Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~1~7134
BACK~RO~ D OF T~E I~JEN~IO~I
~ield of the~lnvention
The invention relates to crystalline aluminosilicate
zeolite composltions. More parti~ularly, it relates to crystal-
line zeolites that are crystallized in the presence of certain
metals or metal compounds. It relates further to hydrocarbon
conversion with such catalysts.
Description of the Prior Art
Zeolitlc materials, both natural and synthetic, have
been demonstrated in the past to have catalytic capabillties for
various types of hydrocarbon conversion. Certain zeolitic
- materials are ordered, porous crystalline aluminosilicates having
a definite crystalline structure within which there are a large
number of small ca~ities which are interconnected by a number of
still smaller channels. These cavities and channels are pre-
cisely uniform in size. Since the dimensions o~ these pores are
such as to accept for adsorption molecules of certain dimensions,
while rejecting those of larger dimensions, these materials have
come to be known as "molecular sieves" and are utilized in a
variety of ways to take advantage of these properties.
Such molecular sieves lnclude a wide variety of posi-
tlve ion-contalnlng crystalline aluminosilicates~ both natural
and synthetlc. These alumlnosilicates can be described as a
rlgid three-dimenslonal network of SiO4 and A104 in which the
tetrahedra are cross-linked by the sharing of oxygen atoms
whereby the ratio of the total aluminum and silicon atoms to
oxygen is 1:2. The electrovalence of the tetrahedra-containing
- 2 -
' ~
1127134
aluminum is balanced by the inclusion in the crystal of a
cation, for e~ample, an alkali metal or an alkaline earth
metal cation. This can be expressed by lormula ~herein the
ratio o~ Al to the number of the various cations, such as
Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of
catlon has been exchanged elther ln entirety or partially by
another type of cation utilizin~ ion exchange techniques in a
conventional manner. By means of such cation exchange, it has
been possible to vary the size of the pores in the given
aluminosilicate by suitable selection of the particular cation.
` The spaces between the tetrahedra are occupied by molecules of
water prior to dehydration.
U.S. 3,941,871 discloses and claims a crystalllne
metal organosilicate ha~ing a high silica-to-alumina ratio and
contalnlng, in additlon to sodium, calcium1 nlckel or zinc.
Other prior art techniques have resulted in the
~ormation of a great ~ariety of synthetic crystalline alumino-
silicates. These aluminosilicates have come to be designated
by letter or other con~enient symbol, as lllustrated by zeolite
A (U.S. 2,882,243), zeolite X (U.S. 2,882,244), zeolite ZSM-5
(U.S, 3,702,886), zeolite ZSM-ll (U.S~ 3,709,979), ZSM~12
~U.S. 3,832,449) and zeolite ZSM-35 ~U.S. 4,016,245), merely
to name a ~ew.
SUMMARY OF T~E INVENTION
The pre9ent inventlon relates to stable synthetic
crystalline aluminosilicate æeolite compositions, toa m~hod for
t he ir preparation and to hydrocarbon con~ersion processes
conducted therewith. These composltions, as synthesized, have
-- 3 --
.
~ ::
3~
a definite x-ray diffraction pattern, characteristic of the
ZSM-5 zeolites and shows the significant lines set forth in
Table 1.
TABLE 1
Interplanar spacing d(A~: Relevant Intensitx
11.1 + 0.2 s
10~0 + 0.2 s
7.4 + 0.15 w
7.1 + 0.15 w
6.3 + 0.1 w
6.04)
+ 0. 1 w
5.97)
5.56 + 0.1 w
5.01 + 0.1 w
4.60 + 0.08 w
4.25 + 0.08 w
3.85 ~ 0.07 vs
3.71 ~ 0.05 s
3.04 + 0.03 w
2.99 + 0.02 w
2.94 + 0.02 w
These values were determined by standard technique~.
The radlatlon was the K-alpha doublet of copper, and a sclntilla-
tlon counter spectrometer with a strip chart pen recorder was
used. The peak heights, I, and the positions as a function of
2 times theta, where theta is the Bragg angle, were read from
X
.
1127i;~4
the spectrometer chart. From these, the relative intensities,
100 I/Io, where Io is the intensity of the strongest line or
peak, and d (obs.l, the interplanar spacing in A, corresponding
to the recorded lines, were calculated. In Table 1 the relative
intensities are given in terms of the symbols s = strong, w =
weak and vs = very strong. It should be understood that this
X-ray diffraction pattern is characteristic of all the species
of the present compositions. Ion exchange of the sodium ion
with cations reveals substantially the same pattern with some
minor shifts in interplanar spacing and variation in relative
intensity. Other minor variations can occur depending on the
silicon to aluminum ratio of the particular sample and the
extent of thermal conditioning.
The anhydrous composition can also be identified, in
terms of mole ratios of oxides, as follows:
2 ~W : ~A120~ X : ~sio2Jy : ~M" 0
2 n
wherein W~X is from ~0.5 to <3, Y/X is ~20 and Z/X is from >zero
to ~ ~ 100, R is a nitrogen containing cation. R may include
primary amines containing 2 to 10 carbon atoms and ammonium
cations, preferably the tetraalkylammonium cation in which the
alkyl contains from 2 to 5 carbon atoms, M' is a metal from Group
IA of the Periodic Table, ammonium, hydrogen or mixtures thereof,
and n is the valence of M' or M". With respect to M", the pre-
ferred metals are those selected from the rare earth metals, (i.e.
metals having atomic numbers from 57 to 71), chromium, vanadium,
molybdenum, indium, boron, mercury, tellurium, silver and one of
the platinum group metals, which latter group includes platinum,
palladium and ruthenium.
1127134
It is not known whether the M" is present as a metal
or as a metal compound. The above formula will be understood
to take into account the presence in any of the M" various
states and also to allow for varying amounts thereof. For
example, if it is present in the occluded state, then its
concentration relative to aluminum in the zeolite as synthe-
sized can range up to but less than about 100.
DESCRIPTION OF SPECIFIC EMBODIMEMTS
A reaction mixture containing sources of the tetra-
propylammonium cation tas from the hydroxide), sodium oxide,
silica, water, and sources of, for example, indium, boron,
ruthenium, platinum, chromium, rare earth, vanadium, mercury,
tellurium, silver, palladium, molybdenum and, optionally,
alumina, will yield a ZSM-5 zeolite, but having unexpectedly
improved properties. The content of indium, boron, etc. listed
above can range in the final product from about 0.005~ by weight
to 5.0% by weight.
