Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Field of the Invention
This invention relates to the production of a Y-type
zealot having a high silica to alumina ratio and to the
resulting unique zealot obtained
Description of the Previously Published Art
The Brook U. S. Patent No. 3,130.007 is the basic
patent on Zealot Y and it defines the zealot in terms of
moles of oxides as
0-9 + 0-2 Noah Aye w Sue x HO
where is a value greater than 3 up to about 6 and x may
be a value of up to about 9. The disclosed use for
Zealot Y is as an adsorbent.
Brook discusses two types of silica sources. When the
major source of silica is a lower cost silica source such
as sodium silicate, silica gel or silicic acid, the
zealot Y composition prepared usually has silica/alumina
(Sue) molar ratios ranging from greater than
3 up to about 3.9. Examples are given in Tables III and
IV. The lowest amount of soda used is in Range 5. By
multiplying the lowest ratio of NATO to AYE (which
is I by the lowest Sue ratio of 8, the
lowest possible NATO content is 4.8 moles which is above
line A in Figure 1 to be discussed below.
When it is desired to have zealot Y product
compositions having silica/alumina molar ratios above
about 3.9, then Brook employs as the preferable major
source of silica more expensive silica sources such as
aqueous colloidal silica sots and the reactive amorphous
solid silicas. Since these colloidal silica sots and
reactive amorphous solid silicas are expensive materials
as compared to sodium silicate, Brook does not provide any
teaching as to how to make high silica Y zealot from
lower cost reactants.
I'
V36
Brook also requires a first digestion at ambient or
room temperature. The criticality of this cold aging for
all the production processes is shown in Table V.
The Essay Great Britain Patent No. 1,044,983 discloses
maying type Y zealots having a silica to alumina ratio of
3 to 7 in which the reactants have low ratios of soda to
silica and water to silica. Like the Brook patent, the
preferred silica source and the material used in all of
the examples which are claimed to yield 5.5-6.~
Sue ratio in a well-crystallized Nay form is
a silica 501 which is an expensive material.
The McDaniel et at U. S. Patent foe discloses
the use of seeds or nucleation centers having an average
size below about 0.1 micron to produce Type Y zealots.
In Example II the resultant zealot particles are stated
to possess a silica to alumina ratio of about 5.0 to 6.0,
but no individual values are listed. The Sue to
Aye ratios vary from 9.5 to 14.5 and the amount of
NATO added is listed with the amount in each case being
greater than the amount employed in the present invention.
The Maker et at U. S. Patent No. 3,671,191 discloses
the preparation of high silica synthetic faujasite by
using seeds and a silica to alumina reactant ratio of
about 16:1. At this preferred 16:1 silica to alumina
synthesis ratio the NATO to alumina ratio shown in the
Example is 6.6~ This is identified as point G in Figure
1. Among the products produced is one having a ratio of
5.2 in Example 2 and 5.4 in Example 3.
The Elliott et at U. S. Patent 3,639,099 discloses
producing a faujasite having a silica to alumina ratio
greater than 4 by using seeds. The improvement in this
patent was to use a lower ratio of silica to alumina. A
range of 8-12 Sue to 1 AYE is disclosed with a
preferred silica to alumina ratio in the reaction slurry
of about 9:1. In that case the preferred reactant mixture
has 3.5 0.4 NATO for each AYE. The lowest level
at a 9:1 silica to alumina ratio would be 3.1 moles of
NATO. This point is identified as point F on the
figure. Among the products made from a 10 to 1 ratio in
Table 1 the lowest free NATO used was 3.5 and it
produced a zealot with a Sue ratio of only
5.47.
The Whit tam et at U. S. Patent 4,016,246 discloses the
preparation of zealot Y having a silica to alumina molar
ratio of greater than 3 up to about 6.2. The method
requires the use of an "active" sodium metasilicate
hydrate which is distinguishable from conventional sodium
metasilicates. This unique hydrate is produced by three
methods described in the patent. Since this starting raw
material is difficult to obtain because it requires
special manufacturing techniques, it would appear that
Whit tam's method is also expensive to carry out.
I The Vaughan et at US. Patent 4,178,352 discloses a
synthesis of Type Y zealot using a minimum of excess
reactants. There is a generic statement that the
resulting zealots can have a silica to alumina ratio of
from about 4 to 5.5. However, the highest product ratio
shown in the examples is in Example 6 at a ratio of 5.1.
The final reactant mixtures have for each mole of
AYE from 4 to 7.5 moles of Sue and from 1.2 to 3
NATO. Most of the examples use reactant solutions where
the silica to alumina ratio is 6 to 1 with 1.8 or 1.9
moles of NATO. Point E in the Figure represents this
technique where the silica to alumina mole ratio is 6 and
there is I moles of NATO for one mole of alumina.
