Note: Descriptions are shown in the official language in which they were submitted.
125~38
-- 1 --
TITANIU~-ALUMINUM-SILICON-OXIDE
MOLECULAR SIEVE CO~POSITIONS
FIELD OF THE INVENTION
The pee~ent invention relates to a new
cla~s of molecular ~ieve comeo~ition~ containing
titanuim, aluminum and silicon in the form of
f~amewock tetcahedral oxide unit~. These
composition~ a~e prepared hydrothermally from
~eaction mixtuces containing reactive ~ou~ces of
titanuim, aluminum and silicon and preferably at
least one organic templating agent.
DISCUSSION OP MOLECULAU SIEVE5
~ olecular sieve~ having cry~talline
~tructuces and of the alumino~ilicate tyee are well
known to those familiac with molecular sieve
technology. Both naturally occuccing and ~ynthetic
alumino~ilicates are kno~n to exist and literally
hundceds of fiuch have been reported in the
literature.
Alehough hundreds of alumino~ilicates
(binary molecular sieves) a~e known, the reports
eelating to ternary molecular sieves have been
relatively few. Fucthec, the cepocted tecna~y
molecular sieves having titanium as a component have
been even fewec and in those instances where
titanium has been ceeorted the amount contained in
the molecular ~ieve has been celatively small oc
ere~ent as a depo~ition or surface modifying agent.
One eacly ~epoct of ccystalline
titano-~ilicate zeolites (Of course, these
D-14,340
~S
i2S~1l8~
compositions are not zeolites as the term ~zeolite"
is commonly employed today.) is found in U.S. Patent
No. 3,329,481. The crystalline titano-silicates are
described in U.S. Patent No. 3,329,4Bl by the
formula:
(D2~n)X:TiO2(sio2)y
wherein D is a monovalent metal, divalent metal,
ammonuim ion or hydrogen ion, "n" is tlle valence of
D, "x" is a number from 0.5 to 3 and y is a number
from about 1.0 to 3.5. The crystalline
titano-silicate zeolites are characterized by X-ray
powder diffraction patterns including all the
d-spacings of one of the patterns selected from the
group:
Pattern A: Pattern ~: Pattern C:
7.6 - 7.9A 4.92 + 0.04A 2.82 + 0.03A
3.2 , O.OSA 3.10 + 0.04A 1.84 + 0.03A
The difficulty in obtaining compositions
containing titanuim is evidenced by the disclosure
of U.S. Patent No. 4,358,397 which discloses
modified aluminosilicates. The aluminosilicates are
modified by treating an aluminosilicate with a
compound derived from one or more elements of
titanium, zirconium or hafnium. The resulting
compositions are 6aid to contain a minor proportion
of an oxide of such elements. It is clear that in
the disclosed compositions the oxides of titanuim,
zirconium and hafnium were present as deposited
oxides and were present in a minor proportion.
As above mentioned, although there has been
an extensive treatment in various patents and in t~e
published literature of aluminosilicates and
D-14,340
lZ.)~l8~
recently, aluminophosphates, there has been little
information available on molecular sieves other than
such materials. This is particularly true in the
-area of titanium containing compositions. -~
Molecular sieve compositions wherein
titanium is present in the framework of the
molecular sieve or i8 50 intimately related as to
change the physical and/or chemical characteristics
of the molecular sieve have not been extensively
reported. This is understandable in the ~uestion of
aluminosilicates, as indicated by the article, "Can
Ti4 replase Si4+ in silicates?", Mineralogic31
Magazine, September vol 37, No. 287, pages 366-369
(1969). In this article it is concluded that
substitution of framework silicon by titanium does
not usually occur in aluminosilicates owing to the
preference of titanium to be octahedrally bound
rather than tetrahedrally bound. Even in the
formation of crystalline "titanosilicate zeolites",
as disclosed in U.S. Patent No. 3,329,481 and
discussed above, wherein a metallo-silicate complex
is formed and treated to qive the titano silicate
product the evidence for the claimed titanosilicate
is based on the X-ray powder diffraction patte~n
data which are somewhat suspect as to whether such
show sub6titution of titanium into the silicate
framework inasmuch as the same claimed %-ray
patterns are also obse~ved for the zirconium
silicates. Further, ~imilar X-ray patterns showing
similar interplanar distances for the two values in
pattern B have been reported foI silicalite. (see
GB 2,071,071 A).
D-14,340
iZ~8~
The incorpo~ation o~ titanium in a
silicalite-type steuctu~e is disclosed in ~B
Z,071,071 A, publi&hed December Zl, 1979. The
amount of titanium claimed to be substituted into
the ~ilicalite~type st~uctu~e is ve~y small, being
no more than 0.04 ~ole peccent, based on the nuwbe~
of ~oles of silaca, and ~ay be as low as 0.0005.
The titanium content was dete~mined by chemical
analysis and was not dete~mined to be g~eate~ than
0.023 in any of the cepocted examples. As indicated
by a comparison of Fig. la and Fig. lb of GB
2,071,07~ A, ehe amount of titanium pcesent is so
s~all that no significant change in the X-cay
diff~action pattecn of silicalite was obsecYed and
the ~inor changes observed may simply be due to
occluded titanium dioxide. (Thus, in the absence of
othec analytical data the ~esults a~e not well
defined.) No compaci60n data fo~ titanium dioxide
ace disclosed.
In view of the above, it is cleac that the
~ubstitution of titanium into a zeolitic-type
f~amewo~k although conceived to be possible whe~ein
titanium substitutes fo~ silicon, has been viewed by
those ~killed in the act as ~ost difficult to
achieve.
~ he difficulty which is met in pcepa~ing
titanium-containing molecula~ sieve compositions is
fu~thec demonst~ated by the failu~e of Eucoeean
Patent Application No. 82109451.3 (Publication No.
77.522, published Ap~il 27, ~983) entitled
~Titanium-containing zeolites and method fo~ thei~
pcoduction as well a~ use of said zeolites. n, to
actually pcepa~e titanium-containing molecula~ sieve
compositions. Although the ap21icants claim the
13-14.340
lZS~38
preparation of titano-aluminosilicate having the
pentasil structure, it is evident from an analysis
of the products of the examples that titanium was
not present in the form of a frameworX tetrahederal
oxide. The product of the example of European
patent Application No. 82109451.3 will be discussed
in detail in a comparative example hereinafter.
DESCRIPTION OF THE FIGURES
FIG. 1 is a ternary diagram wherein
parameters relating to the instant compositions are
set forth as mole fractions.
FIG. 2 is a ternary diagram wherei~
parameters relating to preferred compositions are
set forth as mole fractions.
FIG. 3 is a ternary diagram wherein
parameters relating to the reaction mixtures
employed in the preparation o the compositions of
this invention are set forth as mole fractions.
FIG. 4 is an SEM (Scanning Electron
Micrograph) of the product of European Application
No. 82109451.3.
FIG. 5 is an SEM of TASO-45 prepared in
accordance with the instant invention.
SummarY of the Invention
New molecular sieve compositions are
claimed having three-dimensional microporous
crystalline framework 6tructures of Tio2, A102
and SiO2 tetrahedral oxide units. These new
molecular 6ieves have a unit empirical formula on an
anhydrou~ ba6is of:
mR: (TixAlySiz)02
where "R" denominates an organic templating agent
D-14,340
l;~S418~3
pcesent in the intracrystalline pore sy~tem "m"
cepeesents the moles of "R" present per mole of
(TiXAlySz)02 and has a value of ~com zeco to
about 0.3; and "x", "y" and "z" cep~esent the mole
fcaction~ of titanium, aluminum and silicon,
respectively, present a~ framewock tetcahedral oxide
units, ~aid ~ole ~ractions being such that they are
within the tet~agonal area defined by points A, B, C
and D of Fig. 1, where point6 A. B, C and D have the
following values for "x", "y" and "z":
~ ~ole Fraction
Point x ~ z
A .39 .60 0.01
B .98 .01 0.01
C .01 .01 0.98
D .01 .60 0.39
The instant titanium-aluminum-~ilicon-
oxides will be generally cefecred to herein by the
acconym ~TASO-45~ to de~ignate the instant
titanium-alu~inum- silicon-oxide molecular 6ieve~
having a fcamewock structuce of TiO2, A102 and
SiO2 tetrahedral oxide unit~. Thi~ designation i6
an arbitrary one and i~ not intented to denote
~tructural relations to another mate~ial(s) ~hich
may also be chacacterized by a numbecing sy6tem.