The crystalline aluminosilicates prepared by the
~ method of the present invention have high thermal stability and
`~ ~ 20 exhibit superior catalytic performance.
~ The original alkali metal can be replaced, at least in
:
part, in accordance with techniques well-known in the art
by lon exchange wlth other cations. Pre~erred replaciny cations
include metal ions, ammonium ions, hydrogen ions, and mixtures of
the same. Particularly preferred cations are those which render
the zeolite catalytically active, especially for hydrocarbon
conversion. These ir,clude hydrogen, metals of Group II and
VIII of the Periodic Table and manganese.
~'
~lZ7~,34
In a preferred embodiment of the zeolite, the
silica/alumina mole ratio is yreater than 35 and ranges up
to about 3000.
The present zeolites have a high degree of thermal
stability thereby rendering them particularly effective for
use in processes involving elevated temperatures.
The composit~on can be prepared utilizing materials
which supply the appropriate components of the zeolite. Such
components include, for an aluminosilicate, sodium aluminate,
alumina, sodium silicate, silica hydrosol, silica gel, silicic
acid, sodium hydroxide and a tetrapropylammonium compound, e.g.
tetrapropylammonium hydroxide. It will be understood that each
component utilized in the reaction mixture for preparing the
zeolite can be supplied by one or more initial reactants and
they can be mixed together in any order. For example, sodium
can be supplied by an aqueous solution of sodium hydroxide, or
by an aqueous solution of sodium silicate; tetrapropylammonium
cation can be supplied by the bromide salt. The reaction mix-
~ture can be prepared either batchwise or continuously. Crystal
^~ 20 size and crystallization time of the composition will vary with
the nature of the reaction mixture employed. It will be further
understood that in the very high silica-to-alumina ratios, which
, ~
can ln this invention preferably range from greater than 35 to
about 3000 or more, and more preferably about 70 to about 500,
1t may not be necessary to add a source of alumlna to the
reaction mixture since residual amounts in other reactants may
suffice.
, The zeolite can be prepared from a reaction mixture
having a composition, in terms of mole ratios of oxides or in
~ of total moles of oxides, falling within the fcllowing ranges:
llZ7134
~ABLE 2
~ost
Broad Preferred Preferred
OH-~SiO2 0.07-1.0 0.1-0,8 0.2-0.75
R4N ~R4N~ + Na+l 0.2-0.95 0.3-0.9 0.4-0.9
H20~0E 10-300 10-300 10-300
sio2/A123 50-3000 70-1000 70-500
Other metal
(% of total oxides) lx10 -1-0 lx10 -0.1 lx10-5-0 01
R is as deflned hereinabove in the Summary.
.
Typlcal reaction conditions consist of heating the
foregoing reaction mixture to a temperature of from about 95C
to 175C for a period of tlme of from about six hours to 120 days.
A more preferred temperature range is from about 100C to 175C
~: wlth the amount of time at a temperature in such range being from about 12 hours to 8 days.
` ~ The digestion of the gel particles is carried out
-~ untll crystals form. The solid product is separated from the
2~ reaction medium, as by cooling the whole to room temperature~
filtering and water washing.
The ~oregoing product ls dried, e,g~ at 230F, for
~,,
from about 8 to 24 hours. Of course, milder conditions may be
`~ employed i~ deslred, e.g room temperature under vacuum.
:
2~ The zeolite can have the alkali metal associated
therewith replaced by a wide variety of other cations according
; to technlques well-known in the art. Typical replaclng cations
would lnclude hydrogen, ammonium and metal cations includlng
- mixtures of the same. Of the replacing metallic cations, par-ticular preference is given to cation of metals such as rare
earth metal, manganese and calcium, a~ well as metals of Groups
II and VIII of the Periodic Table, e~g,~ zinc or platinum,
_ 8 -
~i27~34
Typical ion exchange techniques include contacting
the zeolite with a salt of the desired replacing cation or
cations. Although a wide variety of salts can be employed,
particular preference is given to chlorides, nitrates and
sulfates.
Representative ion exchange techniques are disclosed
in a wide variety of patents including United States 3,140,249;
United States 3,140,251; and United States 3,140,253.
Following contact with the salt solution of the
desired replacing cations, the zeolites are then preferably
washed wlth water and dried at a temperature ranging from 150F
to about 600F and thereafter calcined in air or other inert
gas at temperatures ranging from about 500F to 1500F for
periods of time ranging from 1 minute to ~8 hours or more.
Regardless of the cations replacing the sodium in
its synthesized form, the spatial arrangement of the aluminum,
silicon and oxygen atoms which form the basic crystal lattices
of the zeolite remains essentially unchanged by the described
.~:
replacement of sodium or other alkali metal as determined by
taking an X-ray powder diffraction pattern of the ion-exchanged
materials. Such X-ray diffraction pattern of the ion-exchanged
-~ product reveals a pattern substantially the same as that set forth
in Table 1 above.
The aluminosilicates prepared by the instant invention
are formed in a wide variety of particular sizes. Generally
speaking, the particles 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, the aluminosilicate
can be extruded before drying or dried or partially dried and
then extruded.
~127~34
As in the case of many catalysts, it is desired to
incorporate the zeolites with another material resistant to the
temperatures and other conditions employed in organic conversion
processes. Such materials include active and inactive materials
and synthetic or naturally occurring zeolites as well as inorganic
materials such as clays, silica and/or metal oxides. The latter
~ay be either naturally occurring or in the form of gelatinous
precipitates or gels including mixtures of silica and metal
oxides. Use of an active material in conjuctiDn with the present
composition, i.~., combined therewith, tends to improve the
conversion and/or selectivity of the catalyst in certain organic
conversion processes. Inactive materials suitably serve as
diluents to control the amount of conversion in a given process
so that products can be obtained economically ~nd in orderly
manner without employing other means for controlling the rate
or reaction. Normally, zeolite materials have been incorporated
into naturally occurring clays, e.g.bentonite and kaolin, to
improve the crush strength of the catalyst under commercial
; operating conditions. These materials, i.e., clays, oxides,
etc. function as binders for the catalyst. It is desirable
to provide a catalyst having good crush strength, because in
a petroleum refinery the catalyst is often subjected to rough
handling, which tends to break the catalyst down into powder-
like materials which cause problems in processing. These clay
binders have been employed for the purpose of improving the
crush strength of the catalyst.