-- 4
:~f~5~,36
The McDaniel US. Patent 3,574,538 discloses using
kaolin and in the preferred embodiment metakaolin and
sodium silicate in the form of water glass to prepare
faujasite materials having a silica to alumina ratio in
excess of 4.5 from inexpensive raw materials. In the
examples, products are made with the highest silica to
alumina ratios of 5.90 and 5.95. However, in industrial
practice it is difficult to obtain kaolin and/or
metakaolin that meet the desired chemical and physical
properties which optimize this process.
The Wilson Great Britain Patent No. 1,431,944
discloses making a crystalline alumino-silicate zealot
having a silica-to-alumina mole ratio in the range of 5.5
to 8Ø The method requires a series of sequential steps
for the addition of the reactants. First, a faujasite
precursor solution is formed and heated. Then, a sodium
silicate solution is added to increase the
Sue molar ratio. Next, as a critical step,
an aqueous aluminum chloride solution is added to form a
gel slurry. Additional steps require heating, removing
the gel from the slurry and adding further water to the
gel with further heating to promote crystallization. The
Wilson method does not relate to a synthesis procedure in
which all of the reactants are essentially mixed together
at the same time.
Objects of the Invention
It is an object of this invention to produce a Y type
zealot having a high silica to alumina ratio of greater
than 5Ø
It is a further object to produce a Y type zealot
having a high silica to alumina ratio, a high degree of
crystallinity and an absence of occluded silica.
36
It is a further object of this invention to obtain a
high silica Y type zealot that is made from a source of
alumina other than metakaolin or kaolin.
It is a further object of this invention to obtain a
high silica Y type zealot which can be used for catalytic
purposes by employing inexpensive silica sources such as
sodium silicate, silica gel or silicic acid.
It is a further object to lower the active soda
content in the reaction mixture to obtain a high silica Y
type zealot.
It is a further object to use an alum golfed mother
liquor from a previous synthesis as a starting material
when lowering the active soda content to make a high
silica Y zealot.
These and other objects will become apparent as the
description of the invention proceeds.
Summary of the Invention
High silica/alumina sodium Y type faujasite, SAY, is
produced by carefully controlling the active soda content
to a level below the conventionally employed amounts. The
Y type faujasite is made from a source of alumina other
than metakaolin or kaolin while the source of silica is an
inexpensive source such as sodium silicate, silica gel,
silicic acid or mixtures thereof. The soda content can
be reduced by one of two different techniques or a
combination of the two. The first involves adding a
controller of active soda such as an acid and/or an
aluminum salt solution obtained from aluminum and an acid
which reduces the amount of active sodium in the zealot
synthesis slurry. Preferred materials are a dilute acid
or a dilute aluminum sulfate solution. The other
technique involves using as a starting reactant a
combination source of reactive silica and alumina which is
low in active soda. This can be used in conjunction with
the individual source of silica and source of alumina
discussed above. A preferred combination source is a
previous mother liquor which has been treated with an
aluminum salt to obtain an aluminum salt golfed mother
liquor which is low in soda. A preferred aluminum salt
for this embodiment is aluminum sulfate which is also
known as alum.
my lowering the soda level, it is possible to produce
unique well crystallized Nay zealots with a
silca/alumina ratio of 5.0 and higher and especially at
levels of I and higher. These unique high
silica/alumina products can also be ion-exchanged with
rare earth or ammonium cations to even lower levels of
Noah to produce a more thermally and steam stable
zeolitic promoter for petroleum cracking catalysts,
petroleum hydrocracking catalysts, etc.
The Y type faujasites made by this process have a high
degree of crystallinity. When these materials are studied
by magic angle spinning nuclear magnetic resonance
(misnomer.) as discussed more fully infer, the peaks
for the Solely] and So [OAT] are sharper than comparable
commercial samples. By expressing the sharpness relative
to the Swahili] peak and multiplying by ten, a sharpness
index, SKI., is obtained The SKI. for the Solely] peak
is at least 6 and preferably at least 7 while the SKI. for
the Swahili] peak is at least about 2.2 and preferably at
least 2.5.
Brief Description of the Drawing
Fig. 1 is a graph of slurry compositions for producing
Y faujasite products in terms of ratios of Noah and
Sue to Aye.