DETAILED DESCRIPTION OF THE INVENTION
The pre6ent invention relate~ to
titanium-aluminum-6ilicon-oxide molecular sieves
having three-dimen~ional micropo~ou~ cry6tal
~ramework ~tcucture6 o~ Tio2, A10z and SiOz
tetrahedral unit~ which have a unit empirical
D-14,340
1254~8~3
~ocmula on an anhydrous basis of:
ma : (TiXAlySiz)02 (1)
whezein ~ cepeesents at least one ocganic
templating agent pcesent in the intracrystalline
poce ~ystem; "m~ repce~ents the moles of ~R~ esent
pec mole of ~Tix~lySiz)Oz and has a value of
between zeco and about 0.3~; and "x", ny~ and "z"
cepeesene the mole fractions of titanium, aluminum
and silicon, respectively, pcesent as tetrahedcal
oxides, ~aid mole fractionæ being such that they ace
within the tetragonal compositional a~ea defined by
eoints A, B, C and D FIG. 1 and cep~esenti~g the
following values for N~ Uy~ and "z":
Mole Fractio~ _
Point Y x z_
A 0.60 0.39 0.01
B O . OL O . 98 0.01
C 0.0~ 0.01 0098
D 0.60 0.01 0.~9
The pacameters ~xn, "y" and "z" ace peefecably
within the compositional area defined by points a,
b, and c of ehe te~na~y diagcam which i~ Fig. 2 of
the drawing$, said points a, b, and c cepcesentinq
the following ralues for "Y", ~y" and "z":
Mole Fcaction
Point x y z
a 0.49 0.01 0.50
b 0.01 0.49 O.S0
c 0.01 0.01 0. 98
In a moce pee~eceed ~ubclass the value of "Y~ i8
between about 0.024 and about 0.118, ~y" is between
D-14,340
l~S~
-- 8
about O.Q20 and about 0.051 and "z" is between about
0.831 and about 0.~56.
- The molecular sieves of the present
invention are generally employable as catalysts for
various hydrocarbon conversion processes.
The term "unit empirical formula~ is used
herein according to its common meaning to designate
the simplest formula which gives the relative number
of moles of titanium, aluminum and silicon which
form the TiO2, A102 and SiO2 tetrahe~ral unit
within a titanium-aluminum-silicon-oxide molecular
sieve and which forms the molecular framework of the
TAS0-45 composition(s?. The uni~ empirical formula
i8 given in terms of titanium, aluminum and ~ilicon
as shown in Formula (1), above, and does not include
other compounds, cations or anions which may be
present as a result of the preparation or the
existence of other impurities or materials in the
bulk composition not containing the aforementioned
tetrahedral unit. The amount of template R is
reported as part of the composition when the
as-synthesized unit empirical formula is given, and
water may also be reported unless such is defined as
the anhydrous form. For convenience, coefficient
"m" for template "R" is reported as a value that is
normalized by dividing the number of moles of
organic by the total moles of titanium, aluminum and
silicon.
The unit empirical formula for a given
TAS0-45 can be calculated using the chemical
analysis data for that TAS0-45. Thus, for example,
in the preparation of TAS0-45 disclosed hereinafter
D-14,340
8t~
the over all composition of the as- ynthesized
TAS0-45 is calculated using the chemical analysis
data and expressed in terms of molar oxide ratios on
an anhydrous basis.
The unit empirical formula for a TAS0-45
may be given on an "as-synthesized" basis or may be
given after an "as-synthesized" TAS0-45 composition
has been subjected to some post treatment process,
e.g., calcination. The term "as-synt~esizedl' herein
shall be u6ed to refer to the TAS0-45 composition(s)
formed as a result of the hydrothermal
crystallization but before the TAS0-45 composition
has been subjected to post treatment to remove any
volatile components present therein. The actual
value of "m" for a post-treated TAS0-45 will depend
on several factors (including: the particular
TAS0-45, template, severity of the post-treatment in
terms of its ability to remove the template from the
TAS0-45, the proposed application of the TASO-45
composition, and etc.) and the value for "m" can be
within the r~nge of values as defined for the
as-synthesi2ed TAS0-4S compositions although such is
generally less than the as-synthesized TAS0-45
unless such post-treatment process adds template to
the TAS0-45 so treated. A TA50-45 composition which
is in the calcirled or other post-treatment form
generally has an empirical formula represented by
Formula (1), except that the value of "m" is
generally less than about 0.02. Under sufficiently
severe post-treatment conditions, e.g. roasting in
air at bigh temperature for long periods (over 1
hr.), the value of "m" may be zero (0) or, in any
D-14,340
12S~88
-- 10 --
event, the template, R, is undetectable by normal
analytical procedures.
The molecular sieves of the instant
inven~ion are generally synthesized by hydrothermal -
~crystallization from a reaction mixture comprising
reactive sources of titanium, aluminum and silicon,
and preferably one or more ~rganic templating
agents. Optionally, alkali metal(s) may be present
in the reaction mixture. The reaction mixture is
placed in a pressure vessel, preferably lined with
an inert plastic material, sueh as
polytetrafluoroethylene, and heated, preferably
under the autogenous pressure, at a temperature of
from about 50C to about 250C, until crystals of
the molecular sieve product are obtained, usually
for a period of from 2 hours to 2 wee~s or more.
While not essential to the synthesis of the instant
molecular sieves, it has been found that in general
stirring or other moderate agitation of the reaction
mixture and~or seeding the reaction mixture with
seed crystals of either the TASO-45 to be produced,
or a topologically similar composition, facilitates
the crystallization procedure. The product is
recovered by any convenient method such as
centrifugation or filtration.
After crystallization the ~ASO-45 may be
isolated and washed with water and dried in air. As
a result of the hydrothermal crystallization, the
as-synthesized TASO-45 contains within itS
intracrystalline pore system at least one form of
any template employed in its formation. Generally,
the template is a molecular species, but it is
D-14,340
iZ5~88
possible, steric considerations permitting, that at
least some of the template is present as a
charge-balancing cation. GeneralIy the template is
too large to move freely through the -~
intracrystalline pore system of the formed TAS0-45
and may be removed by a post-treatment proces , such
as by calcining the TAS0-45 at temperatures of
between about 200C and to about 700C so as to
thermally degrade the template or by employing some
other post-treatment process for removal of at least
part of the template from the TAS0-45. In some
instances the pores of the TAS0-45 are sufficiently
large to permit transport of the template, and,
accordingly, complete or partial removal thereof can
be accomplished by conventional desorption
procedures such as carried out in the case of
zeolites.
TA80-45 compositions are formed from a
reaction mixture containing reactive sources of
TiO2, A1203, and sio2 and an organic
templating agent, said reaction mixture comprising a
composition expressed in terms of molar oxide ratios
of:
2 ( x y z 2 2
wherein "R" is an organic templating agent; "a" has
a value large enough to constitute an effective
amount of "R" said effective amount being that
amount which form said TASG-45 compositions and
preferably has a value of from greater than zero to
about 100 and more preferably between about 1 and
about 50; "b" has a value of from zero to 400 and
D-14,340
:- . .
