Note: Descriptions are shown in the official language in which they were submitted.
~12368~5
F-3358
PREPARATIQ~ EDIFIED ZE;Or.ITES AND THEIR UTTL~$ION
This invention is concerned with the catalytic corlver-
soon of hydrocarbons and other organic compound over
crystalline alumlnosilicate zealot of the ZSM-5 type which
have been modified by treatment with ~F3, to provide
enhanced selectivity, activity, or both, and with the
method or preparing such catalysts.
Zeolltlc materials, both natural and synthetic, have
been demonstrated in the past to have catalytic prapertles
for various type of conversion. One such conversion which
has generated considerable interest it the production of
hydrocarbons, including olefins and gasoline from alcohols
and ethers.
U.S. 4,025,575 describes a process by which lower
alcohol and/or their eighth are converted to a mixture of
C2-C5 olefins by contact at subatmo~pheric inlet partial
pressure with a crystalline aluminosilicate zealot of the
ZSM-5 type.
l~Z368~5
U.S. 3,931,349, issued January 9, 1976, also disk
closes a process for the conversion of methanol to
gasoline utilizing a ZSM-5 type catalyst.
U.S. 4,083,888, issued on April 11, 1978, discloses
a process for the manufacture of hydrocarbons by the
catalytic conversion of methanol in the presence of a
substantially an hydrous delineate and a ZSM-5 type zealot.
There are many other patents and publications which
describe the conversion of methanol to hydrocarbons,
including gasoline, such as U.S. 3,931,349; 3,969,426;
3,899,544; 3,894,104; 3,904,916; and 3,894,102. Other
conversions include, for example, propylene oligomeri-
ration, Tulane disproportionation, zillion isomerization,
alkylation of aromatics with alcohol or olefins, such as
Tulane + ethylene -- p-ethyltoluene, and dew axing, i.e.,
shape-selective cracking of wax molecules.
U.S. 4,163,028 discloses the isomerization of a
feed stock containing zillion in the presence of ZSM-5.
U.S. 4,268,420 describes a crystalline borosilicate
AMS-lB (ZSM-5) which can be used as a catalyst in the
isomerization of zillion.
U.S. 4~292,457 discloses the alkylation of aromatic
hydrocarbons in the presence of a borosilicate AMS-lB (ZSM-
5) catalyst. U.S. 4,269,813 discloses the use of this gala-
lust in disproportionation and transalkylation processes
as well as in zillion isome~ization. Similar processes in
%;~;815
the presence of ZSM-4 and ZSM-5 catalysts are also
disclosed in U.S. 4,377,502.
U.S. 4,208,305 and U.S. 4,238,318 disclose, in add-
lion to the above catalytic processes, upgrading cracked
gasoline and naphtha, preparation of olefins from Alcoa
hots, preparation of olefinic gasoline, alkylation of
olefins, separation of hydrogen mixtures, and catalytic
hydrodewaxing of hydrocarbon oils in the presence of
zealot catalysts.
The present invention is directed to a method for
modifying the catalytic activity of a crystalline zealot
having a constraint index of 1 to 12 and a silica-to-
alumina ratio of 30 to no greater than 300, which method
comprises contacting said zealot with gaseous boron
trifluoride under conditions effective to reduce the
alpha activity of the zealot.
A ZSM-5 type zealot is advantageously modified by
contacting the zealot with gaseous an hydrous boron
trifluoride at moderately elevated temperature, such
as 150C, and for a relatively short time, such as 30
minutes, as more fully described hereinbelow. Surprise
tingly, the novel product exhibits reduced activity for
cracking a refractory hydrocarbon such as normal hexane,
as measured by the alpha test conducted at 538C, but it
exhibits enhanced activity for the conversion of methanol
to hydrocarbons, as more fully described hereinbelow.
Furthermore, as will be shown by example, the novel
modified zealot catalysts in general show a much higher
catalytic activity for conversions of less refractory
feed stocks than normal hexane than would be expected from
their alpha values. Such catalytic conversions of organic
compounds include olefin oligomerization, Tulane Diaspora-
lZ36815
portionation, zillion i30merization, catalytic dew axing, and the cavern of methanol to hydrocarbons, including olefin~
and/or guy line.