I
Fig. 2 is the decon~oluted ASSAY NOR spectra for the
high silica Y zealot according to the present invention and for
commercial Nay
Fig. 3 is a graph of Sue ratio versus unit
cell length for high silica to alumina ratio faujasite type Nay
Thus, and in accordance with the present teachings,
there is provided a process of producing zealot Y having the
formula in terms of moles of oxides as
0-9+ 0-2 Noah Aye wish zoo
where w is a value greater than 5.0 and x may have a value of
up to about 9, comprising:
pa) forming a reaction slurry by mixing a source of
alumina other than metakaolin or kaolin;
a source of silica selected from the group consisting
of sodium silicate silica gel, silicic acid and mixtures
thereof;
a source of soda;
a source of seeds or nucleation centers; and
a further reactant which is either
(I) a controller of active soda selected from the
group consisting of an acid, a solution of a salt obtained
from aluminum and an acid, and mixtures thereof;
(II) a combination source of reactive silica and
alumina which is low in active soda; or
~III) a mixture of (I) and IT
said sources and said further reactant being selected to
control the active soda concentration in the reaction slurry,
as measured by the ratio of moles of active NATO to one
mole of AYE, below the value given by line in Figure 1
for the corresponding ratio of moles of silica to one mole of
alumina in the reaction slurry, said line being based on at
least the following points for ratios in the synthesis slurry
--8--
36
Sweeney Aye
.
Ratio Ratio' _
16~ 6:1
9:1 3.1:1
S 6:1 1.8:1
and
(b) heating the reaction slurry product of step (a)
to crystallize zealot Y.
In accordance with a further aspect of the present
teachings, a high silica, well crystallized polite Y with
little occluded amorphous silica having a formula as
crystallized in terms of moles of oxides as
ox + 0.2 Noah: Aye: wish: XH2
where w is a value greater than 5.0 in the crystalline lattice
of the zealot Y, x has a value up to about 9, and having a
sharpness index, SKI., of at least 6 for the Sill Alp peak and
at least about 2.2 for the Silo Al] peak based on the sharpness
index formula
SKI. = 10 Sweeney I
I Sue Alp
where n is O or 1 and where the sharpness, S, is defined as
S = peak area
width at 1/2 height) G
where the peak area and width are measured on deconvoluted
magic angle spinning nuclear magnetic resonance peak spectra
of silicon-29, said zealot Y having a unit cell size of 24.64
or less and having no impurities from metakaolin or kaolin.
Description of the Preferred Embodiments
... .. . _ .
The high silica/alumina sodium Y faujasites are made
from sources of alumina, silica, soda, seeds or nucleation
centers, and a further reactant which permits a reduced active
soda concentration to be present in the reaction mixture.
The more preferred sources of the alumina can ye
either alumina trihydrate, alumina MindWrite, a sodium
acuminate solution, or an aluminum sulfate (alum) solution.
-pa-
I
Other possible alumina sources could be alumina gel, aluminum
hydroxide, aluminum chloride, aluminum nitrate or other salts
of aluminum and acids. It is particularly desired not to
use kaolin or metakaolin because in industrial practice it is
difficult to obtain these two materials in a form that meets
the desired chemical and physical properties which optimize
this process.
The preferred silica sources are inexpensive sources
such as sodium silicate, silica gel, silicic acid or mixtures
of these materials. It is particularly desired for industrial
application not to use the more expensive sources of silica
such as aqueous colloidal silica sots or the more expensive
forms of reactive amorphous solid silicas. Another possible
silica source is an alum golfed mother liquor to be discussed
more below.
The preferred source of soda is obtained from the
sodium salt form of the compounds used to supply the
-8b-
V;36
silica and alumina, namely sodium silicate and sodium
acuminate. Other possible soda sources are sodium
hydroxide and sodium carbonate although it must be
remembered that the goal of this invention is to reduce
the amount of soda in the reaction mixture.
Seeds or nucleation centers can be the conventional Y
zealot seed material or the mother liquor from the
production of zealots A, X or Y or alum golfed mother
liquors. One preferred method of making the seeds is set
10 forth in the McDaniel et at US. Patent 3,808,326 and is
described in Example 1 below.
The further reactant which permits a reduced active
soda concentration to be present in the reaction mixture
can be added in one of two forms or a combination of the
two. In the first form the material is considered a
controller of active soda since it will react with the
excess active soda to bind it up so that it does not
adversely affect the synthesis of the high silica Y
zealot. Examples of materials which control this active
soda concentration are acids, salts obtained from reacting
aluminum with an acid, and mixtures of these two
materials. The acid is preferably added in the dilute
form and a preferred acid is sulfuric acid. In the
preferred embodiment these added controllers of active
soda are added at the time of mixing of the slurry or they
are added within about 3 hours of the time that the slurry
has been heated to obtain the most effective results.
