mixture canalso be seeded with SSZ-26 crystals both to direct, and
accelerate the crystallization, as well as to minimize
the formation of undesired aluminosilicate contaminants.
If the reaction mixture is seeded with SSZ-26 crystals,
the concentration of the organic compound can be greatly
reduced.
The synthetic SSZ-26 zeolites can be used as
synthesized or can be thermally treated (calcined).
Usually, it is desirable to remove the alkali metal cation
by ion exchange and replace it with hydrogen, ammonium, or
any desired metal ion. The zeolite can be leached with
chelating agents, e.g., EDTA or dilute acid solutions, to
increase the silica:alumina mole ratio. These methods may
also include the use of (NH4)2SiF6 or acidic ion-exchange
resin treatment. The zeolite can also be steamed; steam-
ing helps stabilize the crystalline lattice to attack fromacids. The zeolite can be used in intimate combination
with hydrogenating components, such as tungsten, vanadium,
molybdenum, rhenium, nickel, cobalt, chromium, manganese,
or a noble metal, such as palladium or platinum, for those
applications in which a hydrogenation-dehydrogenation
function is desired. Typical replacing cations can
include metal cations, e.g., rare earth, Group IA,
Group IIA and Group VIII metals, as well as their mix-
3 tures. Of the replacing metallic cations, cations ofmetals such as rare earth, Mn, Ca, Mg, Zn, Ga, Cd, Pt, Pd,
Ni, Co, Ti, Al, Sn, Fe and Co are particularly preferred.
The hydrogen, ammonium, and metal components can
be exchanged into the zeolite. The zeolite can also be
4 impregnated with the metals, or, the metals can be
01 -8- 1 3 3 5 6 0 0
-
physically intimately admixed with the zeolite using
standard methods known to the art. And, the metals can be
05 occluded in the crystal lattice by having the desired
metals present as ions in the reaction mixture from which
the SSZ-26 zeolite is prePared.
Typical ion exchange techniques involve
contacting the synthetic zeolite with a solution contain-
ing a salt of the desired replacing cation or cations.Although a wide variety of salts can be employed, chlo-
rides and other halides, nitrates, and sulfates are
particularly preferred. Representative ion exchange
techniques are disclosed in a wide variety of patents
lS including U-S. Nos. 3,140,249; 3,140,251; and 3,140,253.
Ion exchange can take place either before or after the
zeolite is calcined.
Following contact with the salt solution of the
desired replacing cation, the zeolite is typically washed
with water and dried at temperatures ranging from 65C to
about 315C. After washing, the zeolite can be calcined
in air or inert gas at temperatures ranging from about
200C to 820C for periods of time ranging from 1 to 48
hours, or more, to produce a catalytically active product
especially useful in hydrocarbon conversion processes.
Regardless of the cations present in the
synthesized form of the zeolite, the spatial arrangement
of the atoms which form the basic crystal lattice of the
zeolite remains essentially unchanged. The exchange of
cations has little, if any, effect on the zeolite lattice
structures.
The SSZ-26 aluminosilicate can be formed into a
wide variety of physical shapes. Generally speaking, the
zeolite can be in the form of a powder, a granule, or a
molded product, such as extrudate having particle size
sufficient to pass through a 2-mesh (Tyler) screen and be
retained on a 400-mesh (Tyler) screen. In cases where the
catalyst is molded, such as by extrusion with an organic
binder, the aluminosilicate can be extruded before drying,
or, dried or partially dried and then extruded.
-9- 1 3 3 5 6 0 0
-
The zeolite can be composited with other
materials resistant to the temperatures and other condi-
05 tions employed in organic conversion processes. Such
matrix materials include active and inactive materials andsynthetic or naturally occurring zeolites as well as inor-
ganic materials such as clays, silica and metal oxides.
The latter may occur naturally or may be in the form of
gelatinous precipitates, sols, or gels, including mixtures
of silica and metal oxides. Use of an active material in
conjunction with the synthetic zeolite, i.e., combined
with it, tends to improve the conversion and selectivity
of the catalyst in certain organic conversion processes.
Inactive materials can suitably serve as diluents to
control the amount of conversion in a given process so
that products can be obtained economically without
using other means for controlling the rate of reaction.
Frequently, zeolite materials have been incorporated into
naturally occurring clays, e.g., bentonite and kaolin.
These materials, i.e., clays, oxifles, etc., function, in
part, as binders for the catalyst. It is desirable to
provide a catalyst having good crush strength, because in
petroleum refining the catalyst is often subjected to
rough handling. This tends to break the catalyst down
into powders which cause problems in processing.
Naturally occurring clays which can be
composited with the synthetic zeolites of this invention
include the montmorillonite and kaolin families, which
families include the sub-bentonites and the kaolins
commonly known as Dixie, McNamee, Georgia and Florida
clays or others in which the main mineral constituent is
halloysite, kaolinite, dickite, nacrite, or anauxite.
Fibrous clays such as sepiolite and attapulgite can also
be used as supports. Such clays can be used in the raw
state as originally mined or can be initially subjected to
calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the
SSZ-26 zeolites can be composited with porous matrix
materials and mixtures of matrix materials such as
o ~ -lo- t 3 3 5 ~ O O
-
silica, alumina, titania, magnesia, silica:alumina,
silica-magnesia, silica-zirconia, silica-thoria, silica-
S beryllia, silica-titania, titania-zirconia as well as
ternary compositions such as silica-alumina-thoria,
silica-alumina-zirconia, silica-alumina-maqnesia and
silica-magnesia-zirconia. The matrix can be in the form
of a cogel.
The SSZ-26 zeolites can also be composited with
other zeolites such as synthetic and natural faujasites
(e.g., X and Y), erionites, and mordenites. They can also
be composited with purely synthetic zeolites such as those
of the ZSM, EU, FU, and NU series. The combination of
zeolites can also be composited in a porous inorganic
matrix.
SSZ-26 zeolites are useful in hydrocarbon
conversion reactions. Hydrocarbon conversion reactions
are chemical and catalytic processes in which carbon
containing compounds are changed to different carbon con-
taining compounds. Examples of hydrocarbon conversion
reactions include catalytic cracking, hydrocracking, and
olefin and aromatics formation reactions. The catalysts
are useful in other petroleum refining and hydrocarbon
conversion reactions such as isomerizing n-paraffins and
naphthenes, polymerizing and oligomerizing olefinic or
acetylenic compounds such as isobutylene and butene-l,
reforming, alkylating, isomerizing polyalkyl substituted
aromatics (e.g., metaxylene), and disproportionating
aromatics (e.g., toluene) to provide mixtures of benzene,
xylenes and higher methylbenzenes. The SSZ-26 cataly.sts
have high selectivity, and under hydrocarbon conversion
conditions can provide a high percentage of desired
products relative to total products.