Naturally occurring clays which can be composited
with the catalyst 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
~12~134
kaolinite, dickite, nacrite or anauxite. Such clays can be
used in the raw state as originally mined, or they can be initially
subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the
catalyst can be composited with a porous matrix material such
as silica, alumina, silica-alumina, silica-magnesia, silica-
zirconia, silica-thoria, silica-beryllia, silica-titania
as well as ternary compositions such as silica-alumina-thoria,
silica-alumina-zirconia, silica-alumina-magnesia and silica-
magnesia-zirconia. The matrix can be in the form of a cogel.
The relative proportions of finely divided crystalline alumino-
silicate and inorganic oxide gel matrix vary widely, with the
crystalline aluminosilicate content ranging from about 1 to
about 90 percent by weight and more usually, particularly when
the composite is prepared in the form of beads, in the range
of about 2 to about 50 percent by weight of the composite.
While the catalyst is useful in cracking and hydro-
cracking, it is outstandingly useful in other petroleum refining
processes, indicating again the unique catalytic characteristics
of these zeolites. The latter processes include isomerization
of n-paraffins and naphthenes, polymerization o~ compounds con-
talning an olefinic or acetylenic carbon-to-carbon linkage such
as isobutylene and butene-l, reformlng, alkylation, isomerlzation
`, of polyalkyl substituted aromatics, e.g. ortho-xylene, and
disproportionation of aromatics, such as toluene, to provide a
mixture of benzene, xylenes and higher methylbenzenes. The
catalysts have exceptional high selectivity and, under the
conditions of hydrocarbon conversion, provide a high percentage
of desired products relative to total products compared with
known zeolite hydrocarbon conversion catalysts.
7134
AS indicated above, the zeolite is also useful in
other catalytic processes, such as catalytic cracking of
hydrocarbons and hydrocrac~ing. In addition to the thermal
stability of this family of zeolites under these conditions,
they provide conversion of the cracked oil to materials
having lower molecular weights and boiling points, which are
of greater economic value. The ability to be physically stable
under high temperatures and/or in the presence of high tempera-
ture steam is extremely important for a cracking catalyst.During catalytic conversion, the reaction which takes place is
essentially a cracking to produce hydrocarbons. However, this
cracking is accompanied by a number of complex side reactions
such as aromatization, polymerization, alkylation and the li~e.
As a result of these complex reactions, a carbonaceous deposit
is laid down on the catalyst which is referred to by petroleum
engineers as "coke". The deposit of coke on the catalyst tends
to seriously impair the catalyst efficiency for the principal
reaction desired and to substantially decrease the rate of
conversion and/or the selectivity of the process. Thus, lt
is common to remove the catalyst after coke has been deposited
thereon and to regenerate it by burning the coke in a stream of
oxidizing gas. The regenerated catalyst is returned to the
converslon stage of the process cycle. The thermal ~tabllity
of the 2eolite is advantageous in this re~ard.
~ he products can be used either in the alkali metal
form, e.g., the sodium form, in the ammonium form, the hydrogen
form, or another univalent or multivalent cationic form.
Preferably, one or the other of the last two forms is employed.
They can also be used in intimate combination with a hydro-
genating component such as tungsten, vanadium, molybdenum,
rhenium, nickel, cobalt, chromium, manganese, or a noble metal
such as platinum or palladium where a hydrogenation dehydrogena-
tion functlon is to be performed. Suah component can be exchanged
12
7~34
into the composition, impregnat~d therein or physically intim-
ately admiYed therewith. Such component can be impregnated
in or onto the zeolite, such as, for example, by, in the case of
platinum, treating the zeolite with a platinum metal-containing
ion. Thus, suitable platinum compounds include chloroplatinic
acid, platinous chloride and various compounds containing the
platinum ammine complex.
The compounds of the useful platinum or other metals
can be divided into compounds in which the metal is present in
the cation of the compound and compounds in which it is present
in the anion of the compound. Both types of compounds which
contain the metal in the ionic state can be used. A solution in
which platinum metals are in the form of a cation or cationic
complex, e.g. Pt(NH3)6C14 is particularly useful. For some
hydrocarbon conversion processes, this noble metal form of
the catalyst is unnecessary such as in low temperature,
liquid phase ortho-xylene isomerization.
When it is employed either as an adsorbent or as a
catalyst in one of the aforementioned processes, the catalyst
should be at least partially dehydrated. This can be done by
heating to a temperature in the range of 200 to 600C, in an
atmosphere such as air, nitrogen, etc. and at atmospheric or
subatmospheric pressures for between 1 minute and 48 hours~
Dehydration can also be performed at lower temperautres merely
by placing the catalyst in a vacuum, but a lon~er time is
required to obtain a sufficient amount of dehydration.
The following examples will illustrate the invention~
'~r ;.r
~127~34
E~AMPLE 1
Solution 1
Q Brand Silicate240 gms
Distilled ~20 300
- 540
Solution 2
Distilled H20~10 gms
Tetrapropyl Ammonlum Bromide 30
~; Conc. H2S04 20
CrK(S04)2~l2H2012,25
Q Brand ls a Phlladelphia Quartz Co. commercial brand of
sodium sllicate. Typlcal Analysis: 8.9% Na20, 28.7 S102,
62.4% H20.
Solutlon 1 was placed into a 4-neck 2 1. flask wlth
overhead stirrer. Solution 2 was added wlth stirring. The
solutlon became very gelatlnous, A small amount of X-ZSM-5
(about O.lg) was added for seeding. Heating was begun and
the solutlon was allowed to heat to about 205F~ The variac
; ~ setting was the only control on the temperature so it varied
20 ~ + 3C depending on voltage variations during the day. After
a few days, the solutlon lost lts gelatinous character and
became more ohalX-like. Crystallization~ as determined by
X-ray, took 5-6 days. The catalyst was flltered and washed
with about 4 llters of distilled H20. The yield was 60-70 gms
of catalyst.
The catalyst was dried at 70C and calcined in a
crucible in a muffle furnace at 75 to 1000F for 12 hours.
The catalyst was placed in a 200 ml flask with 100 cc f H20
and 10 gm of NH4N03 and refluxed at 100C for 1 hour, The
catalyst was filtered, washed and NX4~03 e~changed reoeatedly
for 5 hours. The catalyst was again filtered, washed and
- 14 -
,
1127134
exchanged re~eatedly for about' 16 hours. ~he catalyst was
~_l'erec, -~as'r.ed thoroughly and drie~ -~ 70C ~or ebou~ ~
hours. The catalyst was calcined again in a muffle furnace
at 75 to 1000F for 6 hours.