The other form of the further reactant is to provide a
combination source of reactive silica and alumina which is
low in active soda. This can be done by adding an
aluminum salt to the silica containing mother liquor from
a previous production to precipitate a silica/alumina
hydrogen which is low in active soda. Examples of
I
aluminum salts include aluminum sulfate, aluminum
chloride, aluminum nitrate or mixtures thereof. Aluminum
sulfate (alum) is the preferred salt. A preferred example
of this recycle technique is disclosed in the Elliott US.
Patent No. 4,164,551 where alum, which is aluminum
sulfate, is added to the filtered mother liquor to
precipitate a silica/alumina hydrogen. This hydrogen is
referred to as AGML or alum golfed mother liquor and it or
other aluminum salt golfed mother liquors can be used
directly as a starting material when making the high
silica faujasite according to the present invention.
According to this invention, the active soda content
is to be reduced below the conventionally employed
levels. Referring to Fig. 1, line A illustrates the
conventional formulations that produce a Nay faujasite
having 5.0 Sue to AYE ratio. For a reaction
slurry at point G with 16 moles of Sue for every mole
of AYE it has been traditional to have the NATO:
Allah ratio at about 6.6. For a reaction slurry at
point F with 9 moles of Sue for each mole of AYE,
the aye: AYE ratio has its lowest value at about
3.1 while for a reaction slurry at point E with 6 moles of
Sue for each mole of AYE, the NATO: AYE
ratio is about 1.7. Thus line A is based on at least the
following points for ratios in the synthesis slurry
Sue NATO : AYE
Ratio Ratio
16:1 6.6:1
9:1 3.1:1
6:1 1.8:1
According to the present invention the soda levels are
reduced to levels below line A by the addition of a
-- 10 --
SLY
controller of active soda such as an acid and/or a salt of
aluminum and an acid. This salt can be added as a
solution. The preferred forms of the acid or salt are
dilute solutions and a preferred form of the salt is a
dilute aluminum sulfate (alum) solution. In the more
preferred embodiments the active soda content is lowered
down to the levels shown in line B of the figure where for
a reaction slurry with 16 moles of Sue for each
AYE, the NATO: AYE ratio will be about 5.0
and for a reaction slurry with 3 moles of Sue for each
AYE, the NATO: AYE ratio will be about 2.4.
Using this starting composition, lay faujasites are
obtained having a 5.8-6.0 Sue to AYE ratio.
Thus line B is based on at least the following points for
ratios in the synthesis slurry
Sue NATO : OWE
Ratio Ratio
.
16:1 5.0
9:1 2.4
When adding the materials to the reactor, care must be
taken that gels are not formed which are subsequently
difficult to disperse or dissolve. When adding the
materials sequentially a preferred order is to first add
diluted sodium silicate, to next slowly add the dilute
acid with stirring, to then slowly add the dilute Sydney
acuminate with continued stirring and finally to add the
seeds. Another preferred method to speed up the addition
of the reactants is to feed the reactants in three streams
to a high speed mixer which forms a soft gel that can be
directly fed to the crystallizing reactor. One stream
I
contains sodium silicate and seeds, the ~econcl stream is a
dilute acid stream and the third stream is a dilute sodium
acuminate stream.
In another embodiment after an initial heating of the
reactant mixture, the liquid volume of the slurry can be
reduced by decanting so that the ensuing crystallization
carried out for a relatively long period of time can be
done with a significantly reduced reactant volume such as
a 2/3 reduction in volume due to the removal of the extra
liquid. The period of initial heating can vary from a
relatively short time such as about 15 minutes to longer
periods such as a day. Since the reaction is carried out
in all aqueous system, the mixture can be heated to
temperatures of about 100C without toe need for
pressurized equipment.
Vying a reaction slurry which has a ratio of 16 Sue
to 1 Aye, sodium Y type faujasites are obtained with
Sue ratios in the range of about 5.4 to about
6.0 depending on the reduced amount of active soda
present. Using a reaction slurry which has a ratio of 9
Sue to 1 AYE, sodium Y type faujasites are
obtained with Sue ratios in the range of
about 5.3 to about 5.8 depending on the reduced amount of
active soda present.
The HAY zealot, like conventional Nay type zealots,
may be ion exchanged with solutions of rare earth salts or
salts of other metals or ammonium ion salts or
combinations thereof to reduce the No ion level in the
zealot to make a thermally and hydrothermally stable
promoter for catalyst for treating petroleum fractions.