SSZ-26 zeolites can be used in processing
hydrocarbonaceous feedstocks. Hydrocarbonaceous feed-
stocks contain carbon compounds and can be from many
different sources, such as virgin petroleum fractions,
recycle petroleum fractions, shale oil, liquefied coal,
tar sand oil, and, in general, can be any carbon
-11- 1 3~5~00
containing fluid susceptible to zeolitic catalytic
reactions. Depending on the type of processing the hydro-
05 carbonaceous feed is to undergo, the feed can contain
metal or be free of metals, it can also have high or lownitrogen or sulfur impurities. It can be appreciated,
however, that in general processing will be more efficient
(and the catalyst more active) the lower the metal,
nitrogen, and sulfur content of the feedstock.
The conversion of hydrocarbonaceous feeds can
take place in any convenient mode, for example, in fluid-
ized bed, moving bed, or fixed bed reactors depending on
the types of process desired. The formulation of the
catalyst particles will vary depending on the conversion
process and method of operation.
Other reactions which can be performed using the
catalyst of this invention containing a metal, e.g., a
Group VIII metal such as platinum, include hydrogenation-
dehydrogenation reactions, denitrogenation and
desulfurization reactions.
SSZ-26 can be used in hydrocarbon conversion
reactions with active or inactive supports, with organic
or inorganic binders, and with and without added metals.
These reactions are well known to the art, as are the
reaction conditions.
Using SSZ-26 catalyst which contains a
hydrogenation promoter, heavy petroleum residual feed-
stocks, cyclic stocks and other hydrocrackate charge
stocks can be hydrocracked at hydrocracking conditions
including a temperature in the range of from 175C to
485C, molar ratios of hydrogen to hydrocarbon charge from
1 to 100, a pressure in the range of from 0.5 to 350 bar,
and a liquid hourly space velocity (LHSV) in the range of
from 0.1 to 30.
The hydrocracking catalysts contain an effective
amount of at least one hydrogenation catalyst (component)
of the type commonly employed in hydrocracking catalysts.
The hydrogenation component is generally selected from the
4 group of hydrogenation catalysts consisting of one or more
01 -12- 1 3 3 5 6 0 0
metals of Group VIB and Group VIII, including the salts,
complexes and solutions containing such. The hydrogena-
05 tion catalyst is preferably selected from the group of
metals, salts and complexes thereof of the group con-
sisting of at least one of platinum, palladium, rhodium,
iridium and mixtures thereof or the group consisting of at
least one of nickel, molybdenum, cobalt, tungsten,
titanium, chromium and mixtures thereof. Reference to the
catalytically active metal or metals is intended to encom-
pass such metal or metals in the elemental state or in
some form such as an oxide, sulfide, halide, carboxylate
and the like.
lS The hydrogenation catalyst is present in an
effective amount to provide the hydrogenation function of
the hydrocracking catalyst, and preferably in the range of
from 0.05 to 25% by weight.
The catalyst may be employed in conjunction with
traditional hydrocracking catalysts, e.g., any aluminosil-
icate heretofore employed as a component in hydrocracking
catalysts. Representative of the zeolitic aluminosili-
cates disclosed heretofore as employable as component
parts of hydrocracking catalysts are Zeolite Y (including
steam stabilized, e.g., ultra-stable Y), Zeolite X,
Zeolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20
(U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent
No. 3,415,736), faujasite, LZ-10 (U.K. Patent 2,014,970,
June 9, 1982), ZSM-5-type zeolites, e.g., ZSM-5, ZSM-ll,
ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline
silicates such as silicalite ~U.S. Patent No. 4,061,724),
erionite, mordenite, offretite, chabazite, FU-l-type
zeolite, NU-type zeolites, LZ-210-type zeolite and mix-
tures thereof. Traditional cracking catalysts containing
amounts of Na2O less than about one percent by wei~ht are
generally preferred. The relative amounts of the SSZ-26
component and traditional hydrocracking component, if any,
will depend at least in part, on the selected hydrocarbon
feedstock and on the desired product distribution to be
obtained therefrom, but in all instances an effective
01 -13- 1 3 3 5 6 0 0
.
amount of SSZ-26 is employed. When a traditional hydro-
cracking catalyst (THC) component is employed the relative
S weight ratio of the THC to the SSZ-26 is generally between
about 1:10 and about 500:1, desirably between about 1:10
and about 200:1, preferably between about 1:2 and about
50:1, and most preferably is between about 1:1 and about
20:1.
The hydrocracking catalysts are typically
employed with an inorganic oxide matrix component which
may be any of the inorganic oxide matrix components which
have been employed heretofore in the formulation of
hydrocracking catalysts including: amorphous catalytic
inorganic oxides, e.g., catalytically active silica-
aluminas, clays, silicas, aluminas, silica-aluminas,
silica-zirconias, silica-magnesias, alumina-borias,
alumina-titanias and the like and mixtures thereof. The
traditional hydrocracking catalyst and SSZ-26 may be mixed
separately with the matrix component and then mixed or the
THC component and SSZ-26 may be mixed and then formed with
the matrix component.
SSZ-26 can be used to dewax hydrocarbonaceous
feeds by selectively removing straight chain paraffins.
The catalytic dewaxing conditions are dependent in large
measure on the feed used and upon the desired pour point.
Generally, the temperature will be between about 200C and
about 475C, preferably between about 250C and about
450C. The pressure is typically between about 15 psig
and about 3000 psig, preferably between about 200 psig and
3000 psig. The liquid hourly space velocity (LHSV)
preferably will be from 0.1 to 20, preferably between
about 0.2 and about 10.
Hydrogen is preferably present in the reaction
zone during the catalytic dewaxing process. The hydrogen
to feed ratio is typically between about 500 and about
30,000 SCF/bbl (standard cubic feet per barrel), prefer-
ably about 1000 to about 20,000 SCF/bbl. Generally,
hydrogen will be separated from the product and recycled
to the reaction zone. Typical feedstocks include light
ol 1 335~00
-14-
-
gas oil, heavy gas oils and reduced crudes boiling about
350F
The SSZ-26 hydrodewaxin~ catalyst may optionally
contain a hydrogenation component of the type commonly
employed in dewaxing catalysts. The hydrogenation com-
ponent may be selected from the group of hydrogenation
catalysts consisting of one or more metals of Group VIB
and Group VIII, including the salts, complexes and solu-
tions containing such metals. The preferred hydrogenation
catalyst is at least one of the group of metals, salts and
complexes selected from the group consisting of at least
one of platinum, palladium, rhodium, iridium and mixtures
thereof or at least one from the group consisting of
nickel, molybdenum, cobalt, tungsten, titanium, chromium
and mixtures thereof. Reference to the catalytically
active metal or metals is intended to encompass such metal
or metals in the elemental state or in some form such as
an oxide, sulfide, halide, carboxylate and the like.
The hydrogenation component is present in an
effective amount to provide an effective hydrodewaxing
catalyst preferably in the range of from about 0.05 to 5%
by weight.
SSZ-26 can be used to convert light straight run
naphthas and similar mixtures to highly aromatic mixtures.