X-ray powder diffraction patterns of the crystalline
product, both in the as-synthesized form and after the treat-
ments descrlbed a bove, are given in Table 3~
While this Example illustrates the use of the
ammonium cation, other cations such as alkyl ammonium, metals
and hydrogen may be used.
As set forth in Table 3, minor differences are
observed between the X-ray diffraction patterns of the as-synthe-
sized zeolite and the same zeolite after ion exchange and thermal
treatments. These differences are changes from singlets to
doublets and other doublets to singlets between the two patterns
resulting ~rom mlnor shiPts in interplanar spacings and varla-
tlons in relatlve lntensities. These observed differences
reflect minor variations ln lattice parameters and crystal
symmetry.
~127134
~ABLE 3
~s Syn~hesize~ ~inished O~t21 ~st
2~ d(A)I/I(0) 2e d(A) I/I(0)
7.89 11.20 367 ' 85 11.26 100
8 78 10.07 26 8.75 10.11 59
9 01 9.81 9 9.05 9.77 14
9.84 8.9g 3 9.80 -9.02
10.98 8. o6 1 10.95 8.08
11.88 7.45 11 11.85 7.47
12.49 7.09 5 12.50 7.08
13.15 6.73 6 13.17 6.72 8
13.89 6.38 14 13.88 6.38 11
14.60 6.07 9~
! 14.72 6.02 17
14.79 5 - 99 10
~ 14.90 5.95 2
15.48 5.72 9 15.50 5.72 8
15.89 5.58 11 15.85 5.59 11
16.46 5.39 3 16.50 5.37 3
17.25 5.14 ~ 17.23 5.15 2
17.65 5.02 2 17.60 5,04 4
17.75 5~00 4 17.76 4.99 5
18.13 4.89
- 18.80 4.72
19.25 4.61 9 19.21 4.62 4
19.90 4.46 3 19.85 4.47
20.35 4.36 11 20.32 4.37 6
20.85 4.26 12 20.82 4.27 8
21.75 4.09 2 21.75 4.09 3
22.19 4.01 8 22.16 4.01 4
23.15 3.84 100 23.13 3.85 65
23.25 3.83 28
23.67 3.76 24 23.63 3.76 16
23.~2 3.72 45 23,90 3.72 30
~-24.30 3.66 8
24.38 3.65 30
~ 24.52 3.63 8
;~ ~ 24 75 3.60 2
25 55 3.49 4 25.50 3.49 3
25.90 3.44 12 25.84 3,45 5
26.35 3.38 2 26.15 3.41 2
26 68 3.34 7 26.53 3.36 5
26 95 3.31 9 26.92 3.31 7
~27.38 3.26 3
27 - 45 3.25 3 ~7.63 3.23
28.05 3.18 2 28.13 3.17
28.45 3 - 14 3~28 40 3; 146 13
29.25 3.05 11~29.35 3.04 3
~29.85 2~99 12
29.~5 2.98 12
~30.18 2.96 5
30.35 2.94 6 30,52 2.93
31.23 2,86 2 31.20 2 ~ 87 2
31.50 2 ~84
32 15 2.78 1 32.12 2 ~7~ 1
32 80 2.73 3 32.71 2.7~ 2
~127134
TABLE 3 ( CO~TT ' D )
33.45 2.68 1 33,36 2.69
33.80 2.65 1 33.69 2,66
34.38 2,61 4 34.33 2.61 2
34.71 2.58 - 1 34.55 2.60 2
34.95 2.57 - 1
35, o6 2,56 2
35.18 2.55
35.75 2.51 3 35,63 2,52 2
~36, o4 2.49 3
36.10 2.49 5
(36,28 2,48 2
36.72 2.45 1 36,58 2.46
37.11 2.42 3 37,18 2,42 2
37.53 2.4~ 4 37,56 2,39 2
38.31 2.35
38.79 2,32
39.17 2,30
40,39 2,23 1~
40,45 2,23
40.62 2.22 1
40.99 2,20 1 40,99 2.20
41.45 2.18 1 41,43 2.18
41 78 2 16 1 41.80 2,16
42 50 2 13 1 42,48 2.13
42,88 2,11 ^ 1 42,83 2,11
43 24 2,09 1 43.13 2.10
43 56 2,08 1 43.53 2,08
43,81 2.07
45.15 2.01 9 45.02 2.01 6
45.48 1.99 9 45.50 1.99 5
46.25 1.96
46 51 1.95 3 46.50 1.95 2
47 50 1.91 3 47,42 1.92 2
48.44 1.88 2
48.60 1.87 4
~48.83 1.86
49.48 1.84 1 49.53 1,84
49,78 1.83 1 49,92 1.83
50.18 1.82 1 5~,27 1,81
50,87 1,79
51 40 1,78 1 51,27 1,78
51 60 1.77 2 51,66 1.77
51,90 1,76 52 25 1 75
53.21 1,72 1 53,17 1.72
53.50 1.71 54 23 1 7619
54.93 1.67 2 54.92 1.67
55.25 1.66 3 55.05 1,67
55.55 1.65 1 55.70 1.65
55.92 1.64 1 56.19 1.64
56.69 1.62 1 56.55 1,63
56.90 1.62 ~1
57.19 1.61 58'25 1 6518
59.04 1,56 1 58.96 1.57
- 17 -
.
:, , , :~
In the rollowing Examples (i.e. Examples 2-8) x-ray
diffraction pattern for the catalytic form of the respecti~e
.-~a.erials is shown ~n .he table followlng t;~e Example.
EXAMPLE 2
- Same as Example 1 with the e~ception that 5 gm o~
RuC13.3~20 and 35 gm of HCl were used in place o~ the chromium
compound and the sul~urlc acid.
X-ray dlr~raction patterns for this material show
subs~antially all the characterlstic lines for the ZSM-5
zeolites as shown in Table 1. As in the ~irst e~ample, treat-
ments of the zeolltes o~ this and the six following examples
byi~n~exchange~ thermal conditlonln~ or other treatments lead
to slmilar ~inor varlations in lnterplanar spacings, lattice
symmetry, and relative lntensity.