1~5~l88
12
qceate~, pceferably from about 50 to about 100:
~Y~, "y" and "z" represent the mole fcac~ionsO
reseectively of titanium, aluminum and silicon in
the tTiXAlySiz)02 con~tituent, and each has -~
a value of at least 0.01 and being within the
tetcagonal compositional area defined by points, E,
F, G and H vhich is Fig. 3 of the drawings, said
points E, F, G and H cepcesentinq the following
values foc uy--, ay~ and "z~:
~ole Fraction
Point x Y z
E 0.39 0.60 O.ol
F 0.98 0.01 0.01
G 0.01 0.01 0.98
H 0.01 0.60 0.39
The ceaction ~ixtuce~ from which TASO-45 is
~ocmed genecally contain one oc moce ocganic
temelating agents (temelates) which can be most any
of tho~e hecetofoce pcopo~ed foc use in the
synthesis of aluminosilicates and
aluminophosphates. The template pcefecably contains
at least one element of Group VA of the Periodic
Table, earticularly nitcogen, ehosehocug, arsenic
andJoc antimony, moce pcefecably nitrogen oc
ehosehorus and most pceferably nitrogen and are of
the formula ~4~ wherein ~ i~ selected from the
group consisting of nitrogen, eho~phocus, acsenic
and~or antimony and R may be hyd~ogen, alkyl, aryl,
araalkyl, or alkylaryl qcoup and is pcefecably aryl
or alkyl containing between 1 and 8 carbon atoms,
although more than eight cacbon atoms may be eresent
~ of group of the te~plate.
D-14,340
12S'~
Nitrogen-containing templates are preferred,
including amines and quaternary ammonium compounds,
the latter being represented generally by the
formula R'4N+ wherein each R' is an alkyl, aryl,
alkylaryl, or araalkyl group: wherein R' preferably
contains from 1 to 8 carbon atoms or higher when R'
is alkyl and greater than 6 carbon atoms when R' is
otherwise, a~ hereinbefore discussed. Polymeric
quaternary ammonium salts ~uch as [(C14H32N2~
(OH)2]X wherein "x" has a value of at least 2
may also be employed. The mono-, di- and
tri-amines, including mixed amine may also be
employed as templates either alone or in combination
with a quaternary ammonium compound, quaternary
phosphonium compound or another template. The exact
relation6hip of variou~ templates when concurrently
employed is not clearly understood.
Representative templates which may be
employed include: tetramethylammonium,
tetraethylammonium, tetrapropylammonium or
tetrabutylammonium ions: di-n-propylamine;
tripropylamine; triethylamine; triethanolamine;
piperidine; cyclohexylamine; 2-methylpyridine;
N,N-dimethylbenzylamine; N,N-diethylethanolamine;
dicyclohexylamine; N,N-dimethylethanolamine;
1,4-diazabicyclo (2,2,2) octane;
N-methyldiethanolamine, N-methyl- ethanolamine;
N-methylcyclohexylamine; 3-methyl- pyridine;
4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone.
D-14,340
i2S~38
- 14 -
If an alkoxide is selected as the reactive
aluminum, silicon or titanium source, the
corresponding alcohol is necessarily present in the
reaction mixture since it is a hydrolysis product of
the al~oxide. It has not as yet been determined
whether this alcohol participates in the synthesis
process as a templating agent, or in some other
functio~ and, accordingly, is not reported as a
template in the unit formula of TASO-45, althouqh
such may be acting as templates.
Alkali metal cations if present in the
reaction mixture may facilitate the crystallization
of TASO-45, although the exact function of such
cations, when present, in crystallization, if any,
is not presently known, Alkali cations present in
the reaction mixture generally appear in the formed
TASO-45 composition, either as occluded (extraneous)
cations and/or as structural cations balancing net
neqative charges at various sites in the crystal
lattice, It should be understood that although the
unit formula for TASO-45 does not specifically
recite the presence of alkali cations they are not
excluded in the same sense that hydrogen cations
and/or hydroxyl groups are not specifically provided
for in the traditional formulae for zeolitic
aluminosilicates,
Most any reactive titanium source may be
employed herein, The preferred reactive titanium
sources include titanium alkoxides, water-soluble
titanates and titanium chelates.
Most any reactive source of silicon can be
employed herein. The preferred reactive sources of
D-14,340
125~88
-- 15 --
5ilicon are silica, either as a silica sol or a~
fumed ~ilica, a ~eactive solid amorphou6
precipitated ~ilica, silica gel, alkoxides of
~ilicon, ~ilicic acid oc alkali metal silicate and
~mixtures thereof.
~ o~t any reactive aluminum ~ource may be
employed he~ein. The preferred ~eactive aluminum
~outces include aluminum alkoxides, such as aluminum
isop~opoxide, and pseudoboehmite. C~ystalline or
amorphous aluminosilicates which are a suitable
sou~ce of silicon are, of course, also suitable
~outces of aluminum. Other sou~ces of aluminum used
in zeolite synthesi~, 6uch as gibbsite, ~odium
aluminate and aluminum tcichlo~ide, are believe
employable hecein.
The following examples a~e provided to
exemplify the invention and are not meant to be
limiting the~eof in any way.
EX~MPI,ES 1-66
ta) Examples 1 to 66 were ca~ried out to
demonstcate the prepacation of the TASO-45
composition~ of thiff invention. The TASO-45
composition~ were carried out by employinq the
hydrothermal crystallization pcocedure discussed
~upra. aeactiOn mixtu~es wele p~epa~ed for each
example using one or more of the following
prepa~ative reagents:
(1) Tipro: Titanium i~opcopoxide:
(2) AA: TYZOR AA, Titanium,
bi~(2,4-pentanedionate-0,0')
bi~(2-propanolato)-;
D-14, 340
~z~
( 3 ~ TE: TYZOR TE, Ethanol,
2,2',2"-nitrilotris-, ti~anium (4+)
salt:
(4) LA: TYZOR LA, Titanate ~2-),dihydroxy -
~bis [~-hydroxypropanato(2)-0102]-;
(5) DC: TYZOR DC, Titanium
bis(ethyl-3-oxobutanolato-01,03)bis
(2 propanolato~-
(6) ANF: TYZOR ANF, Titanium,bis(2,4-pentanedionato-O,O')bis(2-propan
olato)-
C7) LUDOX-LS: Trademark of DuPont for an
aqueous solution of 39 weight percent
SiO2 and 0.1 weight percent Na20:
(8) Sodium aluminate;
(9) Sodium hydroxide;
(10~ TBABr: tetrabutylammonium bromide;
(11~ TEABr- tetraethylammonium bromide;
(12) TPABr: tetrapropylammonium bromide;
(13) TPAOH: tetrapropylammonium hydroxide;
(14) Kaiser alumina.
The designation TYZOR in the abo~e list is
the Trademark of DuPont for the identified titanium
compounds. The method of addition of the abo~e
mentioned componen~s to the reaction mixture was
done according to th~ee methods (A, B and C). In
some of the examples seed crystals of silicalite
(U.S.P. 3,941,~71~ were added to the reaction
mixtures. Methods A, B and C are as follows:
METHOD A
LUDOX-LS and two-thirds of the water were
blended to form a homogeneous mixture. The
D-14,3~0
- ~ZS'~88
- 17 -
remaining water and odium hydroxide were blended to
form a homogeneous mixture. Sodium aluminate was
dissolved in this ~econd mixture and the two
mixtures blended to form a homogeneous mixture. The
titanium source was blended into this mixture after
which the organic templating agent (referred to
herein as "template") was added to this mixture and
blended until a bomogeneous mixture was observed.