Thus, normal and slightly branched chained hydrocarbons,
preferably having a boiling range above about 40C and
less than about 200C, can be converted to products having
a substantial higher octane aromatics content by contact-
ing the hydrocarbon feed with the zeolite at a temperature
in the range of from about 400C to 600C, preferably
480C-550C at pressures ranging from atmospheric to lO
bar, and liquid hourly space velocities (LHSV) ranging
from O.l to 15.
The conversion catalyst preferably contains a
Group VIII metal compound to have sufficient activity for
commercial use. By Group VIII metal compound as used
herein is meant the metal itself or a compound thereof.
The Group VIII noble metals and their compounds, platinum,
-15- 1 3 3 5 6 0 0
palladium, and iridium, or combinations thereof can be
used. Rhenium or tin or a mixture thereof may also be
05 used in conjunction with the Group VIII metal compound and
preferably a noble metal compound. The most preferred
metal is platinum. The amount of Group VIII metal present
in the conversion catalyst should be within the normal
range of use in reforming catalysts, from about 0.05 to
2.0 weiqht percent, preferably 0.2 to 0.8 weight percent.
The zeolite/Group VIII metal conversion catalyst
can be used without a binder or matrix. The preferred
inorganic matrix, where one is used, is a silica-based
binder such as Cab-O-SilTMor LudoxTM Other matrices such as
magnesia and titania can be used. The preferred inorganic
matrix is nonacidic.
It is critical to the selective production of
aromatics in useful quantities that the conversion cata-
lyst be substantially free of acidity, for example, by
poisoning the zeolite with a basic metal, e.g., alkali
metal, compound. The zeolite is usually prepared from
mixtures containing alkali metal hydroxides and thus have
alkali metal contents of about 1-3 weight Percent. These
high levels of alkali metal, usually sodium, potassium or
2 cesium, are unacceptable for most catalytic applications
because they greatly deactivate the catalyst for cracking
reactions. Usually, the alkali metal is removed to low
levels by ion-exchange with hydrogen or ammonium ions. By
alkali metal compound as used herein is meant elemental or
ionic alkali metals or their basic compounds. Surprisingly,
unless the zeolite itself is substantially free of
acidity, the basic compound is required in the present
process to direct the synthetic reactions to aromatics
production.
The amount of alkali metal necessary to render
the zeolite substantially free of acidity can be calcu-
lated using standard techniques based on the aluminum
content of the zeolite. Under normal circumstances, the
zeolite as prepared and without ion-exchange will contain
sufficient alkali metal to neutralize the acidity of the
01 -16- 1 3 3 5 6 0 0
catalyst. If a zeolite free of alkali metal is the
starting material, alkali metal ions can be ion exchanged
05 into the zeolite to substantially eliminate the acidity of
the zeolite. An alkali metal content of about 1003, or
greater, of the acid sites calculated on a molar basis is
sufficient.
Where the basic metal content is less than 100%
of the acid sites on a molar basis, the test described in
U.S. Patent No. 4,347,394 can be used to determine if the
zeolite is substantially free of acidity.
The preferred alkali metals are sodium, potas-
sium, and cesium. The zeolite itself can be substantially
free of acidity only at very high silica:alumina mol
ratios; by "zeolite consisting essentially of silica" is
meant a zeolite which is substantially free of acidity
without base poisoning.
Hydrocarbon cracking stocks can be catalytically
cracked in the absence of hydrogen using SSZ-26 at liquid
hourly space velocities from 0.5 to 50, temperatures from
about 260F to 1625F and pressures from subatmospheric to
several hundred atmospheres, typically from about
atmospheric to about 5 atmospheres.
For this purpose, the SSZ-26 catalyst can be
composited with mixtures of inorganic oxide supports as
well as traditional cracking catalyst.
The catalyst may be employed in conjunction with
traditional cracking catalysts, e.g., any aluminosilicate
heretofore employed as a component in cracking catalysts.
Representative of the zeolitic aluminosilicates disclosed
heretofore as employable as component parts of cracking
catalysts are Zeolite Y (including steam stabilized
chemically modified, e.g., ultra-stable Y), Zeolite X,
2eolite beta (U.S. Patent No. 3,308,069), Zeolite ZK-20
(U.S. Patent No. 3,445,727), Zeolite ZSM-3 (U.S. Patent
No. 3,415,736), faujasite, LZ-10 (U.K. Patent 2,014,970,
June 9, 1982), ZSM-5-type zeolites, e.g., ZSM-5, ZSM-ll,
zSrl-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, crystalline
Ol -17- 1 3 3 5 6 0 0
silicates such as silicalite (U.S. Patent No. 4,061,724),
erionite, mordenite, offretite, chabazite, FU-l-type
05 zeolite, NU-type zeolites, LZ-210-type zeolite and
mixtures thereof. Traditional cracking catalysts
containing amounts of Na2O less than about one percent by
weight are generally preferred. The relative amounts of
the SSZ-26 component and traditional cracking component,
if any, will depend at least in part, on the selected
hydrocarbon feedstock and on the desired product distri-
bution to be obtained therefrom, but in all instances an
effective amount of SSZ-26 is employed. When a tradi-
tional cracking catalyst (TC) component is employed the
relative weight ratio of the TC to the SSZ-26 is generally
between about 1:10 and about 500:1, desirably between
about 1:10 and about 200:1, preferably between about 1:2
and about 50:1, and most preferably is between about 1:1
and about 20:1.
The cracking catalysts are typically employed
with an inorganic oxide matrix component which may be any
of the inorganic oxide matrix components which have been
employed heretofore in the formulation of FCC catalysts
including: amorphous catalytic inorganic oxides, e.g.,
catalytically active silica-aluminas, clays, silicas,
aluminas, silica-aluminas, silica-zirconias, silica-
magnesias, alumina-borias, alumina-titanias and the like
and mixtures thereof. The traditional cracking component
and SSZ-26 may be mixed separately with the matrix
component and then mixed or the TC component and SSZ-26
may be mixed and then formed with the matrix component.
The mixture of a traditional cracking catalyst
and SSZ-26 may be carried out in any manner which results
in the coincident presence of such in contact with the
3 crude oil feedstock under catalytic cracking conditions.
For example, a catalyst may be employed containing the
traditional cracking catalyst and a SSZ-26 in single
catalyst particles or SSZ-26 with or without a matrix
component may be added as a discrete component to a
traditional cracking catalyst.
l -18- 1 3 3 5 6 0 0
SSZ-26 can also be used to oligomerize straight
and branched chain olefins having from about 2 to 21 and
S preferably 2-5 carbon atoms. The oligomers which are the
products of the process are medium to heavy olefins which
are useful for both fuels, i.e., gasoline or a gasoline
blending stock and chemicals.
The oligomerization process comprises contacting
the olefin feedstock in the gaseous state phase with
SSZ-26 at a temperature of from about 450F to about
1200F, a WHSV of from about 0.2 to about 50 and a hydro-
carbon partial pressure of from about 0.1 to about 50
atmospheres.