The boron trifluoride treated zealot catalyst make it
possible to use lower operating temperature or, quite
obviously, to use the same temperatures as generally
employed in the prior art but at higher Race velocities.
It is immediately apparent that having a catalyst of
enhanced activity has the potential for lowering operating
costs due to the fact that lower temperatures can be used
and allowing for a greater throughput due to the fact that
higher space velocities can be employed.
The treatment with boron trlfluoride by the method
described also imparts change in chemical composition and
physical properties as well as catalytic properties. These
ware illustrated by Example 21. This example suggest that a
reaction occurs between the zealot and BF3. It also
demonstrates that the modified zealots have somewhat
smaller pores and therefore will favor formation of
thinner molecules such as ethylene yin methanol con-
version) and para-xylene (in zillion isomerization).
¦ The novel catalyst of this invention is prepared
simply by treating a ZSM-5 type zealot at least partially
yin the acid form, preferably HZSM-5, with boron in-
fluoride. The treated zealot preferably is purged to
remove any excess BF3 that may be present. The method of
~236t3~S
treatment is not narrowly critical and typical conditions
utilize boron trifluoride flowing at 30 cc/mln. through 1
gram catalyst bed maintained at 150 C. However, it it
noted that flow rates of 1 to 600 cc/min. through 1 gram of
catalyst bed maintained at a temperature of from 25 to 500
C are also operable to produce the enhanced catalyst of this
invention. The time at which the boron trifluoride is
contacted with the catalyst is also not narrowly critical
and activation can be obtained at period of lime ranging
from 0.01 hour to 10 hours and preferably from about 0.1
to 2.0 hours. Following treatment with boron trifluoride,
the catalyst is ready for use, but it may be air calcined,
if desired. Contacting with boron trifluoride it highly
effective at atmospheric prosier, but suba~mospheric or
elevated pressure may be used.
¦ The conversion of lower alcohols, their ether, or
mixtures thereof to C2-C5 olefins and to heavier hydrocarbons
Rand the conversion of methanol to olefin~, to gasoline, and
to other hydrocarbon with ZSM-5 type catalyst it well
known. The conditions for these reactions are well
documented in the patents incorporated herein by reference.
the modified zealots of this invention are advantageously
used in these conversions. Other conversions in which the
modified zealots are advantageously used will now be
described.
¦ Oligomerlzation and polymerization involve the linking
of similar molecules in the presence of heat and a catalyst
S
. ,
1Z3681S
It form bigger molecule. Ollgomerization involves the
forming of divers, trimmers and quatramer8, whereas a typical
polymerization concern the joining of light olefins to form
pa very long chain olefin. Olefin oligomerizat~on and polyp
¦merizatlon condition include a temperature of from about
950 to about 935 F, preferably form about 390 F to about
810 F, a pressure of from about atmospheric to about 10,000
prig, preferably from about atmospheric to about 2,000 prig,
a WHSV (when a flow operation) of from about 0.1 Harley to
about 50 Harley, preferably from about 0.5 Harley to about
10 Harley, and a contact time (when a batch operation) of
from about 0.1 hour to about 48 hours, preferably from about
0.5 hour to about 24 hours and a hydrogen/olefin mole ratio
of from about 0 to about 20, preferably from about 0 to 10.
l Olefin oligomerizatlon, e.g., propylene may be carried
tout at temperatures below 525 C and preferably at about
13000 C, at WHSV's from 0.1 to 50, preferably at about 30, at
pressures from 350 prig to 550 prig.
l Tulane disproportionation is carried out at
temperatures from 90 C to 550 C, preferably at about 500
I at pressures from 0 prig to 3000 prig, at WHSV's from
¦0.01 Harley to 90 Harley, preferably at about 10.
l Zillion isomerization may be carried out at
temperature from 230 C to 540 C, more preferably from
230 C to 300 C, at pre9sureg up to 1500 prig, preferably
from 20 to 400 slug, at WHSV's from 0.1 to 200, preferably
from 0.5 to 50, and more preferably from 5 to 25, and even
:1236815
more preferably at about 10.