- 15 . TABLE 4
d(A) ~sO
7.90 11.2 100
8.79 lo.0 57
9.07 9.7 11
9.81 9.0
10.95 8.08
11.8~ 7.46
: 12.4~ 7.0g
13.20 6.71 8
13.90 6.3t11
4.75 6.0118
14.92 5.94 3
ls.52 5.71 9
: ~5.88 5.5812
16.50 5.37 3
17.27 5.13 3
1~.61 5.04 5
17.81 4.~8 6
18.1S 4.89
18.83 4.71
19.23 4.62 4
19.87 4.47
20.35 4.36
20.84 4.25 8
21.79 4.08 2
22.18 4.01 3
il27134
TABLE 4 CONTD~
23 . 083 . 85 66
- 23.28 3.8232
23 . 6s3 . 76 16
23.92 3 . 72 36
24.29 3.66 9
24.53 3.63 9
24.78 3.59 3
24.54 3.49 3
25.85 3.45 5
26.18 3.40 2
26.52 3.36 4
26.92 3.31 6
2~.38 3.26 3
27.63 3.23
28.04 3.18 7
28.43 3.14 2
29.22 ~.06 2
29.30 3.05 2
29.87 2.99 9
30.20 2.96 6
30.55 2.93
31.23 2.86 2
31.55 2.84 a
32.15 2.~8
32.?~3 2.?4~ 2
33.37 2.69
33.75 2.66
~ ~ .
, 34.30 2.61 2
34.60 2.59 2
35.04 2.56 6
35.63 2.52 2
36 09 2.49 3
'36 33 2.47 2
36.60 2.46
37.18 2.42 2
37.54 2.40 2
:
--19 --
~Z~34
~ABLE 4 CON~D.
2~ t " I/
40.99 2.20
41.45 2.18
41.73 2.16
42.50 2.13<1
- 42.88 2.11
43.14 2.10` ` 1
43.53 2.08 -1
45.04 2.~1 7
4S.52 1.99 5
46.48 1.95 2
47.40 1.92 2
48.47 1.88 2
48.83 1.86
49.50 1 . 84
49.83 1.83
;50.23 1.82<1
-go 1.7S <1
51.24 1.78
51.74 1.77
52.05 1.76
52.33 1.75
53.15 1.72 - <1
53.65 1.7t <1
54.30 1.6~ 3
~54.98 1.67 3
55.30 1.66
55.75 1.65
`56.05 1.64 <1
56.55 1.63
57.20 1.61
; 59.03 1.56
- 20 -
llZ7134
EXAMæLE 3
S-ame as Example 1 except that 2 gm of H2PtC16.nH20
was used instead of the chromium compound. Also 35 gm of HCl
replaced the H2S04.
TABLE 5
2e - d(A~ / o
7.90 11.2 100
8.80 10.0 60
9.10 9.7 14
9.85 9.0 2
11.02 8.03
11.92 7.42 2
12.53 7.06
13.23 6.69 8
13.93 6.3612
14.77 6.0018
15.04 5.89 3
15.54 5.7010
15.89 5.5~313
16.54 5.36 4
17.27 5.13 2
17.58 5.04 5
17.80 4.98 6
18.20 4.87
18.80 4.72
19.25 4.61 5
19.90 4.46 2
; 20.37 4.36 7
20.85 4.2610
21.80 4.08 3
22.21 4.00 5
22.50 3.95 3
23.10 3.8565
23.34 3.8135
23.72 3.7522
23.95 3.7239
24.33 3.6614
24.57 3.6213
24.86 3.58 3
25.53 3.49 3
25.87 3.44 6
26.13 3.41 3
26.57 3.35 5
26.97 3.31 8
27.42 3.25 4
27.62 3.23
28.08 3.18
28.44 3.14
X
1127~34
~ E C ~
29.17 3.06 2
29.40 3.04 4
29.90 2.99 13
30.22 2.96 7
30.55 2.93 1
31.23 2.86 2
31.58 2.83
32 lS 2 ~8
32 79 2 73 3
33.47 2.68
33.79 2.65
.
34.37 2.61 2
34 67 2 59 2
35 05 2 56 2
35.70 2.52 3
36.12 2.49 4
36.25 2.48 2
36.~0 2.45
37.23 2.42 2
37 56 2 39 3
38 25 2 35
38.72 2.33
39.20 2.30
39 ~5 2 2~ 2
40 30 2 24
40.62 2.22
41.03 2.20
41.48 2.18
41.81 2.16
42.50 2.`13 <1
42.95 2.11
43.20 2.10
43.53 2.08
45 13 2.01 a
45 60 1.99
46.13 1.97 2
46.55 1.95 3
47.45 1.92 2
48.51 1.88 2
48.83 1.86 2
49.55 l.B4
49.85 1.63
50.20 l.a2 ~1
so.a8 l.~o <1
51.18 1.7~ <1
51.70 1.77 <1
51.98 1.76
52.27 1.75
53.25 1.72 <1
53.63 1.71 <1
- 22 -
;
:
1127134
~ ~ ~ 5 C Gt~TI~ .
-
2a ~L / c
54 . 93 1 . 67 3
55 . 18 1 . 66 2
55.65 1.65
55.93 1.64 <1
56.50 1.6~ 1
56.90 1.6.2 <1
S~.20 1.61
58.30 1.58 a
58.98 1.5 7
; ~
:: ~
23
.
. . ...
EXAMPLE` 4
Same as Example 1 except 6~3 gm of In2(S04~3 was used
in place of the chromium potassium sulfate.
TAB~E 6
2e d~A) I/Io
7.90 11.2 100
8.80 10.0 41
9.05 9.8 13
9.85 9.0
10.98 8.06
11.85 7.47
12.50 7.08
13.22 6.70 8
13.92 6.36 12
14.75 6.01 13
14.90 5.95 2
15.53 5.71 8
15.91 5.57 11
16.52 5.37 3
17.25 5.14 2
17.63 5.03 4
17.82 4.98 5
18.18 4.88
18.83 4.71
19.27 4.61 4
19.93 4.45
20.40 4.35 6
20.88 4.25 8
: ~
21.83 4.07 2
22.22 4.00 4
23.10 3.85 75
23.30 3.82 40
23.68 3.76 17
23.95 3.72 30
24 30 3.66 8
24 55 3.63 8
25.57 3.48 2
25.90 3.44 5
26~22 3.40 2
26.57 3.35 4
26.97 3.31 7
27.40 3.26 3
; 27.65 3.23
28.08 3.18
28.45 3.14
~,,
:`
~` 24
~:
'
X~
,
:: ::
~,
1~27~34
md~LE ~, A?l`!LD `
29.23 3.06 2
29.33 3.05 2
29.90 2.99 8
30.18 2.96 5
30.50 2.93
31.25 2.86 2
31.53 2.84
32.1~ 2.~8
32.~8 2.~3 2
33.43 2.68
33.73 2.66
.:
34.33 2.61 2
34.60 2.59
35.10 2.56
35.68 2.52 2
36.10 2.49 3
36 30 2.47
36 62 2.45
.:
~ 3~.24 2.41 2
; ~ 3~.57 2.39 2
. .