Also, temperatures below about 450F may be used
to oligomerize the feedstock, when the feedstock is in the
liquid phase when contacting the zeolite catalyst. Thus,
when the olefin feedstock contacts the zeolite catalyst in
the liquid phase, temperatures of from about 50F to about
450F, and preferably from 80 to 400F may be used and a
WHSV of from about 0.05 to 20 and preferably .1 to 10. It
will be appreciated that the pressures employed must be
sufficient to maintain the system in the liquid phase. As
is known in the art, the pressure will be a function of
the number of carbon atoms of the feed olefin and the
temperature. Suitable pressures include from about 0 psig
to about 3000 psig.
The zeolite can have the original cations
associated therewith replaced by a wide variety of other
cations according to techniques well known in the art.
Typical cations would include hydrogen, ammonium and metal
cations including mixtures of the same. Of the replacing
metallic cations, particular preference is given to
cations of metals such as rare earth metals, manganese,
calcium, as well as metals of Group II of the Periodic
Table, e.g., zinc, and Group VIII of the Periodic Table,
e.g., nickel. One of the prime requisites is that the
zeolite have a fairly low aromatization activity, i.e., in
which the amount of aromatics produced is not more than
about 20% by weight. This is accomplished by using a
1 335600
o 1 - 1 9 -
zeolite with controlled acid activity [alpha value] offrom about 0.1 to about 120, preferably from about 0.1 to
05 about 100, as measured by its ability to crack n-hexane.
Alpha value are defined by a standard test known
in the art, e.g., as shown in U.S. Patent No. 3,960,978,
If required, such zeolites may be obtained by steaming,
by use in a conversion process or by any other method
which may occur to one skilled in this art.
SSZ-26 can be used to convert light gas C2-C6
paraffins and/or olefins to higher molecular weight
hydrocarbons including aromatic compounds. Operating
temperatures of 100C-700C, operating pressures of 0 to
1000 psig and space velocities of 0.5-40 hr 1 WHSV (weight
hourly space velocity) can be used to convert the C2-C6
paraffin and/or olefins to aromatic compounds. Preferably,
the zeolite will contain a catalyst metal or metal oxide
wherein said metal is selected from the group consisting
of Group IB, IIB, VIII and IIIA of the Periodic Table, and
most preferably gallium or zinc and in the range of from
about 0.05 to 5% by weight.
SSZ-26 can be used to condense lower aliphatic
alcohols havinq 1 to 10 carbon atoms to a gasoline boiling
point hydrocarbon product comprising mixed aliphatic and
aromatic hydrocarbon. The condensation reaction proceeds
at a temperature of about 500F to 1000F, a pressure of
about 0.5 to 1000 psig and a space velocity of about 0.5
to 50 WHSV. The process disclosed in U.S. Patent
No. 3,984,107 more specifically describes the process
conditions used in this process.
The catalyst may be in the hydrogen form or may
be base exchanged or impregnated to contain ammonium or a
metal cation complement, preferably in the range of from
about 0.05 to 5% by weight. The metal cations that may be
present include any of the metals of the Groups I through
VIII of the Periodic Table. However, in the case of
-20- l 3 3 5 6 0 0
Group IA metals the cation content should in no case be so
large as to effectively inactivate the catalyst.
S The present catalyst is highly active and highly
selective for isomerizing C4 to C7 hydrocarbons. The
activity means that the catalyst can operate at relatively
low temperature which thermodynamically favors highly
branched paraffins. Consequently, the catalyst can pro-
duce a high octane product. The high selectivity means
that a relatively high liquid yield can be achieved when
the catalyst is run at a high octane.
The present process comprises contacting the
i somerization catalyst with a hydrocarbon feed under
isomerization conditions. The feed is preferably a light
straight run fraction, boiling within the range of 30F to
250F and preferably from 60F to 200F. Preferably, the
hydrocarbon feed for the process comprises a substantial
a~ount of C4 to C7 normal and slightly branched low octane
~U hydrocarbons, more preferably C5 and C6 hydrocarbons.
The pressure in the process is preferably
between 50 psig and 1000 psig, more preferably between 100
and 500 psig. The liquid hourly space velocity (LHSV) is
preferably between about 1 to about lO with a value in the
range of about 1 to about 4 being more preferred. It is
also preferable to carry out the isomerization reaction in
the presence of hydrogen. Preferably, hydrogen is added
to give a hydrogen to hydrocarbon ratio (H2/HC) of between
0.5 and 10 H2/HC, more preferably between 1 and 8 H2/HC.
The temperature is preferably between about 200F and
about 1000F, more preferably between 400F and 600F. As
is well known to those skilled in the isomerization art,
the initial selection of the temperature within this ~road
range is made primarily as a function of the desired con-
version level considering the characteristics of the feed
and of the catalyst. Thereafter, to provide a relatively
constant value for conversion, the temperature may have to
be slowly increased during the run to compensate for any
deactivation that occurs.
~ -21- 1 3356GO
A low sulfur feed is especially preferred in the
present process. The feed preferably contains less than
S 10 ppm, more preferably less than 1 ppm, and most prefer-
ably less than 0.1 ppm sulfur. In the case of a feed
which is not already low in sulfur, acceptable levels can
be reached by hydrogenating the feed in a presaturation
zone with a hydrogenating catalyst which is resistant to
sulfur poisoning. An example of a suitable catalyst for
this hydrodesulfurization process is an alumina-containing
support and a minor catalytic proportion of molybdenum
oxide, cobalt oxide and/or nickel oxide. A platinum on
alumina hydrogenating catalyst can also work. In which
case a sulfur sorber is preferably placed downstream of
the hydrogenating catalyst, but upstream of the present
isomerization catalyst. Examples of sulfur sorbers are
alkali or alkaline earth metals on porous refractory
inorganic oxides, zinc, etc. Hydrodesulfurization is
typically conducted at 315C to 455C, at 200 to
2000 psig, and at a liquid hourly space velocity of 1
to 5.
It is preferable to limit the nitrogen level and
the water content of the feed. Catalysts and processes
which are suitable for these purposes are known to those
skilled in the art.
After a period of operation the catalyst can
become deactivated by sulfur or coke. Sulfur and coke can
be removed by contacting the catalyst with an oxygen-
containing gas at an elevated temperature. If the
Group VIII metal(s) have agglomerated, then it can be
redispersed by contacting the catalyst with a chlorine gas
under conditions effective to redisperse the metal(s).
The method of regenerating the catalyst may depend on
whether there is a fixed bed, moving bed, or fluidized bed
operation. Regeneration methods and conditions are well
known in the art.
The conversion catalyst preferably contains a
Group VIII metal compound to have sufficient activity for
commercial use. By Group VIII metal compound as used
_ -22- 1 3 3 5 6 G O
herein is meant the metal itself or a compound thereof.