¦ A it known in the art, Z~M-5 type zeolitic materials
ware member of a novel class of zealots that exhibit
unusual propertle~. Although these zealots have unusually
slow alumina contents, i.e. high silica to alumina ratio,
they are very active even when the silica to alumina ratio
exceeds 30. the activity it surprising since catalytic
activity is generally attributed to framework aluminum atoms
Andre cations associated with these aluminum atom. These
solute retain their cry~tallin~ty for long periods in
spite of the presence of steam at high temperature which
induces irreversible collapse of the framework of other
solutes, e.g. of the X and A type.
An important characteristic of the crystal structure of
thus class of zeollteg it that it provide constrained
axis to and egress from the intracrystalline free space by
virtue of having an effective pore size intermediate between
the small pore Line A and the large pore Line X, i.e. the
spore windows of the structure have about a size such as
would be provided by 10-membered rings of oxygen atoms. It
is to be understood, of course, that these ring are those
formed by the regular disposition of the tetrahedral making
p the anionic framework of the crystalline aluminosilicate,
the oxygen atoms themselves being bonded to the silicon or
aluminum atom at the centers of the tetrahedral Briefly,
the preferred type zeoliteg useful in this invention
obsess, in combination: a silica to alumina mole ratio of
~368~5
it least about 12s and a structure providing constrained
access to the crystalline free space.
¦ The silica to alumina ratio referred to may be deter-
wined by conventional analyst. This ratio I meant to
represent, as closely as possible, the ratio in the rigid
anionic framework of the zealot crystal and to exclude
aluminum in the binder or in cationlc or other loam within
the channels. Although zealots with a silica to alumina
ratio of at least 12 are useful, it is preferred to use
solutes having higher ratios of at least about 30. Such
solutes, after activation, acquire an intracrystalline
sorption capacity for normal hexane which is greater than
that for water, i.e. they exhibit hydrophobic properties.
Kit is believed that this hydrophobic character is ad van-
¦tageous in the present invention.
¦ The preferred zealots useful in this invention have an
effective pore size such as to freely sorb normal hexane.
yin addition, the structure must provide constrained access to
larger molecules. It is sometime possible to judge from a
known crystal structure whether such constrained access
exits. For example, if the only pore window in a crystal
no formed by 8-membered rings of oxygen atoms, then access
to molecules of larger cross-section than normal hexane it
excluded and the zealot is not of the desired type. Win-
owe of 10-membered ring are preferred, although in some
intones excessive puckering of the ring or pore blockage
Jay render these zealots ineffective. 12-membered rings
~236~31S
usually do not offer sufficient constraint to produce the
advantageous conversions, although the puckered 12-ring
structure of TEA offretite show constrained access. Other
wrung structures may exist which, due to pore blockage or
to other cause, may be operative.
¦ Father than attempt to judge from crystal structure
whether or not a zealot possesses the necessary constrained
access to molecules larger than normal paraffins, a simple
determination of the constraint Index or KIWI., as herein
defined may be made by passing continuously a mixture of an
equal weight of normal hexane and 3-methylpentane over a
small sample, approximately one gram or less, of zealot at
atmospheric pressure according to the following procedure.