METHOD B
LUDOX-LS and one half of the water were
blended to form a homogeneouQ mixture. The titanium
~ource was added to this mixture and blended to form
a homogeneous mixture. The sodium aluminate was
dissol~ed in approximately one fourth the water and
added to the previous mixture until a homogeneous
mixture was observed. The sodium hydroxide was
di~colved in one fourth of the water and blended
with the previous mixture. T~e organic template was
added to this mixture and blended until a
homogeneous mixture was observed.
METHOD C
LUDOX-LS and one-third of the water were
blended to form a homogeneous mixture. The sodium
hydroxide was dissolved in one-sixth of the water
and added to this mixture and blended to form a
homogeneous mixture. Kaiser alumina was dissolved
in one-sixth of the water added to the NaOH solution
and blended. The mixture was then added to the
LUDOX solution and blended. The titanium source was
added to this mixture and blended to provide a
homogeneous mixture after which the organic template
(in one-third of the water) was added and the
D-14,340
~ZS4~8
- 18 -
mixture again blended until a homogeneous mixture
was observed.
(b) ~he ~-ray patterns appearing herein
were obtained using standard x-ray powder
diffraction techniques or by use of copper K-alpha
radiation with computer based techniques using
Siemens D-500 ~-ray powder diffractometers, Siemens
Type K-805 X-ray sources, available from Siemens
Corporation, Cherry Hill, New Jezsey, with
appropriate computer interface. The standard X-ray
technique employs as ~he radiation ~ource a
high-intensity, copper target, X-ray tube operated
at 50 Kv and 40 ma. The diffraction pattern from
the copper K radiation and graphite monochromator is
suitably recorded by an X-ray spectrometer
scintillation counter, pu~se height analyzer and
strip chart recorder. Flat compressed powder
samples are scanned at 2(2 theta) per minute, using
a two second time constant. Interplanar spacings
(d) in Angstrom units are obtained from the position
of the diffraction peaks expressed as 29 (theta)
where theta is ~he Bragg angle as observed on the
fitrip chart. Intensities were determined from the
heights of diffraction peaks after ~ubtracting
background, "Io" being the intensity of the
strongest line or peak, and "I" being the intensi~y
of each of the other peaks. When Relative
Intensities are reported the following abbreviations
mean: vs = very strong; s s strong; m = medium, w =
weak; and vw = very weak. Other abbreviations
include: sh = shoulder and br = broad.
As will be understood by those skilled in
D-14,340
12S~8~
-- 19 --
the art ~he determination of the parameter 2 theta
is subject to both human and mechanical error, which
in combination, can impose an uncer~ainty of about
+0.4 on each reported value of 2 theta. This
uncertainty is, of course, also manifested in the
reported values of the d-spacings, which are
calculated f~om the 2 theta values. This
imprecision is general throughout the art and is not
sufficient to preclude the differentiation of the
present crystalline materials from each other and
from the compositions of the prior art.
(c) The preparative examples were carried
out by preparing reaction mixtures having molar
amounts of components expressed by:
e R:f Al203:g SiO2:h Tio2:i NaOH:j H20
wherein "R" is at least one organ;c template as
hereinbefore define; and e, f, g, h, i and j are the
number of moles of template, Al203, SiO2,
Tio2, NaOH and H20, respectively. The values
for e, f, g, h, i and j are set forth in Table I for
the ~ASO-45 products prepared in examples l to 66:
D-14,340
125'~t88
N
O t~ d ~C e ~
O O O ,~ D
~~ C
:-~ .~
6 ~ r r~ -~ ~r o ;r o ~ o ~r o ~ o ~ o4~ K S
o ~
~ O -
u~ o o ~ u~ o 8 u~ g 8 ~ ~ ~ u~
e ,~ O ~ ~
~ r.l r~ r~ r~ ~ ~ x oo ~ ~ ~ e
Z ~r7 r~ ~4 ri r~ r~ ri ~I r~ r~ ~I r- ri r~ r~ r1 r~ r~ r~ o /~ ~
E~
~ooooooooooooooooo
~r r~ r~ r~ r~ r~ rl r~ r~ r~ rJ r~ r~ ~ r~ r~ r~ r~ r~ ~ ~ S
~ ~ v, tu
s ~ ~ o
S rl ~ ~ ~ ~ O ~ U ~
~ ,~ v,. ,u. ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ a ,"c~,
. ~ ~WO ~
O ~ 2 ~ ~ 2 S o ~ 2 2 ~ ~ 2 C u
7-1 N ~ ~ li 1 ~ i' 00 O` O r~ N ~ ~ r1 ~1 ~ ~i ` O ~ U~ ~ O
bl rl ~i
G2~
~ZS~l8
c ~ ¢ ~ e ~
s~
t. 2 2 2 ~, 1. 2
o ~ o e
E-' ' . ~ e K
'O ~ 0 0~ ~ O u~ O ~ ~ ~ " o e
r~ ~ C 'E~
I ~ ~0
. U~
. l ~ ~ ~
~ L ~O
_ ~ ~ r~ O O ~ ~ O o o O ~ o O 00 0 rl
I ~ S ~0
~'0
O
O l0 ~0 10 10 N 10 ~O 10 10 0 0 10 ~ ) ~ e
e .
e
.o oo
~ ~ o ~ 3 ~ ., o o o
Q
a ~ u
~1 N N N N N ~D N CO Cr~ ~ rl N r~ ~ `O 1~ ~10 Cr~ ,~ ~ e u
,~ ~
12S4~8~
.~ ~
~ ,~
o O C O L I
_
:~
"5~ O ~ O ~ o r O ~ ~ O ~ O ~ ~ L
~ ~ 1 0
.~ V -
C O :1
O O O 1~ 0 0 0 0 ~ O O O O O O O O O O O O O O O O O O --~ ~
,, ~ ~ U. ~ V. o ~ Y' ~ ~ 2 ,, ,, 2 ,. ~ ~ 2 ~ ~ 2 ~ c
C ~ ~ ~-,
~ l~ ~ ~ N ~1 C'J 1~ I` 1~ r~ U~ u) ~ 1~ U7 ~ 1~ 1 ~ O' V'l ~ ~ C: ~
c ~ ~ 5 ~ 5 ~ F ~ o
C .
In ~ ~ ~ U~
I ~ o o o o o o o o ~ ~ ~ o ~ ~ ,9 e ~ ~ ~
o
O L
U~
~;r
Irl U~ N N N N N N C'J N ~ U~ U~ u~ t~ 1 u~ ~' O O ~r
.
~0 ~ ~ O O O O O O O O u~ u~ ~ ~ U- u~ ~ u~ ~ ~ ~ ~ U~ u~ u~ ~ ~ ~ ~
o ~ ~o o
oooo~'~ooooooooooooooo
O O O O O O O O ~
e _- N .0
_~ ~ ~ C ~ ~ ~ C
~ ~ ~e ~
~ Q ~ L~
O O r~ N ~ ~C ~ CO O` O r~ N t~ `O r~ 00 t~` rl ,o ~ ~o ~1 ~ ~ ~ O e,~
rl N
~æ
lZS~88
- 23 -
EXAMPLE 67
(a) Products from examples 8, 37, 40 and
44 were calcined and treated as hereinafter
described and were then employed to determine
adsorption capacities of TAS0-45. The adsorption
capacities were measured using a standard
McBain-Bakr gravimetric adsorption apparatus on
~amples activated in a vacuum at 350C.
The data for TAS0-45 as prepared in
examples 8, 37, 40 and 44 were as follows:
(b) (ExamPle 8):
Kinetic Pressure Temp. wt %
Diameter, A (Torr) (C? Adsorbed*
2 3.46 105 -183 15.0
2 3.46 741 -183 18.7
Cyclohexane 6.0 65 23.6 4.9
Neopentane 6.2 739 23.5 2.0
H20 2.65 4.6 23.8 6.6
H20 2.65 20.0 29.013.1
*Calcined air at 500C for 1.5 hours prior to
activation.