Such ion exchange may be carried out by contacting the
HAY which has a % NATO content as synthesized of about
10-15~ with a water solution of any salt mentioned above
- 12 -
~5~3~;
or one minute to 100 hours at temperatures of 0vC to
100C, filtering the mass, and washing the filter cake of
zealot. Repeated exchanges with or without calcination
of the exchange zealot may be done to reduce the No
ion content of the exchanged zealot to as low as 0.1-5
NATO depending upon the use to be made of the ion
exchanged ISSUE promoter. These ion exchange procedures
are ~ell-known to those in this art. Alternatively toe
ion exchanging can be done after the HAY promoter has
been made into a catalyst.
The high silica Y-zeolites made by this process are
believed to be unique and this is characterized by their
high degree of crystallinity as measured by the sharpness
index of their Nor spectra to be discussed below and by
the absence of occluded silica. As the Sue
ratio increases there is a change in the nature of the
chemical bonding involved. S. Remedies et at in their paper
"Ordering of Aluminum and Silicon in Synthetic
Faujasites", Nature, Vol. 292, July I 1981, at pages
228-230, report that zealots may have five types of
bonding of silicon to silicon or aluminum. These five
types of bonding are expressed in a notation which gives
the number of aluminum atoms to which the silicon is
bonded through oxygen atoms. Mach silicon is bonded to
four oxygen atoms which in turn are each bonded to silicon
or aluminum. The five types of bonding are Sue Al), Sue
Al), Sue Al), Sill Al), and Sue Al). Thus, when silicon
is bonded through the four oxygen atoms to four aluminum
atoms, the notation is Sue Al). See also Klinowski et at
"A Reexamination of Sisal Ordering in Zealots Nix and
Nay in J. Chum. So., Faraday Trans. 2, 78, 1025-1050
(1982).
- 13 -
~5~3~
The Remedies et at authors identified the five types ox
bonding by the use of nuclear magnetic resonance. In
Table 1 below is the distribution of the five types of
bonds for a conventional Nay having a Sue
ratio of 4.8 and the theoretical distribution for a
HSAY-type material with a Sue ratio of 6-0-
For comparison, the table also lists the idealized
possible boning for Nix type faujasite.
Table 1
Type of Faujasite
Nix Nay HAY
Swahili Ratio 2.4 4.8 6.0
Bonding Distribution (Idealized)
Sly Al) 16 0 0
Sue Al) 8 4 0
Sue Al) 0 16 16
Sill Al) 0 12 16
Sue Al) 2 2 4
The HAY type material when made according to the
present invention has more Sill Al) and Sue Al) bonds
than conventional Nay zealot and less Sly Al) bonds.
To measure these 5 types of bonding experimentally, a
high resolution Sue NO spectra is obtained as
illustrated in Figure 3 of the Remedies et at article and a
computer-sim~lated curve is generated based on Gaussian
peak shapes. The area under the curves represents the
relative populations of the five puzzle ordering modes.
14 -
This new analytical technique has also been used to
determine the actual Sue ratio in the crystal
lattice, to identify occluded silica if present, and to
determine how well crystallized is the sample. The
technique uses Nuclear Magnetic Resonance (NOR) spectra of
silicon-29, which is an isotope of silicon present to the
extent of 4.7% of all the silicon atoms. The spectra are
obtained at 79.45 MHz using magic angle spinning (MA)
which is a technique that greatly improves the resolution
of the NOR spectra. Two samples of HAY labeled and B
made by the present invention and a commercial sample of
Nay made by the process taught by US. Patent 3,639,099
were studied by this NOR technique using MAST Sample A
was made by the process similar to the one set forth in
Example 15 infer and Sample B was made by the process
similar to the one set forth in Example 5. The NOR
results showed the HAY has a Sue ratio in
the lattice of 5.6 0.4, that it had no occluded silica,
and that it was very well crystallized. For the purposes
of this case, the Sue ratio will be
determined by the conventional wet chemical method. The
ratio as determined by NOR data has been given because
that value is strictly in terms of the amounts of silica
and alumina in the crystalline structure. If there is any
occluded silica present, it will not be included in the
ratio determined by NOR. However, the NOR data is less
precise as seen by the greater uncertainty for the values
as repotted in Table 2.
The MA spectra were obtained at 79.45 MHz and
referenced to tetramethyl Solon using external HODS
(hexamethyl disiloxane) reference standard and assuming
HODS = -I 6.7 Pam with respect to TAMS
(tetramethylsilane). The spectra show five peaks
- 15 -
~56~6
characteristic of the five possible environments possible
for tetrahedral framework silicon in eta structures as
indicated on the spectra shown in Figure 2. The scale in
Fig. 2 is relative to TO with the peak for TAMS occurring
at zero.
The spectra were deconvoluted into the separate
components assuming that these were Gaussian in nature.