PA sample of the zealot, in the form of pellets or extra-
date, is crushed to a particle size about that of coarse
sand and mounted in a glass tube. Prior to testing, the
zealot is treated with a stream of air at 1000 for at
least 15 minute. The zealot is then flushed with helium
and the temperature is adjusted between 550 and 950 F to
give an overall convection between 10~ and 60%. The mixture
of hydrocarbon it pasted at 1 liquid hourly space velocity
(i.e. 1 volume of liquid hydrocarbon per volume of zealot
or hour) over the zealot with a helium dilution to give a
ilium to total hydrocarbon mole ratio of sly. After 20
inures on stream, a sample of the effluent is taken and
analyzed, most conveniently by gag chromatography, to deter-
mine the fraction remaining unchanged for each of the two
lZ3G815
¦ hydrocarbon
The KIWI. is calculated a follows:
KIWI. = KIWI (fra~lQn of Nixon ~emalninqL
logl~fraction of 3-methylpentane remaining)
l The Constraint Index approximates the ratio of the
¦ cracking rate constants for the two hydrocarbon. Zealots
¦ suitable for the prevent invention are those having a Con-
¦ strait Index of 1 to 12. KIWI. values for Rome typical
¦ zealot are:
~2368~5
ZSM-4 5
ZSM-5 By
ZSM-ll 8.7
ZSM-12 2
ZSM-23 9.1
ZSM-35 4 5
ZSM-38 2
TEA Offretlte 3.7
Beta 0.6
H-Zeolon (mordant) 0.4
RYE 0 4
Amorphous Silica-Alumlna 0.6
Erlonlte 38
The above-described Constraint Index I an important
and even critical deflnltlon of those zealots which are
useful in the ln~thnt invention. The very nature of this
parameter and the recited technique by which it it deter-
mined, however, admit of the posalblllty that a given zoo-
lute can be tested under somewhat different conditions and
thereby have different Constraint Indexes. Constraint Index
seems to vary somewhat with severity of operation
(conversion) and the presence or absence of binders. There-
fore, it will be appreciated that it may be possible to a
select text conditions to establish more than one value in
~lZ368~5
the range of 1 to 12 for the Constraint Index of a part-
cuter zealot. Such a zealot exhibits the constrained
access as herein defined and is to be regilded as having
a Constraint Index of 1 to 12. Also contemplated herein
as having a Constraint Index of 1 to 12 and therefore
within the scope of the novel class of highly siliceous
zealots are those zealots which, when tested under two
or more sets ox conditions within the above-specified
ranges of temperature and conversion, produce a value of
the Constraint Index slightly less than 1, e.g. 0.9, or
somewhat greater than 12, e.g. 14 or 15, with at least
one other value of 1 to 12. Thus, it should be under-
stood that the Constraint Index value as used herein is
an inclusive rather than an exclusive value. That is,
a zealot when tested by any combination of conditions
within the testing definition set forth hereinabove and
found to have a Constraint Index of 1 to 12 is intended
to be included in the instant catalyst definition regard-
less that the same identical zealot tested under other
defined conditions may give a Constraint Index value
outside of 1 to 12.
Tune class of zealots defined herein is example-
fled by ZSM-5, ZSM-ll, ZSM-12, ZSM-21, ZSM-23, ZSM-35,
ZSM-38, ZSM-48, and other similar materials. U.S. Patent
3,702,886 describes and claims ZSM-5.
ZSM-ll is more particular lye described in U.S. Patent
3,709,979.
,,.
1Z;36815
ZSM-12 is more particularly described in U.S. Patent
3,832,449.
ZSM-21 is more particularly described in U.S. Patent
4,046,859.
ZSM-23 is more particularly described in U.S. Patent
4,076,842.
ZSM-35 is more particularly described in U.S. Patent
4,016,245.
ZSM-38 is more particularly described in U.S. Patent
4,046,859.
Natural zealots may sometimes be converted to
this type zealot catalyst by various activation prove-
dunes and other treatments such as base exchange,
steaming, alumina extraction and calcination, in come
binations. Natural minerals which may be so treated
include ferrierite, brewsterite, stilbite, dachiardite,
epistilbite, heulandite, and clinoptilolite. The pro-
furred crystalline zealots are ZSM-5, ZSM-ll, ZSM-12,
ZSM-21, %SM-23, ZSM-35, ZSM-38 and ZSM-48, with ZSM-5
and ZSM-11 particularly preferred. In some instances,
it is advantageous to steam the frost zealot to no-
dupe its activity and thereby improve its selectivity
,.~
:~Z368~5
prior to use. Such improvement has been noted with
steamed ZSM-5.