D-14,340
lZS~8~
- 24 -
(c) (Exam~le 371:
Kinetic Pressure Temp. wt %
Diameter, A (Torr) (C) Adsorbed~ -~
2 3.46 106 -183 12.1
2 3.46 744 -183 14.4
Cyclohexane 6.0 82 23.9 5.6
Isobutane 5.0 740 24.2 6.2
Neopentane 6.2 741 25.3 1.7
H20 2.65 4.6 24.9 5.5
H20 2.65 19 24.8 9.8
~Calcined at 600C in air for one hour prior to
activation.
(d) (ExamPle 40):
Rinetic Pressure Temp. wt %
Diameter, A (Torr) ~C) Adsorbed~
2 3.65 lOS -183 13.6
2 3.65 7g7 -183 17.7
Cyclohexane 6.0 71 23.5 7.3
Neopentane 6.2 7S0 23.5 2.7
H20 2.65 4.6 23.5 7.7
H20 2.65 19 23.4 15.5
:
~Calcined at 500C in air for one hour prior to
activation.
D-14,340
:lZS~8~
- 2S -
~e~ (Example 44):
Kinetic Pressuce Temp. ~t ~
Diameter, A lTo~) (C1 Ad60rbed*
-Oz 3.65 l0~ -183 ~6.7
X 3.65 747 -183 18.3
Cyclohexane 6.0 7L 23.5 0.7
Neopentane 6.2 750 23.5 0.4
H2O 2.65 4.6 23.5 5.3
H2O 2.h5 l9 23.4 l~.5
~Calcined in ai~ at 500C fo~ vne hour ~rio~ to
activation.
() F~om the data ~et ~orth in pa~ts (b),
(c), (d) and (e) it wa~ dete~mined that the eo~e
~ize of TASO-45 is about 6.0A.
EX~MPLE 68
~ ) The as-synthesized p~oducts o
exa~ples 8. 12, 29, 37, 40, 42, 44, 51 and 66 we~e
analyzed (chemical analysis) to dete~mine the weight
eeccene ~l2O3, SiO2, Tio2, LOI (Loss on
Ignition), ca~bon (C) and nitrogen (N) p~esent as a
cexult of the template. The ~esult~ of these
analyse6 we~e as follows:
D-14.340
lZS4~8~3
- 26 -
(b) (~xamDle 8~:
Component ~eiaht Percent
A123 Z.83
sio2 7~.8
Tioz LL.3
~a2o 1. O
C 6.3
.70
LOT lZ.4
The above chemical analy~is gi~es an
anhydrous formula of:
0,044 ~ (Alo 040~io,859Ti0.101)
tc~ tExamPle 1.. ?.1: -
ComPonent ~eiaht Pe~cent
A123 3.01
sioz ~4.1
Tioz 8.45
Na20 1.08
C 6.5
N 0.70
T.O~ 12.0
The abo~e chemical analy~is givesn an
anhydrous formula of:
0,045 ~ (A10 042fiio,882Ti0.076)
D-14,340
12S4~8~3
(d) (ExamPle 29):
Component Weiaht Peccent
2o3
SiO2 76.8
TiO2 6.2
NazO 0.95
C 7.3
N 0.75
LOI 12.3
The above chemical analysis gives an
anhydcou~ foc~ula of:
0,053 ~ (Alo o5Lsio ggsTio.0$5)
(e) L~xamPle 37~:
ComPonent Weiqht Peccellt
A12 3 2.88
i2 67.0
Tio2 lZ.5
NazO 4,34
C 4.7
N 0.44
LOl 12.8
The above chemical analysis gives an
anhyd~ous ~ocmula of:
o 033 ~ ~Alo o435io,83gTiO.118)
D-14,340
lZS~8~
- 28 -
(f) ~ExamPle 40L:
Co~POne~t Wei ht P~rcent
A123 2.8
SiO2 66.7
Tio2 12.3
2~ 3.3
C 5.5
N 0.58
L01 14,5
The above chemical analy~i~ give~ an
anhydcou~ formula of:
00038 ~ (~lo o42sio~g42Tio~ll7)
(g) (ExamPle 42):
Comp~nene ~eiqht Percent
A123 2.6
Si~2 65.2
Tio2 10.7
NazO 6.2
C 4.6
N 0.48
L01 L4.3
The above chemical analysis gives an
anhydrous focmula of:
0.032 ~ (Alo o405io,gs4TiO.106)
D-14,340
i~S~188
(h) (Example 44L:
ComPonent Wei~ht Pe~cent
~123 1.4
- SiO2 80.3
TiO2 2.7
Na20 1.8
C 6.0
~ 0.64
LOI ~3.0
The abov~ chemical analysis gives an
anhydrous ~o~mula o~:
0.042 R (Alo oZosio~gs6Tio~o24)
til (ExamPle 51):
ComPonent ~eiqht Percent
A123 1.5
SiO2 80.5
TiO2
Na20 1.7
C 6.7
N 0.59
LOI 12.7
The above chemical analysis gives an
anhydcous fo~mula of:
0.047 R (~lo ozLSiO,gslTio~ozg)
D-14,340
- ~2S41 88
- 30 -
(i) (Example 66~:
ComDonent Wei~ht Percent
A123 2.BO
~ SiO2 73.L
Tio2 12.4
Na20 0.92
C 6~7
N 0.63
LOl 11.1
The above chemical analy~i gi~es an
anhydrous formula of:
0,047 ~ (Alo 039sio~8s3Tio~lo9
(k) EDAX tenergy dispersive analy~is by
x-ray) microprobe analysi~ was carried out on clean
crystal~ on the TAS0-45 products pceeared in
examples 8, 12 and 29, supra. The EDAX microprobe
analysis showed that at least 7.1 weight eercent
tieanium was pcesent as an integral part of the
cry~tal parti~le of each of the TASO-45
compo~itions. The ~elative amounts of SiO2,
A1203, and Tioz, expressed as a relative
~eight ~ercent ~as a~ follow~:
ExamPle 29
Aveca~e of SPot Pcobe~
Ti 1.5
Si 9,7
Al o,g
D-14.340
lZS~188
ExamPle 8
Averaae of SPot Probes
Ti 0.7
Si 10.0
Al
Example lZ
Avera~e of SPot Probes
Ti 0.2
si ~o.o
~1 0.5
~XAMPLE 69
(a) TAS0-45, as referred to in
example 12, was ~ubjected to x-ray analy6is.