The complete assignment of the spectrum is given in Table
2 below together with the peak areas corrected for the
small differential effects of sideband corrections. These
small differences in the shift values in the Table,
compared to those on the spectrum, are due to the overlap
between the peaks. The areas of each peak were adjusted
so that the sum of the areas of the five peaks equaled
100. The width, w, of each peak at 1/2 peak height was
also calculated. The Sill Alp and Silt Al] peaks of the
HAY sample in Figure 2 are sharper than the comparable
peaks of the commercial Nay This sharpness can be
defined mathematically as follows. If the area of the
Sue Al] peak of each Y sample is used as a reference, a
dimensionless sharpness factor, S, for each peak is
defined as
S = peak area
(width at 1/2 height) we
Then the sharpness index, SKI., of each peak other than5 the Sue Al] peak can be defined as
SKI. = 10 Sweeney Al]
S
Sue Al]
These values for n-0 and 1 are set forth in Table 2
below.
- 16 -
36
Tab e 2
Commercial HAY
Sample_ A B
Sue Ratio
By NOR 5.2+0.4 5.6+0.4 6.0-~0.4
By Chemical Analysis 5.0+0.1 5.9+0.1 6.0+0.1
Peak Types
Sue Al)
Area, A 36.0 34.5 33.7
Width, w, at 1/2 Height 3.1 3.35 3.;2
Sharpness, A/w 3.75 3.07 3.29
Sill Alp
Area, A 42.4 47.5 47.1
Width, w, at 1/2 Height 5.1 4.6 4.0
Sharpness, A/w 1.63 2.24 2.94
Sharpness Index* 4.3 7.3 8.9
Sue Al)
Area, A 9.0 9.3 13.6
Width, w, at 1/2 Height 3.6 2.8 4.0
Sharpness, A/w 0.69 1.19 0.85
Sharpness Index* 1.8 3.9 2.6
*Sharpness Index = Sharpness of Sill Al) or Sue Al)
peak x 10/sharpness of Sue Al) peak.
-- 17 --
3g~
The data in Table 2 shows that the HAY Sill Al] and
Sue Al] peaks are much sharper than the same peaks of
commercial Nay The So [l Al] peak has a sharpness index,
SKI., of at least 6 and preferably at least 7 while the So
[0 Al] peak has a SKI. of about 2.2 and preferably at
least 2.5. This sharpness of the Sill Al] and Sue Al]
peaks of the present HAY demonstrates the high
Sue ratio of the HAY crystal lattice and the
high degree of crystallinity of the HAY.
lo As discussed above the magic angle NOR spectra can
indicate if occluded silica is present since there will be
a characteristic separate peak for silica which is
characterized by silicon atoms that are only bonded to
oxygen atoms where the oxygen atoms are not further bonder
to any other atoms than silicon.
The presence of occluded silica can also be determine
from unit cell length data. E. Dempsey et at, in the
Journal of Physical Chemistry, 73 (2), 387-390, (1969)
compared the chemical analysis versus the unit cell length
of various samples of Nix and Nay faujasite. They found
that the lowest unit cell length among their samples of
Nay was 24.66 A for a Nay which has a Swahili of
5.32 by chemical analysis. However, their plot of unit
cell length versus number of aluminum atoms per unit cell
(Figure l in their paper) shows the lowest number of
aluminum atoms per unit cell is 53, corresponding to cell
size or unit cell length of AYE where A is Angstrom
units. Although they examined several other Nay samples
where the chemical analysis indicated ratios of up to
5.83, none of the Nay samples had a unit cell smaller in
length than AYE. Therefore they suggest the high
Swahili ratio samples contain amorphous silica.
- 18 -
5~3~i
If a Nay sample contains amorphous silica intimately
mixed with the crystalline Nay the apparent ratio by bulk
chemical analysis will be higher than the actual ratio in
the crystalline lattice. Their data, taken from their
Table Issue been plotted in Figure 3 as unit cell size
versus Sue ratio. The open squares in figure
3 show their data for well-crystallized samples of Nay
the unit cell length is inversely proportional to the
Sue ratio. The triangles in Figure 3
demonstrate that the Nay samples which had a high ratio by
chemical analysis do not show a progressive cell length
shrinkage with increasing ratio; these samples plotted as
triangles probably contain occluded, amorphous silica.