In a preferred aspect of this invention, the
zealots selected are those having a crystal framework
density, in the dry hydrogen form, of not less than about
1.6 grams per cubic centimeter. It has been found that
zealots which satisfy all three of these criteria are
most desired. Therefore, the preferred zealots of this
invention are those hosing a Constraint Index as defined
above of about 1 to 12 and a dried crystal density of not
less than about 1.6 grams per cubic centimeter. The dry
density for known structures may be calculated from the
number of silicon plus aluminum atoms per 1000 cubic
Angstroms, as given, e.g., on Page 19 of the article on
elite Structure by WOMB. Meter. This paper is included
in "Proceedings of the Conference on Molecular Sieves,
London, April 1967," published by the Society of Chemical
Industry, London, 1968. When the crystal structure is
unknown, the crystal framework density may be determined
by classical pyknometer techniques. For example, it may
be determined by immersing the dry hydrogen form of the
zealot in an organic solvent not sorbed by the crystal.
Or, the crystal density may be determined by mercury
porosimetry, since mercury will fill the interstices
between crystal but will not penetrate the intracry-
stalling free space. It is possible that the unusual
sustained activity and stability of this class of
,~;;
~23681S
solutes is associated with its high crystal anionic frame-
work density of not less that about 1.6 grams per cubic
centimeter. This high density must necessarily be also-
shouted with a relatively small amount of free space within
the crystal, which might be expected to result in more
stable structures. This free space, however, it important
was the locus of catalytic activity.
~236~31S
Crystal framework densities of some typical zealot
¦ including some which are not within the purview of they'll
¦ invention are:
Void Framework
Zealot Volume Density
Ferrlelrite 0.28 cc/cc 1.76 g/cc
Morden:lte aye 1 .7
ZSM-5, 11 .29 1.79
ZSM-12 - 1.8
ZSM-23 - 2.0
Dachia:cdite .32 1.72
L .32 1.61
Cllnoptllollte .34 1.71
Laminate .34 1,77
ZSM-4, Omega .38 1.65
Heulandlte .39 1.69
P .41 1.57
Offret.Ite .40 1.5S
Levynite .40 1.54
Erionilte ,35 1.51
Gmelin.ite ,44 1.46
Chabaz:Lte ,47 1,45
A ,5 1.3
Y .48 1.27
~Z36815
When sinusoid in the alkali metal form, the ZSM-5
type zealot before treatment with BF3 is conveniently con-
vented to the hydrogen form, generally by intermediate
formation of the ammonlum form a a result of ammonium ion
exchange and calcination of the ammonium form to yield the
hydrogen form, i.e. HZSM-5. In addition to the hydrogen
loam, other form of the zealot wherein the original alkali
metal has been reduced to lets than about 1.5 percent by
weight may be used.
In practicing the desired conversion process, it may
be desirable to incorporate the above-described crystalline
alumlnosilicate in another matrix resistant to temperature
and other conditions employed in the process. However, it
has been found that such incorporation preferably should not
take place until after the Zulu ha been treated with
boron trifluoride since the presence of some matrices, for
reasons which are not completely understood, interferes with
the activation procedure This is particularly true for
alumina or alumina-contalnlng) matrices. Silica matrices
Jay not be detrimental to the activation procedure and
could be composite with the zealot prior to activation
with boron trifluoride.
The modified zealot, if treated with 8F3 in the
absence of binder, may be incorporated with any conventional
matrix material. Such matrix maternal include synthetic or
naturally occurring substances a well a inorganic materials
such as clay, silica Andre metal oxides. Natural clays
lZ36815
which can be compocited with the zealot include those of
the montmorlllonite and kaolin families, which families
include the sub-bentonitea and the kaolin commonly known as
Dixie, McNamee-Georgia and Florida clay or others in which
the main mineral constituent Lo hollowest, coolant,
Dakota, nacrite or Anita.