The Group VIII noble metals and their compounds, platinum,
palladium, and iridium, or combinations thereof can be
used. Rhenium and tin may also be used in conjunction
with the noble metal. The most preferred metal is
platinum. The amount of Group VIII metal present in the
conversion catalyst should be within the normal ran~e of
use in isomerizing catalysts, from about 0.05 to 2.0
weight p~rcent, preferably 0.2 to 0.8 weight percent.
SSZ-26 can be used in a process for the
alkylation or transalkylation of an aromatic hydrocarbon.
The process comprises contacting the aromatic hydrocarbon
with a C2 to C4 olefin alkylating agent or a polyalkyl
aromatic hydrocarbon transalkylating agent, under at least
partial liquid phase conditions, and in the presence of a
catalyst comprising SSZ-26.
For high catalytic activity, the SSZ-26 zeolite
~()
should be predominantly in~its hydrogen ion form.
Generally, the zeolite is converted to its hydrogen form
by ammonium exchange followed by calcination. If the
zeolite is synthesized with a high enough ratio of organo-
nitrogen cation to sodium ion, calcination alone may be
sufficient. It is preferred that, after calcination, at
least 80% of the cation sites are occupied by hydrogen
ions and/or rare earth ions.
The pure SSZ-26 zeolite may be used as a
catalyst, but generally it is preferred to mix the zeolite
powder with an inorganic oxide binder such as alumina,
silica, silica/alumina, or naturally occurring clays and
form the mixture into tablets or extrudates. The final
catalyst may contain from 1 to 99 wt % SSZ-26 zeolite.
Usually the zeolite content will range from 10 to 90 wt %,
and more typically from 60 to 80 wt %. The preferred
inorganic binder is alumina. The mixture may be formed
into tablets or extrudates having the desired shape by
methods well known in the art.
Examples of suitable aromatic hydrocarbon
feedstocks which may be alkylated or transalkylated by the
-23- 1 3 3 5 6 0 0
process of the invention include aromatic compounds such
as benzene, toluene and xylene. The preferred aromatic
05 hydrocarbon is benzene. ~ixtures of aromatic hydrocarbons
may also be employed.
Suitable olefins for the alkylation of the
aromatic hydrocarbon are those containing 2 to 4 carbon
atoms, such as ethylene, propylene, butene-l, trans-
butene-2 and cis-butene-2, or mixtures thereof. The
preferred olefin is propylene. These olefins may be
present in admixture with the corresponding C2 to C4
paraffins, but it is preferable to remove any dienes,
acetylenes, sulfur compounds or nitrogen compounds which
may be present in the olefin feedstock stream, to prevent
rapid catalyst deactivation.
When transalkylation is desired, the
transalkylating agent is a polyalkyl aromatic hydrocarbon
containing two or more alkyl groups that each may have
from 2 to about 4 carbon atoms. For example, suitable
polyalkyl aromatic hydrocarbons include di-, tri- and
tetra-alkyl aromatic hydrocarbons, such as diethylbenzene,
triethylbenzene, diethylmethylbenzene (diethyltoluene),
di-isopropylbenzene, di-isopropyltoluene, dibutylbenzene,
and the like. Preferred polyalkyl aromatic hydrocarbons
are the dialkyl benzenes. A particularly preferred
polyalkyl aromatic hydrocarbon is di-isopropylbenzene.
Reaction products which may be obtained include
ethylbenzene from the reaction of benzene with either
ethylene or polyethylbenzenes, cumene from the reaction of
benzene with propylene or polyisopropylbenzenes, ethyl-
toluene from the reaction of toluene with ethylene or
polyethyltoluenes, cymenes from the reaction of toluene
with propylene or polyisopropyltoluenes, and sec-
butylbenzene from the reaction of benzene and n-butenes or
polybutylbenzenes. The production of cumene from the
alkylation of benzene with propylene or the transalkyl-
ation of benzene with di-isopropylbenzene is especially
preferred.
' -24- 1 3 3 5 6 0 0
When alkylation is the process conducted,
reaction conditions are as follows. The aromatic
05 hydrocarbon feed should be present in stoichiometric
excess. It is preferred that molar ratio of aromatics to
olefins be greater than four-to-one to prevent rapid
catalyst foulinq. The reaction temperature may range from
100F to 600F, preferably, 250F to 450F. The reaction
pressure should be sufficient to maintain at least a
partial liquid phase in order to retard catalyst fouling.
This is typically 50 to 1000 psig depending on the feed-
stock and reaction temperature. Contact time may range
from 10 seconds to 10 hours, but is usually from 5 minutes
to an hour. The weiqht hourly space velocity (WHSV), in
terms of grams (pounds) of aromatic hydrocarbon and olefin
per gram tpound) of catalyst per hour, is generally within
the range of about 0.5 to 50.
When transalkylation is the process conducted,
the molar ratio of aromatic hydrocarbon will generally
range from about 1:1 to 25:1, and preferably from about
2:1 to 20:1. The reaction temperature may range from
about 100F to 600F, but it is preferably about 250F to
450F. The reaction pressure should be sufficient to
maintain a least a partial liquid phase, typically in the
range of about 50 psig to 1000 psig, preferably 300 psig
to 600 psig. The weight hourly space velocity will range
from about 0.1 to 10.
SSZ-26 can also be used as an adsorbent, as
a filler in paper, paint, and toothpastes, and as a
water-softening agent in detergents.
The present invention will be more fully
understood by reference to the following examples. They
are intended to be purely exemplary and are not intended5 to limit the scope of the invention in any way.
EXAMPLES
Example 1
[4.3.3.0] Propellane-8,11-dione was prepared
according to the Cook and Weiss [J. Org. Chem. 41 4053
(1976)]. The dione was then heated for 16 hours in a
01 -25- 1 3 3 5 ~ O O
~ closed pressure vessel with Dimethylformamide and Formic
acid (88%) in a Leukart-type reaction. The reaction is
05 cooled to room temperature, dissolved in water, brought to
a pH of 12 with alkali, and extracted twice with equal
volumes of diethyl ether. The extract is dried over
sodium sulfate and the solvent removed. The N,N,N',N'-
tetramethyl [4.3.3.0] propellane-8,11-diamine product
(which has an elemental analysis consistent with the theo-
retical structure of the diamine) is dissolved in
chloroform and an excess of methyl iodide is added and the
reaction is stirred overnight to produce the crystalline
diquaternary ammonium product ta small amount of mono
amine is also produced in this reaction sequence. It can
be carried through all steps without adversely effecting
the zeolite synthesis or can be removed by fractional
crystallization from hot ethanol once the quaternized
product has been achieved). The crystalline product having
~0 a melting point of 304-306C is N,N,N,N',N',N'-Hexamethyl
[4.3.3.0] Propellane-8,11-diammonium diiodide. At this
stage three isomeric forms of the compound may be possible.
The orientation of the diammonium groups relative to the
carbocyclic skeleton may be syn,syn or syn,anti, or
anti,anti. The template can be further purified by
recrystallization from Ethanol/water t20/1). This greatly
I diminishes the formation of other zeolite impurities.