For these high ratio samples the cell length remains at
15 24.66 - AYE even though the ratio increases from So to
5.8. One concludes that the highest ratio in the
crystalline lattice of the Nay samples which they studied
was about 5.3. The solid squares in Figure 3 are a plot
of unit cell length versus Sue ratio for high
silica/alumina ratio faujasite type Nay of the resent
invention. The solid squares appear to be generally an
extension of the open squares and demonstrate that HAY
samples of the present invention have a unit cell length
proportional to the Sue ratio obtained by
chemical analysis. The solid squares continue down to a
unit cell length of AYE corresponding to a ratio of
6Ø Therefore the HAY samples of the present inventive
do not contain occluded, amorphous silica intimately mixed
with the faujasite. Moreover, the ratio obtained by
I chemical analysis of each sample is indeed the actual
Sue ratio in the crystal lattice.
The unique high silica Y-zeolites made by the present
invention with its high degree of crystallinity and
- 19 -
Jo
Jo
..., ,.
absence of occluded silica is very useful as a catalyst
material. These catalysts can be made using procedures
set forth in the prior art. The HAY is ion exchanged to
lower the alkali metal content and to add stabilizing,
catalytically active ions. Typically, the HAY is
exchanged with rare earth ions and/or ammonium and
hydrogen ions. The HAY may be ion exchanged either
before or subsequent to inclusion in an inorganic oxide
matrix. Furthermore, the ion exchanged HAY may be
calcined, it heated at temperatures from about 200; to
700C either prior to or after inclusion in a catalyst
matrix. Preferably, the HAY, when employed as a
hydrocarbon cracking catalyst, will possess alkali metal
content, usually expressed as soda content, NATO, of
below about 6 percent by weight.
Conversion of the HAY zealot into usable
particulate catalyst is achieved by dispersing the finely
divided HEY zealot into an inorganic oxide matrix. Tune
inorganic oxide matrix may comprise or include
silica-alumina, alumina, silica sots or hydrogels, in
combination with additives such as clay, preferably
kaolin, and other zealots, such as ZSM type zealots.
The catalyst compositions may be prepared in
accordance with the teachings of US. 3,957,689 which
comprises combining a finely divided zealot and clay with
an aqueous slurry which is spray dried and ion exchanged
to obtain a highly active hydrocarbon conversion
catalyst. Furthermore, the catalyst preparation method
may be as generally shown in Canadian 967,136 which
involves combining zealot and clay with an acid alumina
sol binder. when it is desired to obtain a catalyst which
contains a silica alumina hydrogen binder, the processing
methods of US. 3,912,619 may be utilized.
- 20 -
I
As indicated above, the HAY zealot is particularly
resistant to hydrothermal deactivation conditions normally
encountered during regeneration of cracking catalysts.
Regeneration involves high temperature oxidation (burning)
to remove accumulated carbon deposits at temperatures up
to about 1000C. Furthermore, it is found that the
catalysts which contain the HAY described herein are
particularly resistant to the deactivation effects of
contaminant metals such as nickel and vanadium which are
rapidly deposited on the catalyst during the cracking of
residual type hydrocarbons.
Chile the precise reason is not fully understood why
the HAY of the present invention and catalysts containing
the HAY described herein are particularly active and
stable, it is thought that this particularly high degree
of catalytic activity and stability after steam
deactivation and in the presence of contaminant metals is
due to its unique structure as discussed by S. Remedies, et
at in their paper "Ordering Of Aluminum And Silicon In
Synthetic Faujasites", Nature, Vol. 292, July 16, 1981,
pages 228-230.
During use, the catalytic cracking catalysts of the
present invention are combined with a hydrocarbon
feed stock which may typically comprise residual type
petroleum hydrocarbon fractions that contain up to about
1,000 parts per million nickel and vanadium and up to
about 10 weight percent sulfur, 2 weight percent
nitrogen. The cracking reaction is normally conducted at
a temperature ranging from about 200 to 600C using a
catalyst to oil ratio on the order of 1 to 30. During the
cracking reaction the catalyst typically accumulates from
about 0.5 to 10 percent carbon, which is then oxidized
during regeneration of the catalyst. It is found that
- 21 -
36
these catalysts are capable of sustaining degrees of
activity, even after accumulating up to about 4 percent
contaminating metals.
- The catalysts may be advantageously combined with
additional additives or components such as platinum, which
enhances the Cossacks characteristics of the catalyst.
Preferably, platinum is included in the overall catalyst
composition in amounts of from about 2 to 10 parts per
million. Furthermore, the catalysts may be advantageously
combined with So Kettering coJnponents such as
lanthanum/alumina composites that contain on the order of
about 20 percent by weight lanthanum oxide.
Having described the basic aspects of our invention,
the following examples are given to illustrate specific
embodiments thereon.
Example 1
This example illustrates the preparation of nucleation
centers or seeds, as disclosed in the McDaniel et at U. S.
Patent 3,808,326.