In addition to the foregoing maternal the zealots
employed herein may be composite with a porous matrix
material, such as alumina, silica-alumina, ailicA-magnesia,
silica-zirconia, silica-thoria, silica-berylia, silica-
titanic as well as ternary compositions, such a silica-
alumlna-thorla, ~ilica-alumina-zlrconla, ~lllca-alumina-
magnesia and ~ilica-magnesia-zirconla, The matrix may be in
the form of a Vogel. The relative proportions of zealot
component and inorganic oxide gel matrix on an anhydrouc
basis may vary widely with the zealot content ranging from
between about 1 to about 99 percent by weight and more
usually in the range of about 5 to about 80 percent by
weight of the dry composite.
Although there to generally come type of correlation
between alpha value and catalytic activity in the convert
Sweeney contemplated in twig invention, the alpha activity
of the boron trifluoride treated catalyst way much reduced
by the treatment, but the conversion of methanol went up
(Table 1). This is a surprising and unexpected result which
it not understood.
The following examples will illustrate the best mode
lZ36815
contemplated for carrying out the invention.
A sample of HZSM-5 having a silica-to-alumina ratio of
70:1 and without binder was treated with boron trifluoride
by contacting it at 150 C and at atmospheric pressure with
boron trifluoride flowing at 30 cc/min. through a 1 gram
catalyst bed for approximately 10 minute, after which the
zealot way cooled in a steam of dry nitrogen.
EXAMPLE 2-6
The boron trifluoride modified catalyst of Example 1
was then tested for conversion of methanol to hydrocarbons
along with an HZSM-5 type zealot which had not been boron
trifluoride modified. The following Table 1 compares data
from the catalyst of this invention with the catalyst of the
prior art:.
1236815
.. -
V (I I L')
X t) Jo I I I I
I I I I I L'-
r I_ Jo
V
V
I Jo
W ,_
I O ED In Us I I
O do cry I
,,~ I
r
I Cc
. us o I
_ V I o o
'I I
or ¦ ; r; an Al
I
o o o I
O I cut
= I Al
Lo I
n rJ~ r
1 Lo r.
Jo n I
I
to -- I: m rod
lo
I, I I
~23~815
A can be seen from the above table, a space velocity
f approximately 0.5 is required to achieve loo methanol
onverslon at 300 c for an untreated HZSM-5. For the boron
trifluoride modified catalyst, a space velocity of 9.0
chives loo methanol conversion. This corresponds to an
increase in catalyst activity by a factor of approximately
15-20. Even at 280 C, the BF3 modlf$ed catalyst is four to
five times as active as the unmodified catalyst at 300 C.
SXAMPLEi~ 13
A swirls of experiments were carried out in order to
remonstrate the uniqueness of the novel activation procedure
f this invention.
In each of Examples 7-13c HzsM-5 having a lookout-
lumlna ratio of 70:1 was employed. In Examples 7 Anglo,
he conventional HZSM-5 catalyst of the prior art was
employed. In Examples 8 and if, and HZSM-5 treated with
Ron fluoride in the manner set forth in Example 2-6 was
mployedc
In Example 9, an ammonlum fluoride treated catalyst
as employed. This catalyst was prepared by m~xlng 0.46
ram of ammonlum fluoride with lo gram of ~ZSM-5 (no
lender) and healing at 150 C for 10 minutes with argon
flowing at 30 cc/min. These conditions simulate those used
for the preparation of sF3 catalyst. The catalyst of
sample 9 was then calcined in air at 500 C overnight to
overt it to the hydrogen form. In Example 12, a mixture
f HZSM-5 with alumina was treated with BF3 in the manner
1236815
previously described. In Example 13, a hydrogen fluoride
treated catalyst was used. This catalyst way prepared by
flowing a mixture of 3 cc of hydrogen fluoride and 27 cc of
Ron at 300 cc/min. over 1 gram of HZSM-5 (no binder) at
150 C for 15 minutes. The result obtained for methanol
inversion as well as alpha values of the various catalyst
no given in Table 2.
123683.S
' V Jo IT
Jo V _
. Jo
. V _ _
x I _ Jo
V I, . . .
, I
_
Jo
_, V
V ,. o Us
. I, It ox
t X Jo . . .
o o _ o
?
l on
2: 1, I
in fC '3
I O Lo aye .
no o v v I
En
.