TAS0-45 was determined to have a characteristic
x-~ay eowder diffraction ~a~tern which contains at
least the d-spacings ~et ~orth in Table II, below:
TABLE II
2~ d,~A) 100 x I/lo
7.9 11.17 59
a . 810.03 37
11.9 7.46 9
12.5 7.10 4
13.2 6.71 4
13.9 6.38 9
14.7 6.02 9
15.5 5.7Z 6
15.9 5.58 8
17.2 5.14 3
,17.7 5.01 5
D-14.340
i~S~8~
_ 32 --
TAI~LE II ~Cont'd~
2~ d, (A) 100 x I/Io
ls.Z 4.62 5
~0.0 4.45 2
~0.3 4.37 g
20.8 4.27 9
~.Z 4.0~ 5
23.1 3.85 100
23.7 3.76 34
~3.9 3.73 44
~4.4 3.66 Z6
25.8 3.448 9
~6.9 3.314 8
~7.4 3.258 3
.2 3.057 9
~9.9 2.989 12
30.3 Z.95L 5
3~.7 2.738 3
34.4 ~.609 3
34.fl 2.576 2
35,7 z,517 3
36.0 2.495 6
37.2 2.418 2
37.4 2.407 3
37.5 2.400 3
4~.0 z.ols 7
4~.~ Z.005 9
46.4 ~.9~6 2
47.4 . 1.919 3
48.S L.876 4
48.7 1,~7~ z
51.8 1.766 2
54.6 1.680 2
55.0 1.671 3
55.2 ~.664 3
(b) All of the as-synthe~i2ed TAS0-45
compositions fo~ which ~-cay powder difflaction data
have been obtained to date have patte~n~ which ace
chacactelized by the data o~ Table III, belo~:
D-14,340
i~S4~88
_ 33 -
TABLE III
ze d,(A) ~elative Inten~ity
7.9-8.011.17-11.10 ~-v~
~ 8.8-8.9 10.03-9.97 m
23.1-~3.33.85-3.82 ~-vs
23.7-23.83.76-3.75
23.9-~4.03.73-3.71
24.4-24.53.66-3.63 m
(c) A po~tio~ of the a~-synthe~ized
TA50-45 of example 11 vas calcined in aic at 500C
oc 1.5 houc~. The calcined pcoduct was
cha~acte~ized by the x-~ay powdec diff~a~tion
patte~n of Table IV. belo~:
~ABLE IV
Z~ d,(A) 100 x I/Io
8.0 1~.10100
B.9 9.9759
~,9 7.46 4
13.3 6.68 4
~4.0 6.3411
14.9 5.9713
15.6 5.69 8
16 0 5.5610
~7 8 4.97 6
19.3 4.60 4
20.4 4.36 5
20.9 4.25 8
22 3 3~99 4
23 Z 3.B462
23.3 3.8259
23.8 3.7524
24.0 3.7132
24.4 3.66Zl
25.7 3.4743
25.g 3.43~4
D-14,340
125'~88
_ 34 -
TABBE IV ~Cont.)
2~ d.(A) 100 x I/Io
_
26.7 3,334 4
~9.3 3.048 7
- 29.9 ~.989 9
30.4 2.943 5
32.B 2.731 3
36.~ 2.487 4
37.5 ~.400 3
45.1 2.010 5
45.6 1.991 8
48.6 1.873 4
48.8 l.B6B 3
53.5 1.713 5
(d) All of the a~-synthesized and
ealcined TAS0-45 compo~itions ~OL which ~-ray powdeL
difl~action data have been obtained to date have
pattecn~ ~hich a~e chacactecized by the data of
Table V, b~lov:
TABT,E V
2~ d. (A) 100 x l/Io
7.9 -fl.0 11.17-11.1036-L00
8.8-8.9 ~0.03-9.9725-60
9.0-9.1 9.83-9.7214-18
~1.8-~2.0 7.~0-7.38 2-11
12.5-12.6 7.10-7.03 3-6
13.2-13.3 6.7L-6.68 4-7
13.9-14.0 6.38-6.34 6-12
14.7-14.9 6.02-5.97 7-16
15.5-15.6 5.72-5.69 6-12
15.9-16.0 5.58-5.56 6-14
16.5-16.6 5.3'l-5.34 2-3
17.2-17.3 5.14-5.13 2-5
17.7-17.8 5.01-4.97 4-6
19.~-19.3 4.62-4.60 4-8
1~.9-20.0 4~46-4.45 2-3
20.3-20.5 4,37-4.33 5_9
20.8-21.0 4.27-4.23 8-13
D-14,340
l~S~
T~BLE V (Cont.~
2~ d, (A)100 x I/Io
21.7-21.8 4.10-~.081-3
22.1-22.3 4.02-3.993-7
23.1-23.3 3.~5-3.8262-100 -~
23.7-23.8 3.76-3.7524-34
23.9-24.0 3.73-3.7132-50
24.4-2~.5 3.66-3.6321-31
25.4-25.7 3.507-3.479 3-5
25.7-26.0 3.474-3.427 3-9
26.3-26.7 3.389-3.334 sh-8
26.7-27.1 3.339-3.290 4-16
27.3-27.7 3.267-3.220 3-8
28.0-28.4 3.187-3.143 2-3
29.2-29.4 3.057-3.038 7-10
29.9-30.1 2.989-2.969 9-16
30.3-30.4 2.~51-2.943 5-6
32.7-32.8 2.738-2.731 3-4
34.3-34.6 2.614-2.592 3-7
34.6-35.0 2.592-2.564 2-3
35.6-35.8 2.522-2.508 2-4
36.0-3S.3 2.495-2.475 3-9
37.1-37.3 2.423-2.411 2-3
37.4-37.7 2.407-2.386 3-5
41.3-41.5 2.186-2.176 2-3
45.0-45.2 2.015-2.005 5-9
45.3-45.6 2.002-1.991 6-11
46.4-46.5 1.956-1.953 2-3
47.3-47.6 . 1.922-1.910 2-3
48.4-48.6 1.~81-1.873 3-4
g8.7-48.8 1.871-1.868 2-3
51.~-52.0 1.766-1.759 1-3
53.5 1.713 5
S4.4-54.7 1.687-1.678 2-3
54.9-55.1 1.672-1.667 3-5
55.2-55.5 1.664-1.656 3-4
EXAMPLE 70
In order to demonstrate the catalytic
activity of the TAS0-45, calcined samples of the
products of Examples 8, 29 and 37 were then tested
for catalytic crackinq. The test procedure employed
D-14,340
1254~8~
was the catalytic cracking of premixed two (2) mole
% n-butane in helium stream in a 1~2" O.D. quartz
tube reactor over up to about 5 grams (20-40 mesh)
of the TASO-45 sample to be tested. The sample was
activated in situ for 60 minutes at 500C under 200
cm3/min dry helium purge. Then the two (2~ mole
(percent) n-butane in helium at a flow rate of 50
cm3~min was passed over the sample for 40 minutes
with product stream analysis being carried out at 10
minute intervals. The pseudo-first-order rate
constant (kA) was then calculated to determine ~he
catalytic activity of the TASO-45 composition. The
kA value (cm3/g min) obtained for the TASO-45
compositions are se~ forth, below:
Sample Rate Constant (kA)
Ex. 8 5.6
Ex. 29 16.8
Ex. 37 0~2
EXAMPLE 71
This is a comparative example wherein
example 1 of European Patent Application No.
82109451.3 was repeated and the product evaluated by
several techniques as hereinafter discussed:
(a) Example 1 of European Patent
Application No. B2109451.3 was repeated with the
starting reaction mixture having a composition based
on molar ratios of:
1 A1203: 47 SiO2: 1.32 TiO2: 11.7 NaOH: 28 TPAOH- 1498H20
The reaction mixture was divided and placed in two
digestion vessels. At the end of the procedure set
~-14,340
~ZS4~88
forth in example 1 of the European Application a
sample of the product from each digestion vessel was
analyzed and gave the following chemical analyses:
Weiaht Percent
Sam~le 1 SamPle 2
SiO2 75.3 75.9
A123 3.02 2.58
TiO2 3.91 4.16
Na2O 3.66 3.46
C 6.3 6.7
N 0.62 0.65
LOI 14.0 14.0
The two samples were then analyzed by SEM (scanning
electron microscope) and EDAX (energy dispersive
analysis.by X-ray) micropiope. The SEM probe of the
two samples showed four morphologies to be present
and such are shown in FIG. 4 (which should be
compared with FIG. 5 which shows the ~ingle
morphology of crystals of TASO-45 as prepared by the
instant invention). The four morphologies of the
two samples prepared in accordance with the
aforementioned European Application and the EDAX
microprobe analysis for each were as follows:
(1) Smooth, intergrown hexagonal
particles (at B in FIG. 4) which are associated with
a ZSM-5 morphology had an EDAX microprobe of:
Averaqe of SPot Probes
Ti 0
Si 1.0
Al 0 05
D-14,340
12S4~
(2) Flat, smooth plates (at A in F~G.