, -
,~
-- 25 --
' . ' . ' :
.
1127~34
Co,~`,Tr .
29
40.50 2.23 <
41.03 2.20
41.50 2.18
41.80 2.16 <1
42.50 2.13
42.95 2.
43.25 2.10
43.63 2.07
45.05 2.01 5
45.53 1.99 4
46.53 l.9S 2
47.47 1.92 2
48.50 1.8~ 2
48.88 1.86
49.53 1.84
49.90 1.83
50.38 1.81 <1
50.90 1.~9 <1
51.29 1.7a <1
51.75 1.77
52.03 1.76
52.37 1.75
53.20 1.72 a
53.65 1.7~ <
54.20 1.69 <1
S4.g9 1.67 2
55.30 1.66
55.75 1.6
56.10 1.6
56.60 1.63
57.20 1.61
58.35 1.58 <1
59.08 1.56
_ 2~ -
i 127134
.
.
EXA~PLE 5
Same as Example 1 except that 5,8 gm of Ce(S04~2 plus
3.7 o. A12(S04)3.14X20 were used~ 'ne former to repl~ce ~he
chromium compound.
TA~LE 7
29 drAl _ `
7.91 11.2 100
8.83 10.0 60
9.10 9.7 21
9.80 9.0 2
11.02 8.03
ll.gl 7.43 2
12.50 ~.08
13.23 6.69 15
13.92 6.36 17
14.80 5.9920
15.03 5.89 4
15.55 5.7012
15.93 5.5614
16.54 5.36 4
17.30 5.13 3
17.68 5.02 5
~.86 4.97 9
18.22 4.8~ 1
18.85 4.71
19.38 4.58 6
19.93 4.45 2
20.40 4.3510
20.88 4.2513
21.80 4.08 4
22.19 4.01 7
22.60 3.93 3
23.09 3 8582
23.33 3 8138
23.70 3.7524
23.98 3.7147
24.35 3.6614
24.58 3.6213
24.85 3.58 3
25.59 3.48 3
25.91 3.44 8
'
~127134
m.~ E 7 ~ T3 ~
26.34 3.38 3
26.60 3.35 5
26.98 3.30 11
27.42 3.2~ 4
27.58 3.23
28.12 3.17 2
28.47 3.14 2
29.23 3.05 5
29.43 3.04 5
29.92 2.99 15
30.25 2.95 8
30.54 2. g3 2
31.25 2.86 3
31.60 2.83
32.19 2.7~ 2
-32.79 2.73 4
_ _ _
33.42 2.68 2
33.74 2.66 2
33.99 2.64 }
34.37 2.61 3
34.68 2.59 2
35.13 2.55 2
35.71 2.51 3
36.12 2.49 5
36.33 2.47 3
36.64 2.45
37.20 2.42 3
37,56 2.39 3
38.32 2.35
38.77 2.32
',
,~
2 ~ -
:,
~Z71;~4
- 3 __ C ~ ~3 ~
29 d ( ~ )
40.54 2.23
41.03 2.2~ 1
41.47 2.18
42.54 2.13
42.93 2.11 2
43.58 2.08
45.11 2.01 9
4S.58 1.99 9
46.03 1.97
46.55 1.95 3
47.49 1.92 3
48.51 1.88 2
48.88 1.86 2
49.50 1.84
49.98 1.82
50.37 1.81
50.88 l.~o
51.30 1.7~ 1
51.71 1.77
52.00 1.76
52.33 1.75
.
54.93 1.67 2
55.i8 1.66 2
~ 55.55 1.65
- 55.82 1.65
56.S5 1.63 <1
56.98 1.62 <1
~ 57.25 1.61 a
`` ~ 58.35 1.58 <1
~ 59.00 1.57
, .
:`
- 29 -
1127134
EX~MP~E 6
Same as Example 1 except that 2~23 gm of V205 was used
in place of the chromium compo~nd.
TABLE 8
_Z~ ~(A~ /Io
` 7.85 11.3 100
8_76 10.1 55
9.03 9.8 14
9.75 9.1 2
10.908.12
11.807.50
12.477.10
13.236.69 7
13.856.39 9
14.716.02 17
15.005.91 3
15.485.72 7
15.835.60 11
16.485.38 3
17.205.16 2
17.555.05 5
17.764.99 5
18.104.90
18.804.72
19.204.62 4
19.904.46
20.304.37 6
20.794.27 7
21.714.09 2
22.134.02 3
22.493.95 2
23.023.86 60
23.253.83 31
23.623.77 14
23.883.73 34
24.233.67 8
24.473.64 8
24.723.60 2
25.503.49 3
25.803.45 5
~'
.,'
~.
.~
,,
,
.
: ~r
~,
, . :
~1~27134
I''BLE ~ 5C`~?~.
25. 13 3 .41 2
26.51 3.36 S
26.88 3.32 6
27.33 3.26 2
27.58 3.23
28.09 3.18
28.38 3.14
29.13 3.06 4
29.33 3.05 3
29.82 2.99 10
30.11 2.97 7
30.47 2.93
31.1S 2.87
31.63 2.83
32.19 2.78
32.~1 2.74 2
33.36 2.69
33.69 2.66
33.92 2.64 2
34.30 2.61
34.59 2.59 2
35.00 2.56 2
35.63 2.52 2
36.00 2.49 3
36.23 2.48 2
36.61 2.45
:
:
` 3~.18 2.42 2
` 3~.50 2.40 2
38.20 2.36
38.65 2.33
'~
- 31
~13~
.. .. ..
23 d ( A)
40.43 2.23
40.97 2.20
41.40 2.18
41.72 2.16
- 42.50 2.13<1
42.8s 2.11
43.20 2. lo
43.61 2.08
4s .02 2.016
45.48 l . gS 5
4s .92 1.9~1
46.44 1.96
47.35 1.92 2
48.43 l.B8
48.80 1.87
49.s2 1.84<1
49.82 1.83
` 50.20 l.a~<1
50.90 1.~9<1
51.24 1.78C
51.62 1.77
- 51.93 1.76
52.20 1.75
` 53.25 1.72<1
53.65 1.~11
54.9B 1.673
55.25 1.66
` ss.so 1.66
" ss.~5 1.65
6.5s 1.63
56.90 1.6<~
` s7.22 1.61
; s8.45 1.58<1
-- 59.00 1.57
,
. .