Example 2
The product of Exam~le 1 was dissolved in water
tso as to produce a 0.5 to 1.0 M solution) and stirred
overnight with an excess of ~owex 1 AG-X8 hydroxide ion-
exchange resin. The resin was filtered and the basic
solution was titrated with an analytical solution of HCl.
Similarly, other anions such as acetate,
sulfate, bromide, carboxylate and tetrafluoroborate may be
substituted for the hydroxy by using the appropriate ion-
exchange resin.
Example 3
76 Grams of a 0.45 M solution of Template from
Example 2 in its hydroxide form were mixed with 1.58 gms
of NaOH tsolid). After dissolution 0.89 gm of sodium
0! -26- ~ 1 335600
._
aluminate (75% solids) were added with stirring using a
magnetic stir bar. Finally 9.08 gms of Cabosil M5 fumed
05 silica was added. The reactants were loaded into a Parr
300 cc reactor, sealed and heated. The reactor was
stirred at 60 RPM while being heated at 175C for 6 days.
The product after filtration, washing with distilled
water, drying in air and then at 100C was the crystalline
material designated SSZ-26. The X-ray diffraction pattern
of the as-made material is tabulated in Table 3 below.
Table 3
2 e d/n 100 x I/Io Comments
7.83 11.300 100
14.19 6.240 5
15.65 5.660 7
20.28 4.380 61
20.93 4.240 9 QTZ
21.39 4.150 25
22.00 4.040 55
22.82 3.900 45 Sh
23.05 3.860 70
25.26 3.530 9
26.50 3.360 36
26.68 3.340 54 QTZ
QTZ = Quartz
Sh = Shoulder
Example 4
75 Grams of a 0.45 M solution of Template were
mixed with 1.70 gms NaOH(s), and 2.70 gms of SK-40 Y
zeolite (sold by Union Carbide) as source of alumina.
After thorough mixing 7.20 gms of Cabosil was blended in
as silica source. The reaction mixture was heated in a
Parr 300 cc reactor at 175C at 45 RPM for 6 days. Workup
as in Example 3 produced crystalline SSZ-26 and a minor
amount of quartz.
Example 5
In this example Na-Y zeolite (SK-40) was used
again but the initial OH-/SiO2 ratio was lowered to 0.20,
01 -27- 1 3356a~
0.23 gms of SK-40, as source of alumina, was used and
dispersed in 6 ml H2O, 0.07 gm NaOH, and 2.4 gms of a
S 0.5 M Template solution. 0.72 Grams of Cabosil was used
and the reaction was run at 170C but at 30 RPM. At
6 days of reaction the product was crystalline SSZ-26.
The SiO2/A12O3 value of the zeolite is 35.
Example 6
2.4 Grams of a 0.5 M solution of Template was
mixed with 6 ml of H2O, 0.21 gms of NaOH(s), 0.29 gms of
Na-Y zeolite, as source of alumina, and finally 0.72 gms
of Cabosil M5. The mixture was heated at 160C for 6 days
with 30 RPM agitation. The crystalline product was SSZ-26
and has a SiO2/A12O3 ratio of 25.
Example 7
A reaction like Example 6 was set up again.
This time the reactants were increased 15 fold. The
mixture was seeded with a small quantity from Example 6,
and heated static at 160C. The crystalline product after
12 days of reaction and the usual workup was SSZ-26, with
minor quantities of analcime and quartz.
Example 8
The template is prepared as described in
Example 1, but instead of using Ethanol/water in the final
I recrystallization step, Acetonitrile/water is used
(15/1). A lower yield of crystals are recovered but it
gives a correct microanalysis for the desired product.
Even though the integrations are correct for the various
protons as seen in the NMR, the coupling constants are now
markedly different. Also the IR pattern contains some new
bands. Clearly a different isomer has been recovered from
the potential mixture. This new product is converted to
the hydroxide form as in Example 2. 1.2 mmoles of this
form of the template in 7 ml of water are combined with
0.20 gms of NaOH(s), 0.28 gms of SK-40 zeolite, and
finally 0.72 gms of Cabosil. A Teflon ball ~3/4 in.) is
placed in the reactor to aid in stirring. The reactor is
tumbled at 30 RPM while being heated to 170C for 6 days.
The product after the usual workup was well-crystallized
~ -28- 1 3 3 5 6 0 0
SSZ-26. The data for the XRD analysis appears in
Table 4. This example demonstrates that more than one
isomeric conformation is capable of producing SSZ-26 in
the present invention.
Table 4
2 e d/n 100 x I/Io
7.77 11.38 76
8.92 9.91 11 B
9.42 9.39 8 B
13.15 6.73 7 B
14.10 6.28 4
14.77 6.00 6 8
15.25 5.84 6
15.58 5.69 11
19.68 4.51 14 B
20.20 4.396 80
21.24 4.1~3 38
21.84 4.069 72
22.77 3.905 63 Sh
22.92 3.880 100
25.12 3.545 10
26.50 3.363 51
28.38 3.145 6
28.86 3.094 8
30.33 2.947 7
B = Broad
Sh = Shoulder
Example 9
3.75 gms of the template prepared as in
Example 2 (0.63 M) is combined with 0.30 gms of NaOH(s)
and 9.3 ml water. 0.53 gms of SK-40 are added and then
1.35 gms of Cabosil. After placing a Teflon-coated stir
bar in the reactor it is sealed and heated at 170C for
6 days while tumbling at 30 RPM. The product after the
usual workup was SSZ-26 and the XRD data appears in
Table 5.
01 -29-1 3 3 5 6 0 0
Table 5
2 e d/n 100 x I/Io
05
7.74 11.420 90
8.30 10.650 6 B
8.88 9.960 10 B
13.20 6.707 7 B
14.08 6.290 6
15.22 5.821 9 B
15.55 5.698 12
16.63 5.331 2
19.59 4.531 10
1s 20.17 4.402 100
21.26 4.179 40
21.87 4.064 88
22.77 3.905 60 Sh
22.92 3.880 100
25.14 3.542 14
26.45 3.370 60
27.62 3.230 4 B
27.93 3.194 4 B
28.43 3.139 11
28.90 3.089 10
29.60 3.018 3 B
30.33 2.947 11
31.43 2.846 8
31.93 2.803 7
33.19 2.699 12
35.32 2.541 10
35.63 2.520 5
36.30 2.475 3
36.80 2.442 8
37.23 2.415 5
40.17 2.245 6
41.95 2.154 2
43.06 2.101 7
B = Broad
Sh = Shoulder
_ ~30- 1 3 3 5 6 0 0
Example 10
1.2 mm of the template from Example 2 and in
S 8 ml water is combined with 0.12 gms of NaOH(s), 0.28 gms
of SK-40, and finally 0.72 gms of Cabosil. After adding
the Teflon-coated stirrer and closing the reactor, the
reaction is run for about 9 days at 160C and 30 RPM
tumbling. The product was a nicely crystallized sample of
SSZ-26. The product showed a very homogeneous distribu-
tion in the scanning electron microscope. The XRD data is
given in Table 6.