~) had an EDAX microprobe of:
Averaqe of SPot Probes
Ti 0.13
Si 1.0
Al 0.05
(3) Spheres and elongated bundles (at
C in FIG. 4) had an E~AX microprobe of:
A~era~e of SDot Probes
Ti 0.22
Si 1.0
Al 0.05
Na 0.10
(4) Needles or fine rods (at D in
FIG. 4) had an EDAX microprobe of:
Averaae of SPot Probes
Ti 0.05
Si 0.8
Al 0.13
Na 0 05
Cl 0.10
The above SEN and EDAX data demonstrate
that although ZSM-5 eype crystals were formed that
these crystals contained no detectable titanium.
The only detectable titanium was present as impurity
phases and not in crystals having the characteristic
x-ray diffraction pattern of ZSM-5.
The X-ray diffraction patterns of the
as-synthesi2ed materials were obtained and the
following X-ray patterns were obser~ed:
D-14.340
l~S'~8
- 39 -
Table VI tSamDle 1~
5.57715.8467
5.95014.8540
6.04114.6293
6.53513.5251
7.15412.3567
7. ~9S11.1978
8.79810.0504
9.0289.7946
9.7849.0401
11.8467. q708
12.4537.1079
12.7256.9565
13.1616.7267
13.8756.3821
14.6376.0518
14.7106.0219
-15.4615.7310
15.8815.5802
16.4715.3818
17.2185.1498
17.6955.0120
19.2124.6198
lg .8984.4619
20.0454.4295
20.2884.3770
20.8064.2692
21.6814.0988
22.1434.0145
23.0913.8516
23.6413.7632
D-14.340
lZS4~38
- 40 -
Ta bl e VX ( SamPl e 1)_ ( Cont i nued
23.879 3.7263
24.346 3.6559
- 24.649 3. ~116 -
25.548 ~.4865
2~ .828 3.4494
26.228 3.3g76
26.608 3.3501
26. a~7 3.3158
27.422 3.2524
2~ .048 ~ .181~
2~ .356 3.1473
29.191 3.0592
29.912 Z ~ 9870
30.295 2.9502
32.736 2.7356
33.362 2.6~57
- 34.355 2.6102
34.540 2.5894
34.887 2.5716
35.152 2.5529
35.551 2.5252
35.660 2.5177
36.031 2.4926
37.193 2.4174
37 ~ 493 2.3987
45.066 2.0116
45.378 1.9985
46.514 1.9523
47.393 1.9182
D-14,340
~S4~8~
- 41 -
Table VII (SamPl~ 2
5.801 15.2353
6.012 14.701Z
~ 6.169 14.3265
7.970 11.0926
8.E75 9,963S
9.118 9.6981
9.879 a . 953Z
ll.g33 7.4163
12.537 7.0605
12.808 6.9115
13.242 6.6R60
13.957 6.3452
14.71B 6.01B6
1~.810 5.9al3
lS.542 5.7014
15.954 5.5551
16.563 5.3521
17.316 5.1211
17.788 4.9862
19.291 4.6009
20.119 4.4134
20.382 4.3571
20.B79 4.2544
21.735 4.08B7
22.220 4.0007
23.170 3.8387
23.730 3.7494
23.964 3.7133
24.425 3.6442
24.722 3.6011
D-14,340
12541~
- 42 -
Table VI I (Sample 2) (Con ' td )
25.900 3.4399
~ 26.734 3.3345
26.979 3.3047
27.251 3.2724
27.494 3.2440
28.175 3.16~1
28.450 3.1371
29.287 3.0493
29.970 2.9~14
30.371 2.9430
30.694 2.9127
31.312 2.8566
32.825 2.7283
33.457 2.6782
34.426 2.6051
34.723 2.5834
34.879 2.5722
35.709 2.5143
36.125 2.4863
37.248 2.4139
37.490 ~ .3988
45.156 2.0078
45.453 1.9954
46.462 1.9544
46.608 1.9486
D-14,340
l~S'~
Tables VI and VII show an ~-ray pattern
typical of a ZSN-S type product and can be
attributed to the smooth. integrown hexagonal
particles which contained no titanium. The X-ray
patterns of Tables ~I and VII show three peaks (2
= 5.6-5.8, 12.45-12.54 and 24.5-24.72) which could
not be explaine~. The two samples were calcined
according to the conditions ~et forth in the
European application with a portion of both samples
being calcined at 540C for sixteen hours. The
X-ray patterns of the calcined samples were as
follows:
D-14,340
lZS~188
- 44 -
Table VIII (SamPle 1)
6.141 14.3908
6.255 14.1303
8.011 11.035~
8.913 9.9209
9.144 9.6705
9.930 8.9068
11.979 7.3876
12.440 7.1152
13.289 6.6625
14.007 6.3Z24
14.874 5.9557
15.613 5.6757
15.995 5.5~08
16.609 5.3373
17.353 5.1103
17.884 4.9597
19.335 4.5905
20.177 4.4008
20.463 4.3401
20.940 4.2422
21.845 4.0685
~2.291 3.9880
23.186 3.8361
23.362 3.8076
23.817 3.7359
24.031 .3.7031
24.510 3.6317
24.908 3.5747
25.699 3.4664
25.969 3,4309
D-14,340
12S~
- 45 -
Table VIII ~SamPle l)(Cont'd)
26.371 3.3796
26.698 3.3389
27.022 3.2996
~ 27.487 3.2449
28.184 3.1662
28.513 3.1303
29.369 3.0411
30.017 2.9759
30.468 2.9338
31.333 2.8548
32.877 2.7241
3~.490 2.6003
35.062 2.5592
35.800 2.5082
36.186 2.4823
37.324 2.4092
37.654 2.3888
45.195 2.0062
45.631 1.9880
~6.639 1.9474
47.547 1.9123
~8.765 1.8674
D-14,340
lZS41.8~3
- 46 -
Table IX (Sample 2 ~
6.09214.5084
- 6.29514.04~3
7.94111.1328
8.83810.0054
9.8578.9730
11.9217.4236
- 12.3997.13a3
13.2226.6959
13.9376.3539
14.8115.9809
15. ~355.7038
15.9165.5681
16.5325.3620
17.2625.1370
17.8064.9~11
19. Z68q .6064
20.1074.4160
20.3894.3556
2~. ~684.2567
21.8074.0754
22.1974.0047
23.1163.8476
23.2633.8235
23.7553.7455
23.9553.7147
24.4323.6433
24. ~543.5823
25.6533.4725
25.9013.4398
D-14,340
125 ~ 38
- 47 -
Tabl e IX ( Sample 21 ( Cont ' d )
26.265 3.39Z9
26.648 3.3451
26.976 3.3052
27.3~6 3.2566
28.156 3.1692
2~ .495 3.1323
29.304 3.0476
29.969 2.9815
30.384 2.9417
31.283 2.8592
32.819 2.7289
39.423 2.6052
34.993 2.5641
35.716 2.5138
36.146 2.4850
37.295 2.4~ 10
37.562 2.3g4~
45.137 2.0086
45.523 1.9925
46.562 1.9504
47.509 1.9137
D-14,340
~ZS~8~
- 48 -
The ~-ray d;ffraction patterns of the
calcined samples ~how a ZSM-5 ~ype pattern wi~h only
slight differences from the as-synthesized. When
chemical analysis (bulk~ of a portion of the
calcined samples 1 and 2 are carried out the
following is obtained:
Weicht Percent
Sam~le 1 Sample 2
SiO2 79.6 81.2
~12O3 3 2.9
Na2O 4~4 4.1
Tio2 4.6
Carbon 0.11 0.10
LOI~ . 8.1 7.6
*Loss on Ignition
When the molar ratio of oxides is computed
for the above bulk analysis the following is
obtained:
1 SiO2: 0.043 TiO2: 0.021 A12O3: 0.049 Na2O
This compares quite well with the bulk chemical
analysis reported in the European application which
i s :
1 SiO2 0.047 TiO2: 0.023 A1203: 0.051 Na2O
Although it is clear that the product crystals which
ga~e the product an X-ray pattern characteristic of
ZS~-5 contained no titanium, the bulk analysis of
the product shows titanium to be ~resent from
crystals which do not ha~e an X-ray diffraction
pattern characteristic of ZSM-5.