O n
I I
us ? Ye o o o o _ us
Jo , , , . . I
o
O
.,,
Us O Jo
,. o o C o o o , --
. co o o Jo
E N I o Jo
Jo
_ O O Jo O CUD I
Us
I_
a
In V V
I Us Us
V _ O
Us Us
I q I V
Jo 1 I V
I
a 1 V I
D I U
r I ox o 2
'I
Jo
~236~31S
As can be seen from the above table, thy catalyst of
Example 8 had a ~ubstantlally lower alpha activity than the
catalyst of Example 7, yet it had enhanced activity for the
conversion of methanol. The same is equally true with
regard It the catalyst of Simple 11 as compared to the
catalyst of Example 10. Please note that treatment with
ammonium fluoride, i.e. Example 9, and hydrogen fluoride,
it Example 13 did not result in enhancement of methanol
conversion activity and, in fact, Example 13 shows an actual
decline relative to the untreated material.
Example 12 depict the results of incorporating an
~ZSM-5 into an alumina binder prior to treatment with boron
trlfluoride and, as can be seen, a catalyst was obtained
with an alpha of 6 and only slightly enhanced activity at
300 C. The BF3 appears to react much more rapidly with the
alumina binder than with the ZSM-5.
EXAMPLES 14-l7
These examples will illustrate the criticality of the
silica-to alumina ratio of the ZSM-5 type zealot. In
Examples 14 and 15, a crystalline ZSM-5 zealot having a
silica-to-alumina ratio of 800:1 was employed. In Examples
16 and 17, a similar material but having a silica-to-alumina
ratio of 1600:1 was employed. The method of activation with
boron trifluoride wag the game a previously described. The
results are shown in Table 3.
~Z3~}15
.,, ,, V ,
. .,. , . .
,.~ , I, ,
Lo
V
Jo I,
.,~ I 0 I
t, X . . .
o ,
s n o
to
I on UP Jo ED
to Al)
Jo
o , o
o
.0 owe
to o to o o
e E I
to
I o I
, US o
,
v
in
Jo on us n O O
I I I I I
." Jo
to to
o o
I
Jo or us ED t` ^ ^
Jo
. owe
:~Z36~S
l A can be seen from the table, treatment with boron
¦trifluorlde did not enhance the methanol conversion activity
of either of these two ZSM-5's simply because the sllica-to-
alumina ratio was too high.
¦ Therefore, the novel process of this invention it
applicably to ZSM-5 type zealots having a slllca-to-alumina
ratio of 30 to no greater than about 3~0 and, more
preferably, no greater than 100 and, even more desirably,
availing a sillca-to-alumina ratio of from about 30 to 80.
¦ Eye lo
A Cockney trifluoride modified catalyst prepared as in
example 1 was tested for propylene conversion
¦~oligomerizatlon) at 300 C and 30 WHSV. Table 4 compare
the data obtained with the boron trlfluorlde modified
catalyst with data obtained using HZSM-5 of similar activity
alphabet at the same operation conditions.
As can be seen from Table 4, propylene conversion way
approximately 16 time higher for the boron trlfluoride
treated catalyst compared to untreated HZSM-5. on addition,
the boron trifluor~de treated catalyst produced more of
desirable C6+ gasoline range hydrocarbons. Other olefins
would be expected to react similarly to propylene.
6tl15 -
I TAB LYE 4
I
¦ Swahili HZSI~-5
I
. I
temperature, C 300 300
so 30 30
¦~talysl~ Activity 0.14 0.16
conversion, Kit 99 6
Product disttihution, wit
¦ 11ethane no own
I thin no 0. n
I ~I:hylnnla n . 2 n. o
IPro~ane 3,3 1.0
I En p Y l. Q
nlltnnle foe I.
n-Rutane 3.1 2.0
I Olefin~s 11.3 17.0
Us Olefins foe 15.5
C6 Oleelns 13.8 30.2
C7 Olefins lows 10.4
I Olefln~ 33.4 8.4
. Cog Olefin~ 11.5 12.4
Coo Oleflns 2.3 0.2
99.9 100.0
SLUICE
I supply 19
¦ A boron trifluoride catalyst prepared as in Employ 1
wow tested for Tulane disproportionation at 500 C and 10
¦WHSV. Table 2 summarizes the data and compares them with
data obtained using ~2SM-5 of similar activity alphabet
¦ A can be seen from Table I at the same operating
conditions and using catalysts of the same alpha-activity,
the boron trifluorlde catalyst showed approximately 18 tome
higher conversion compared to untreated 82SM-5.