Table 6
As Prepared
2 e d/n100 x I~Io
7.78 11.36 100
8.32 10.63 4 B
8.90 9.94 10 B
13.20 6.71 5
14.15 6.26 5
15.26 5.81 4 B
15.62 5.67 8
15.92 5.57 7
16.74 5.30 2
19.63 4.52 6 B
20.23 4.389 63 B
21.37 4.158 25
21.99 4.042 53
22.85 3.89 46 Sh
23.00 3.867 64
25.20 3.534 9
26.15 3.408 8
26.49 3.365 33
28.51 3.131 8
28.95 3.084 7
B = Broad
Sh = Shoulder
01 -31-
1 335600
Example 11
The crystalline products of Examples 3-10 were
S subjected to calcination as follows. The samples were
heated in a muffle furnace from room temperature up to
540C at a steadily increasin~ rate over a 7-hour
period. The samples were maintained at 540C for four
more hours and then taken up to 600C for an additional
four hours. A 50/50 mixture of air and nitrogen was
passed over the zeolites at a rate of 20 standard cubic
feet per minute during heating. Representative X-ray
diffraction data for the calcined product of Example 8
appears in Table 7.
~ -32- 1 3 3 5 6 0 0
Table 7
05 2 e d/n100 x I/Io Comments
6.1814.300 3 Y zeolite
7.7411.420 100
8.3010.650 3
8.6310.250 3
8.959.880 6
9.449.370 12
9.829.007 6
13.126.748 13
14.086.290 10
14.756.006 6
15 535.706 9
16 005.539 2
16.635.331 5
19.754.495 9
20.184.400 60
20.854.260 5 QTZ
21.274.177 21
21.904.058 55
22.903.883 49 Sh
23.033.862 98
25.173.538 18
26.453.370 58
26 603.351 36 QTZ
28 423.140 12
28.903.089 15
29.633.015 4
30.402.940 10
31.412.848 8
32.002.797 7
33.272.693 11
35.382.537 9
35.622.520 4
36.322.473 4
39.792.443 5
37.332.409 2
38.322.349 4
40.152.246 4
42.002.151
42.422.131
43.762.069 7
QTZ = Quartz
Sh = Shoulder
01 _33_ 1 3 3 5 6 0 0
- Example 12
Ion-exchange of the calcined SSZ-26 materials
05 from Example 8 was carried out using NH4NO3 to convert the
zeolites from their Na form to NH4 and then eventually H
form. Typically the same mass of NH4NO3 as zeolite was
slurried into H2O at ratio of 50/1 H2O to zeolite. The
exchange solution was heated at 100C for two hours and
then filtered. This process was repeated four times.
Finally, after the last exchange the zeolite was washed
several times with H2O and dried. A repeat calcination as
in Example 11 was carried out but without the final treat-
ment at 600C. This produces the H form of SSZ-26
zeolite.
Example 13
The product of Example 6, after sequential
treatment as in Examples 11 and then 12, was subjected to
a surface area and pore size distribution analysis using
N2 as adsorbate and via the BET method. The surface area
of the zeolitic material was 560 m2/gm and the micropore
volume was 0.19 cc/gm.
Example 14
Constraint Index Determination:
0.25 Grams of the hydrogen form of the zeolite
of Example 4 (after treatment according to Examples 11 and
12) was packed into a 3/8" stainless steel tube with
alundum on both sides of the zeolite bed. A Lindburg
furnace was used to heat the reactor tube. Helium was
introduced into the reactor tube at 10cc/min. and atmos-
pheric pressure. The reactor was taken to 250F for40 min. and then raised to 600F. Once temperature equi-
libration was achieved a 50/50, w/w feed of n-hexane and
3-methylpentane was introduced into the reactor at a rate
of 0.62cc/hr. Feed delivery was made via syringe pump.
Direct sampling onto a gas chromatograph began after 10
minutes of feed introduction. The constraint index value
was calculated from gas chromatographic data using methods
known in the art. It can be seen that novel zeolite
SSZ-26 has very high cracking activity.
~ -34- 1 3 3 5 6 0 0
Conversion
Example No. C.I. at 10 min. Temp. F
S 4 0-3 95% 600
Example 15
SSZ-26 was prepared as in Example 9 and treated
as in Examples 11 and 12. The acid form of the zeolite
was then neutralized by refluxinq overnight with dilute
KOH. After washing and drying the zeolite it was calcined
to 1000Y. The KOH treatment was repeated a second time
with subsequent washing, drying and calcination. The
K-exchanged zeolite was impregnated (via incipient
wetness) with 0.8 wt % Pt, dried overnight at 250F and
then calcined 3 hours at 500F; The catalyst was then
evaluated using a light straight run feed. Reactor
conditions:
100 = pSl9
2 = LHSV
3 H2/HC
800F = Temp.
Composition, Wt % Feed Product
C4- 0.0 30.5
Total C5 4.2 12.7
i C6 11.3 11.8
n C6 17.0 4.9
Benzene 0.5 12.5
i C7 14.5 1.7
n C7 16.7 0.6
Toluene 2.4 16.9
i C8+ 0.9 0.0
n C8+ 4.9 0.6
C8+ Aromatics1.4 4.6
LV% 100 64.2
RON 62 88.3
-35- 1 3 3 5 6 0 0
-
As might be anticipated the liquid volume yield
could be improved by further neutralization of the zeolite
S catalyst.
Example 16
The hydrogen form of SSZ-26 can be used in
catalytic cracking. For such purposes, the catalyst
prepared as in Example 9 was tested in a micro-activity
test (MAT) using the procedure developed by ASTM Committee
D-32. The test was run at 925F on fresh catalyst at a
cat/oil ratio of 3 (based upon catalyst calcined to
1100F) and a WHSV of 15-16. Table 8 shows inspections on
the feed and the resulting products. The catalyst was run
at 20 weight % in a kaolin matrix.
Table 8
MAT Test for SSZ-26 Zeolite
Feed:
API 29.09
Aniline pt, F 219.1
Ramsbottom Carbon, wt % 0.3
N(T), ppm 270
N(B), ppm 159
S(T), wt % 0.54
Test Data:
Conversion, wt % 61.0
Coke, wt % 7.8
C5-430F 23.0
403-650F 16.0
650 + 23.0
C3 14.8
C4- 30.2
C4 olefin/C4 total 0.21
Example 17
The hydrogen form of the SSZ-26 zeolite can be
used in hydrocracking conversions of hydrocarbon feeds.
The data shown in Table 9 is for the conversion of a feed
01 -36- 1 3 3 5 6 0 0
made up of representative model compounds. The data
illustrates the high activity and shape-selectivity for
SSZ-26 zeolite in hydroprocessing. The catalyst is active
by itself as used in this example or when a noble metal is
incorporated. One gram (dry basis) of catalyst was loaded
into a 1/4" reactor tube packed with alundum on either
side of the bed. The catalyst was dried at 500F for
30 min. with 1200 psi H2. The hydrogen flow rate is
55 cc/min. at atmospheric pressure and room temperature.