D-14,340
12S'~tb~t~
- 49 -
PROCESS APPLICATIONS
The TASO-45 compositions of this invention
have unique surface characteristics making them
useful as molecular ~ieves and as catalysts or as
bases for catalysts in a variety of separation, -~
hydrocarbon conversion and oxidative combustion
processes. The TASO-45 compositions can be
impregnated or otherwise associated with
catalytically active metals by the numerous methods
known in the art and used, for example, in
fabricating catalysts compositions containing
alumina or aluminosilicate materials.
TASO-45 ~ay be employed for separating
molecular species in admixture with molecular
species of a different degree of polarity or having
different kinetic diameters by contacting such
mixtures with a TASO-45 to allow TASO-4S to adsorb
at least one but not all molecular species of the
mixture based on the polarity of the adsorbed
molecular species and~or its kinetic diameter. When
TASO-45 is employed for such separatioD processes
the TASO-45 is at least partially activated whereby
some molecular species selectively enter ~he
intracrystalline pore system thereof.
The hydrocarbon conversion reactions
catalyzed by TASO-45 compositions include:
cracking; polymerization; reforming; hydrogenation;
dehydrogenation; and ~ydration.
TASO-45 containing catalyst compositions
may be employed in reforming processes in w~ich the
hydrocarbon ~eedstocks contact the catalyst at
temperatures between about 700F and about 1000F,
hydrogen pressures of bet~een about 100 and about
500 p.~.i.g., LHSV values in the range between about
D-14,340
1~5i~
- 50 -
0.1 and about 10 and hydrogen to hydrocarbon molar
ratios in the range between about 1 and about 20,
preferably between about 4 and about 12.
- Further, TAS0-45 containing catalysts which
contain hydrogenation promoters, are useful in
hydroisomerization processes wherein the
feedstock(s), suc~ as normal paraffins, is converted
to saturated branched-chain isomers. Hydroisomer-
ization processes are typically carried out at a
temperature between about 200F and about 600F,
preferably between about 300F and about 550F with
an LHSV value between about 0.2 and about 1Ø
Hydrogen is typically supplied to the reactor in
admixture with the hydrocarbon feedstoc~ in molar
proportions of hydrogen to the feedstock of between
about 1 and about 5.
TAS0-45-containing compositions similar ~.o
those employed for hydroisomerization may also be
employed at between about 650F and about 1000F,
preferably between about ~50F and about 950F and
usually at somewhat lower pressures within the range
between about 15 and about 50 p.s.i.g. for the
~ydroisomerization of normal paraffins. Preferably
the paraffin feedstock comprises normal paraffins
having a carbon number range of C7-C20. The
contact time between the feedstock and the TA50-45
containing catalyst is generally relatively short to
avoid undersirable side reactions such as olefin
polymerization and paraffin cracking. LHSV values
in the range between about 0.1 and about 10,
preferably between about 1.0 and about 6.0 are
~uitable.
D-14,340
1254~88
TAS0-45 containing catalysts may be
employed in catalytic cracking processes wherein
such are preferably employed with feedstocks such as
gas oils, heavy naphthas, deasphalted crude oil
residues etc. with gasoline being the principal -~
desired product. Temperature conditions are
typically between about 850 and about 1100F, LHS~
values between about 0.5 and about 10 pressure
conditions are between about 0 p.s.i.g. and about 50
p.s.i.g.
TAS0-g5 containing catalysts may be
employed for dehydrocyclization reactions which
employ paraffinic hydrocarbon feedstocks, preferably
normal paraffins having more than 6 carbon atoms, to
form benzene, xylenes, toluene and the like.
Dehydrocyclization processes are typically carried
out using reaction conditions similar to those
employed for reforming. For cuch processes it is
preferred to use a Group VIII non-noble metal cation
such as platinum in conjunction with the TAS0-45
composition.
T~S0-45 containing catalysts may be used in
catalytic hydrofining wherein the primary objective
is to provide for the selective hydrodecomposition
of organic sulfur and/or nitrogen compounds without
substantially affecting hydrocarbon molecules
present therewith. For this purpose it is preferred
to employ typical hydrotreatinq conditions. The
catalysts are the same typically of the same general
nature as described in connection with
dehydrocyclization operations. Feedstocks commonly
employed for catalytic hydroforming include:
gasoline fractions; kerosenes; jet fuel fractions;
D-14,340
iZS'~8~3
diesel fractions: light and heavy gas oils:
deasphalted csude oil residua; and the like. The
feedstock may contain up to about 5 weight-percent
-of sulfu and up to about 3 weight-percent of
nitrogen.
TAS0-45 containing catalysts may be
employed for isomerization processes under
conditions similar to those described above for
reforming although isomerization processes tend to
require somewhat more acidic catalysts than those
employed in reforming processes. Olefins are
preferably isomerized at temperatures between about
500F and about 900F, whil~ paraffins, naphthenes.
Particularly desirable isomerization reactions
contemplated herein include the conversion of
n-heptane and/or n-octane to isoheptanes,
iso-octanes, butane to iso-butane,
methylcyclopentane to cylcohexane, l-butene to
2-butene and/or isobutene, n-hexene to isohexane,
cyclohexane to methylcyclopentene etc. The
preferred ca~ion form is a combination of a TA50-45
with polyvalent metal compounds (such as sulfides)
of metals of Group II-A, Group II-B and rare earth
metals.
The TAS0-45 compo6itions of this invention
may be employed in conventional molecular sieving
processes as heretofore have been carried out using
aluminosilicate, aluminophosphate or other commonly
employed molecular sieves. TAS0-45 compositions are
preferably activated pr;or to their use in a
molecular sieve process to remove any molecular
species which may be present in the intracrystalline
pore system as a result of synthesis or otherwise.
.
D-14,340
lZ54'188
- 53 -
.
Foc the TA50-45 compocitions this i~ sometimes
accomplished by thermally de~tcoying the organic
seecies peesent in an as-~ynthe~ized TAS0-45 since
such ocganic species may be too lacge to be de~ocbed
by conveneional means.
The TAS0-45 compo~itions o~ thi~ invention
are also u6eful a6 adso~bents and a~e capable of
separating mixtures of molecula~ species both on the
basis o~ ~olecula~ size (kinetic diamete~s) and
based on the deqree of eolaritY of the molecular
species. When the ~epacation of molecular specie~
is based upon the ~elective ad~ocption ba~ed on
~oleculac ~ize, the TAS0-45 i8 cho~en in view o~ the
di~ensions of its poce~ such that at lea~t the
smalle~t molecular specie of the ~ixtu~e can enter
the intcaccystalline vnid space while at least the
la~gest ~pecie i~ excluded. When the sepa~ation is
based on deg~ee o~ pola~ity it is gene~ally the case
that the more hyd~ophilic TAS0-45 will
p~eferentially adsocb the moee pola~ moleculac
species of a mixtu~e having diffecent deqcees of
polacity even though both molecular speciex can
communicate with the poce sy~tem of the TAS0-45.
The in6tant TAS0-45 comeositions may be
fucthec characteeized and distinguished from
aluminoehosphates by refecence to the catalytic
properties exhibited by the TAS0-45 compositions.
When the TAS0-45 compositions a~e tested for
n-butane cracking and compared with aluminoeho6phate
comeositions having a simila~ topology it ha~ been
observed that ehe TAS0-45 comeositions are moce
active catalysts as indicated by a higher numerical
value fo~ n-butane cracking.
D-~4,340