~ :'
., .
~, ~
,,
~,
~.,
_ 3~ ~
~127~;~4
EXAMPLE 7
Same as Example 1 except that 1.5 gm of Zn2B6011 and
25 gm of tetraet~ylammonium bromide were used to replace the
chromium compound and the tetrapropylammonium bromide, respectiv-
ely.
TABLE 9
2e d~A) I/Io
7.91 11.2 100
8.78 10.1 54
: 9.05 9.8 17
9.80 9.0
10.97 8.07
11.85 7.47
12.47 7.10 <1
13.18 6.72 4
13.92 6.36 6
14.74 6.01 10
14.95 5.93
15 50 5.72 4
15 87 5~58
16.42 5.40
16.59 5.34
17.25 5.14
17.60 5.04 3
17.80 4.98 3
18.15 4.89
18.80 4.72
19.21 4.62 2
19 80 4 48 4
:~ : 20 33 4 37 3
~; 20.83 4.26 5
33
~27134
~ 3 _ _ _ _ _
21.74 4.09
22.23 4.00 2
22.58 3.94
23.05 3.86 77
23.30 3.82 23
23.70 ~ .75 14
23.94 3.72 36
24.32 3.66 10
24.53 3.63 10
24.75 3.60 3-
25.50 3.49 5
25.76 3.46 5
25.92 3.44 5
26.18 3.40 2
26.53 3.36 5
26.94 3.31 5
27.37 3.26 3
2~.58 3.23
28.08 3.18
28.33 3.15 3
28.53 3.13
29.18 3.06 5
29.36 3.04 5
29.87 2.99 13
30.18 2.96 6
30.53 2.93
31.18 2.87 2
31.43 2.85
31.70 2.82
32.10 2.79
32.73 2. ~4 3
. ~ ~
. !
.
:
;'
-- 34 --
~lZ7~34
. ~ ., g C ~ .
d ( A ) / o
33 . 3a 2 . 6a 1 -
33.72 2.~6
33.92 2.64
34. 30 2.612
34.55 2.60 2
SS.05 2.56 2
35.64 2.52 3
36.08 2.49 3
36.28 2.48
36.55 2.46
36.?9 2.44
37.17 2.42 2
37.38 2.41
37.58 2.3g
38.20 2.36
38.63 2.33
38.83 2.32
39.17 2.30
40.38 2.23
40.58 2.22
41.02 2.20
41. 37 2.18
41.65 2.17
42.43 2.13
42.82 2.11
43.11 2.10
43.53 2.08
45.02 2.018
45.53 1.99S
45.95 1.9~1
46.39 1.9b
46.65 1.95
49.90 1.83
50.30 1.81~1
50.95 1.?9
51 2B 1.78
Sl ~0 1.77
5~.95 1.76
52.26 1.75
~4.92 1.67 4
55.13 1.67 2
55.73 1.6S
56.52 1.63
56.61 1.62
57.25 1.6)
58.40 1.58
59.03 1.56
~127134
EXAMPLE 8
Same as Example 1, but usiny 3~97 gm of molybdic acid
~H2MoO4~ to replace the chr~mium compound.
TABLE 10
2e d(A~ / o
7.90 11.2 100
8.79 10.1 55
9.10 9.7 12
9.83 9.0
11.02 a.03
11.80 7.50
12.50 7.08
13.20 6.71 7
13.90 6.3710
14.78 5.9917
15.08 5.87 2
15.52 5.71 7
15.90 5.5711
16.50 5.37 3
17.25 5.14 2
17.60 5.04 5
17.82 4.98 5
18.13 4.89
i 18.90 4.70
i 19.22 4.62 4
19.87 4.47
20.38 4.36 7
20.83 4.26 7
21.25 4.18
21.78 4.08 3
22.17 4.01 4
22.69 3.92 3
23.07 3.8657
23.35 3.8125
23.68 3.7617
23.92 3.7234
24.30 3.6611
24.51 3.6310
24.77 3.59 4
25.53 3.~7 4
25.79 3T45 5
.~
~.
1~27134
_ 10 ''O~Tr_.
2S.203.40 3
26 573.35 4
26.913.31 6
27.373.26 3
27.693.22
28.103.1a
2a.393.14
29.203.06 3
29.413.04 3
29.882.99 10
30.182.96 5
30.522.93
31.212.87
31.602.83 <1
32.1~2.78
32.~72.73 2
33.42 2.68
33.72 2.66
34.32 2.6~ 2
34.68 2.59
35.07 2.56 2
35.67 2.52 2
36.08 2.49 3
36.33 2.47 2
36.65 2.45
3~.20 2.42 2
3?.55 2.40 <1
38.32 2.35
38.63 2.33 ~1
39.26 2.29 2
40.50 2.23
40.g3 2.20
41.25 2.19
41.60 2.17
42.51 2.13 <1
42.gO 2.11 <1
43.20 2.10
43 57 2 oa
45 07 2 01 6
45.53 1.99 5
46.50 1.95 2
.~, ..... .
,
- llZ7134
2~
47.48 l .9Z 2
48.53 1.88 2
48.89 1.86
49.62 1.84
49.97 1.82
50.35 1.81 <1
50.90 1.79 a
51.33 1.78 <1
51.61 1.~7
Sl.90 1.76
52.27 1.75
53.35 1.~2 <1
53.68 1.~ <1
54.25 1.69
54.92 1.6~ 2
55.20 1.66 2
55.~3 1.65
56.10 1.6~ <1
56.55 1.63
56.85 1.62 <1
57.25 1.61 a
58.45 1.58 a
59.09 1.56 a
~:
- 38 -
llZ7~34
EXAMPLE g
This wzs ~.ace si . ~ l e-ly t~ -x2:~01~ 1, e~cseo~, t"a~
5 gm of silver acetate replaced the chromium compound~ The
x-ray analysis showed it to have a pattern similar to the
prevlous Examples.
EXAMPLE 10
Thls was made as shown ln Example 1 except that
~` 35 gm of HC1 was used instead o~ sul~uric acid and 5 gm o~ HgC12
was used instead o~ the chromium compound. The x-ray analysis
showed it to have a pattern similar to the previous Examples.
EXAMPLE 11
This was also made like Example 1, except that 5 gm of
H6TeO6was used instead o~ the chromium compound. The x-ray
analysis showed it to have a pattern similar to the previous
Examples.