¦ TABLE
l BF3-HZSM-5 HZSM-5
I_______________________________
Temperature C 500 500
IWHSV 10 10
Catalyst Activity
¦ alphabet 2.2 2.2
. conversion, White 5.07 0.28
~2368i5
¦ AMPLE 20
¦ A boron trifluorlde catalyst prepared as in Example l
WEBB tested for zillion isomerizatlon at lo WHSV and various
temperatures. Table 6 ~ummarizeg the data and compares them
with Dwight obtained UB1n9 ~ZSM-5 of similar activity alpha-
test).
¦ As can be seen from Table 6, at 300 C and using
catalyst of the tame alpha activity the boron trifluoride
catalyst showed approximately four times higher conversion
compared to untreated HZSM-5. In order to obtain equivalent
conversancy, the temperature of the boron trifluoride
catalyst had to be significantly lowered to 230- C.
I
l BF3-HZSM-5 HZSM-5
I __________ ______
. temperature, C 300 230 300
WHSV lo lo lo
Catalyst Activity
alpha test 2.2 2.2 2.2
~onvec~l~n, it 16.3 4.3 I
29
~236~1S
For the conversion contemplated heroin, it it
referred to use ZSM-5 type zealots having a silica-to-
alumina ratio no greater than 300 and, more preferably, no
treater than loo and, even more de~lr~bly, having a silica-
to alumina ratio of from about 30 to 80.
¦ In audition to the above examples, the catalysts of
the invention may also be used in a wide variety of acid
catalyzed reactions. Dewaxlng, i.e., the selective cracking
of wax molecules, can be carried out at temperature greater
than 175c C ~347 F), more preferably at temperatures from
OWE C (392 F) to 430 C (806 F), and even more preferably
Nat temperature from 260 C (500 P) to 360 C (680 F1.
the dew axing reaction can be carried out at space velocities
¦(LHSV) from 0.1 to lo, more preferably from 0.1 to 50 and
it pressures up to 3000 prig, more preferably from 25 to
1500 p819.
The alkylation of aromatics with alcohols or olefin~
may be carried out at temperatures for 150 C to 750 C,
Gore preferably from 2Z5 C to 600 C, at pressures up to
p500 slug, more preferably from 20 prig to 500 prig, at
~SV's form Owl to 400, more preferably from 3 to 30.
alcohols or oleflns such as methyl alcohol, ethyl alcohol,
ripen, ethylene, butane, l-butene, l-propene, l-dodecene,
can be used
¦ EXAMPLE 21
l Several preparations were made by the method used in
example l and were evaluated for physical properties,
12368~5
¦ including selectivity log ethylene produced when converting
¦ methanol. at 100~ conver~lon. The royalty are summarized in
¦ Table 7.
¦ TABLE 7
¦ Physic]. HZSM-5 Range for
I Property 3-HZSM-5
¦ Alpha Value 150 typical 0 to 29
¦ Crystalllnity, 100 90 to 95
¦ O-xylene sorption)
¦ Capacity, mug ) 50 19
Diffusion time for
30~ of capacity ) 270 900
I for O-xylene, minutes)
¦ White Boron 0 0.1 - 0.5
¦ White Fluorine 0 5 to 10
¦ Ethylene selectivity,)
¦ 100~ Methanol ) 8 18
I Conversion, White )
¦ Although this invention is described particularly with
¦ reference to 8F3, it 18 contemplated to employ other Lewis
¦ acid fluorides such a PF3, AsF3, SbF5 and Bits in place of
¦ BF3-