The feed rate was 50 microliters/min. and the catalyst was
equilibrated for 2 hours at temperature before G.C.
analysis.
Table 9
Hydroprocessing of a
Model Feed ~ith SSZ-26 Zeolite
Feed
Catalyst Alone SSZ-26 SSZ-26
Temp. --- 500F 600F
LHSV
H2 Pressure 1200 1200
Conversion 22.6 37.5
Product/Feed wt ~
Cl-C6 - 20.0 33.1
Hexamethylethane 1.1 1.6 1.8
Marker
Cyclohexane 31.9 18.4 9.0
Isooctane(2,2,4) 4.5 4.0 3.9
Toluene 33.7 33.1 31.2
3,4,Diethyl C6
4-Propyl heptane10.1 11.7 12.2
n-Decane 5.1 2.6 0.7
t-Decalin 5.5 4.9 3.7
c-Decalin 4.5 0 0
n-Dodecane 3.7 1.1 0
As can be seen above the catalyst has surprising
selectivity for n-paraffins, demonstrating its usefulness
1 335600
-37-
for dewaxing, and a selectivity for cis decalin over the
trans isomer. The reactivity is also somewhat pressure
dependent.
Example 18
Due to the strong cracking activity of the
SSZ-26 zeolite it can be advantageously used in the
isomerization of pen-hex streams to upgrade octane
values. Hydrogen SSZ-26 was prepared as in Examples 9,
11, and 12 and was impregnated with 0.8 wt % platinum.
Pure hexane was run over the catalyst using the following
parameters:
5
100 psig
6 H2/HC
3 = LHSV
501F = Temp.
~U
The product distribution from the reaction is given in
Table 10.
Table 10
25 Hydrocarbon Wt %
Methane 0.12`
Ethane 0.21
Propane 1.29
Isobutane 1.05
n-Butane 0.45
Isopentane 1.37
n-Pe~tane 0.65
2,2 DM Butane 15.74
2,3,DM Butane 8.66
2,Methylpentane 31.80
3,Methylpentane 20.99
n-Hexane 17.51
Me,Cyclopentane 0.17
Benzene 0.0
LV% 96.9
RON 75.7
_ ~33~ 1 3 3 5 6 0 0
Example 19
A commercial pen-hex stream, characterized
05 below, was used with a 0.3% Pt catalyst prepared similarly
to the one used in Example 18, and the catalyst run
conditions were:
200 = psig
6 H2/HC
1 = LHSV
485F = Temp.
At 22 hours on stream the product was the followin~:
Feed, Product
Hydrocarbon Wt % Wt
Methane0.0 0.0
Ethane0.0 0.0
Propane0.0 1.81
Isobutane 0.04 6.49
n-Butane0.28 1.15
Isopentane 12.03 22.40
n-Pentane18.93 11.75
2,2, DM Butane 0.58 5.09
Cyclopentane 4.26 3.96
2,3 DM Butane 2.26 4.48
2,Methylpentane12.55 15.14
3,Methylpentane8.19 9.81
n-Hexane 19.74 8.33
Me,Cyclopentane15.04 6.58
Benzene 3.75 0.00
Cyclohexane 1.89 1.91
Isoheptane 0.07 1.11
n-Heptane 0.15 0.00
Toluene 0.00 0.00
LV % 100 93.0
RON(GC) 74.5 79.8
4~
01 _39_ 1 3 3 5 ~ O ~
Example 20
The SSZ-26 zeolite catalyst can be used for
oS hydrocracking in conjunction with a metal component and
under hydrogen. The zeolite of Example 9 was treated as
in Examples 11 and 12 to produce the acidic form. About
0.6 wt % Pd was loaded onto the zeolite by ion-exchange in
a buffered (pH 9.5) solution. Calcination was carried out
in steps to 940F where the product TMs held for 3 hours.
Next the zeolite was bound in Catapal alumina (65/35) and
meshed to 24-40. The experimental conditions and product
properties are given in the tables below.
After hydrogen reduction at 600F and titration
at 350F with Feed A (see Table 11) spiked with 800 ppm N
using n-butylamine, Feed A was hydrocracked over the
catalyst under the conditions given in Table 12. The
product properties are given in Table 13.
Table 11
Properties of Feed A
Nitrogen, ppm 0.3
Sulfur, ppm ~2
API Gravity 32.0
Boiling Range, F
0-5% 454-544
5 50% 544-716
50-90% 716-834
85-100% 866-919
Table 12
Run Conditions For Hydrocracking
Feed A with Catalyst Pd H SSZ-26
Temperature, F 550
WHSV 1.53
Total Pressure, psig 1185
Inlet H2 P~ psia 1129
Gas Rate, SCFB 5707
'
01_40_ 1 3 3 5 6 0 ~
Table 13
05Properties of Hydrocracked Product From Feed A
Using the Catalyst Under Conditions Given in Table 12
Conversion to 450F-, Wt %71.5
C5+ Yield, Wt % ~3.0
C5-180F Yield, Wt % 23.6
180-390F, Wt % 29.9
390-450F, Wt % 0.5
Chem H2 Consumed, SCFB 936
Boiling Range, F
0-5% 41-79
5-50% 79-256
50-70% 256-599
70-90% 599-778
95-99~ 822-890
Example 21
The ability of the SSZ-26 zeolite to catalyze
the alkylation of an aromatic hydrocarbon by an olefin was
demonstrated as follows. SSZ-26 powder from Example 4
after treatment as in Examples 11 and 12 was pressed to
form tablets which were crushed and sieved to obtain
10-20 mesh granules for testing. The granular catalyst
was calcined for 4 hours at 1000F in a muffle furnace,
then weighed and charged to a tubular microreactor. The
catalyst was heated to 325F in flowing nitrogen at
atmospheric pressure. Nitrogen flow continued while the
reactor was pressurized to 600 psig. When the unit
pressure had stabilized at 600 psig, the nitrogen flow was
stopped and liquid benzene was passed upflow through the
reactor. After the reactor was filled with liquid
benzene, liquid propylene was injected into the benzene
feed stream to given benzene/propylene feed molar ratio of
7.2 and a total feed rate of 5.7 grams per gram of
catalyst per hour.
Analysis of the reactor effluent by capillary
gas-liquid-chromatography showed that all of the propylene
had been converted to make a product comprising 93.5%
01 -41- 1 3 3 S 6 0 0
cumene and 5.9% diisopropylbenzenes on a benzene free
weight basis. Since SSZ-26 is also a good transalkylation
catalyst, it is anticipated that the diisopropylbenzene
would be either recycled to the alkylation reactor or
reacted in a separate reactor with benzene to make
additional cumene. The conversion to useful product was
thus better than 99 weight percent based on propylene and
benzene reacted.