Employing the catalyst o~ this invention containing
a hydrogenation component, heavy petroleum residual stocks,
cycle stocks, and other hydrocrackable charge stocks can be
hydrocracked at temperatures between 400F and ~25F using
2Q molar ratios of hydrogen to hydrocarbon charge in the ran~e
between 2 and 80. The pressure employed wlll vary between 10
and 2,500 psig and the liquid hourly space velocity between
0.1 and 10.
Employing the catalyst of this invention ~or catalytic
cracking, hydrocarbon crackin~ stocks can be cracked at a liquid
hourly space velocity between about 0.5 and 50, a temperzture
between about 550F and 1100F, a pressure between about sub-
atmospherlc ~nd sever_l hur.dred atmospheres.
- 39 ~
1127134
Employing a catalytically active form of the zeolites
of this invention cont~ining a hydrogenation component, reform-
ing stocks can ~e reformed employing a temperature between 700F
and 1000F. The pressure can be ~etween lOO and 1000 psig, but
is preferably between 200 and 700 psig. The liquid hourly space
velocity is generally between 0,1 and lO, preferably between
0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally
between 1 and 20, preferably between 4 and 12.
The catalyst can also be used for hydroisomerization of
normal paraf~ins, when provided with a hydrogenation component,
e.g. platinum. Hydroisomerization is carried out at a temperature
between 200 and 700F, preferably 300 to 550F, with a liquid
hourly space velocity between 0.01 and 2, preferably between 0.25
and 0.50 employing hydrogen such that the hydrogen to hydrocarbon
mole ratio is between l:l and 5:1. Additionally, the catalyst
can be used for olefin isomerization employing temperatures
between 30F and 500F. and for methanol and dimethylether
conversion.
Other reactions which can be accomplished employing the
catalyst of this invention containing a metal, e.g. platinum
include hydrogenation-dehydrogenation reactions and desulfuriza-
tion and hydrocarbon oxidation reactions.
The products were tested in several o~ the conversion
processes mentioned above. The result follow:
EVALUATION OF PRODUCTS
_ .
Toluene DisProportionation
Table 11 summarizes data obtained using various samples
of the hydrogen form of the zeolite in toluene conversion. The
runs were made at 600 psig, 3~5 WHSV and a H2-hydrocarbon (H2/HC)
ratiO of 2/l, except where different conditions are noted. The
hydrogen form was obtained by the procedure of Example 1.
~lZ7134
.
TA3LE ,1
?letal Used in T;lt. ,; Tolusne
Synthesis_ Temp., FConve~sion _
Pt (Example 2) 850 31.8
5 V (Example 6) goo 14.0
Mo ~Example 8~ 900 14.7
; Cr (Example 1) 1100 (10 WHSV) 16.9
- Hydrocracking
Table12 shows the results obtained in convertinC
; 10 224F - 365F Buffalo Naphtha using the hydrogen form of the
zeolite at 900 and 1000F. Conversion was at 100 psig,
5 ~HSV and a H2~HC o~ 3/1. The naphtha had the characteristics
shown in the table. The hydrogen form of the zeolite was
obtained as per the description hereinabove.
~;
.
~ 41 -
~127~1 34
.
a~
u~ O L~
C~
.,, . oo,, o
~ :~ ~Itr~ ~ 3
Eo~ O
~' ~ ~ ~ ~ CO '
: V O
I V 1~ ~O~D 3
_I
` .
.. . . ..
~S~ .
~dS
2~V
~ I
C~ ~
rl 0 50 ~J
J~ O .-1 ~1
~0
~1 . '
~ O
~q
) ~a~
V
I ~ I N
~ r-l
::: 3 V
~ ~ .
*. ~e
~: P tn o L~
O t--~ U~ ~ ~
:: Ir~ 3 ~1, ~1 3
.~
. ~ ~
O O O O Z c~ O
. ~ ~ O O O o o O O O ~ ~i ~ O~
E~ ,~1 ~
u~ m .
~_1 ~ a~ a~
O ~ ~
u~ S LS~ ~) ~ h
D ~ ~0 U~ h ¢
¢ + +
:~ ~ ~V H O ~O ~ O C~
C~J
4 -- -- .
.. .
"~
. .
~12'7134
Reaction of Methanol
Yaporized methanol was passed over the hydrogen form
of the zeolite prepared using platinum~ The conditions and
results are shown in Table 13.
,
` :~
~;
::
43
,
'
llZ7134
.
.
o a~
o o a~
C) ,,
,, .
~,,
X~
I U~ 5 l~
Il
C~
~1 ~
O
' ~
:~ , a.
~` 3~1 5 t_ .
: , ¢
, ~ + I O ~
5 a-
,V
,':
O
~ o ~n ,
~ ~ U~
+
0 0~ O ~ '
C
'' : ,
:' ~ ' ~ I
U~ I~
. '~ IL~
~ ~1 ~
:, . ~ ~ O
t_
.
.
- 4 11 -
1~27134
Xylene Isomerization
The same zeolite used for the test su~m2rized in
Table ~ was tested for xylene isomeriza~ion activity. Table
14 summarizes the conditiol~s and results.
~ -~AB~E 14
680F, 200 psig, 5 ~SV And 4/1 H~/HC
Fractions
Obtained ~lt. % % Xylene Charge
Cl-C5 0 . 1
Benzene 2.1 0.1
Toluene 0.2 0.1
EB 16.1 20.9
p-Xyl. 19.1 24.5 2.8
m_Xyl. 41.6 53.3 51.3
o-Xyl. 17.4 22.2 24.5
Cgl Ar 3.4 0.3
The charge set ~orth in Tablel5 was passed over the
same catalyst used as per Tables 13and 14at the conditions
speci~led. A summary of results is shown in the table.
l~Z7134
TA~LE 1
Temp, F 100ûF
PSIG 0
H2 O
WHSV
Charge -Light
Product Woodhaven
Dist ribut ion, Wt . % Re format e
Cl 3.6
C2 s .13 . 8
C3's . 19.2
C4's 4.9
Cs's 0 0.2
C6's 0.5 25.9
; 15 C~' 0.2 25.1
C6H6 11. 8 8 . 6
Cg~s 0 7.6
Tol 33 5 32 .1
CgAr 9 . 6 0 . 5
~' 20 Cg~Ar 2.9
New Aromatics Make,
g/lOOg Charge 16.6
Wt. ~ of Aromatlcs
Made/Conv . 28 . 7
'' .
- 46