A solution of 919 g. of sodium hydroxide in 2,000 ml.
water was heated to dissolve 156 9. alumina trihydrate
(OWE OWE) and the solution was then cooled to
room temperature and designated solution A. A second
solution B was prepared by mixing 3,126 g. of 41.2 Be
sodium silicate (weight ratio 1.0 NATO: 3.22 Sue)
into 1,555 ml. water. Then solution A was mixed into
solution B with rapid stirring. The mixture was aged at
room temperature for about 24 hours and then the slurry ox
nucleation centers or seeds was ready for use.
- 22 -
Examples 2-5
These examples illustrate the production of the high
silica/alumina sodium Y type faujasite where the seeded
slurry has a silica/alumina ratio of 16:1.
The reactant solutions were prepared as follows. A
diluted acid solution was prepared by adding the various
amounts of concentrated sulfuric acid having a specific
gravity of 1.84 as listed in Table I to 100 ml. water and
the mixture was stirred well.
A dilute sodium acuminate solution was prepared by
adding 91 g. of sodium acuminate solution containing 17.2
NATO by weight and 21.8% AYE by weight to 214 g.
water.
A diluted sodium silicate solution was prepared by
pouring 648 g. of 41.2 Be sodium silicate solution having
a ratio of 1.0 Noah Sue in a on ounce blender
cup of a Hamilton Beach Blender and adding 200 ml. water
and the water was thoroughly mixed with the sodium
silicate in the blender. While the blender was mixing,
the diluted acid was added to the diluted silicate and
followed by the addition of the diluted acuminate.
Finally, I grams of seeds slurry was added to the mixture.
The slurry was poured into polypropylene bottles and
capped loosely. The bottles were heated in a water bath
until the slurry reached a temperature of 85C at which
time the bottles were transferred to an oven heated to
100C. Samples of the slurry were taken from time to time
by stirring the contents well and removing 50 ml. of the
slurry. The samples were filtered and washed to a pi of
10-10.5 and dried in an oven at lOODC.
The percent crystallinity of each sample by powder
X-rav diffraction techniques was compared to a well
crystallized, commercial sample of Nay faujasite. The
- 23 -
5~36
nitrogen surface area of the sample was measured, after
the sample was degassed at 1000F for one hour, by the
chromatographic method on a Perkin-Elmer-Shell 212D
Cytometry or by the BET method on an Amino Adsorptomat.
The unit cell size of the cubic unit cell of HAY in
which all three axes have equal length (aback) was
measured as follows. Approximately one gram of SAY
powder which had been equilibrated in a dissector
overnight in a 33~ relative humidity atmosphere was mixed
with about one gram of silicon metal powder. The silicon
served as an internal standard for an X-ray powder
diffraction pattern made using copper radiation filtered
through nickel foil. The diffraction pattern was recorded
from about 522~ to 602~. The position in degrees 2 of
the reflection from the 997 plane ho k=9, and 1=7) and
from the 999 plane was measured. The first appeared at
about 54.0-54.22~ and the second at about 58.7-58.9~2 .
The silicon internal standard has a reflection at 56.122
theoretically. The measured I for the two HAY plates
was corrected by the amount thee the silicon peak varied
from 56.12~. Then the unit cell was calculated using the
Bragg's Law equation:
a - ho+ k2+ 12
2 sin 3
where is the copper I radiation wavelength of 1.54718
A. The unit cell was the average of the a from the 997
plane and from the 999 plane.
The resulting Nay type faujasite products, descried
in Table 3 below, which were crystallized from the
slurries of Examples 2-5 had a high Sue ratio
and especially in Examples 4 and 5.
- 24 -
aye
ox
I . I 0 a
Al I a
I Jo N or
Al N N N N
o
I Al
O Q rd~,l
3 us
Jo ox
Jo h us
Jo
us by
I I owe
z on
d O
, N I I do 1`
Jo Owe o o a on
U on C)
Us o
Jo Al
O I
I
o
Al U
Us
o
Us
a o O
,, ..
O
z
I
.
Z
-- 25 --
I
Examples 6-9
These examples illustrate the production of the high
silica/alumina sodium Y type faujasite where the seeded
slurry has a silica/alumina ratio of 9:1.
The sodium silicate and sodium acuminate solutions had
the same concentrations as in Examples 2-5. The sodium
silicate and 1/2 of the water were blended in the 40 ounce
blender cup of a Hamilton Beach blender. The seeds
prepared according to Example 1 were added in the amounts
listed in Table 4 and blended. The sodium acuminate
solution was mixed with the other 1/2 of the water. The
mixture became very viscous, to the point that the mixture
gels, and the blender was turned off. The gel was
carefully and completely scraped out of the blender cup,
transferred to the bowl of a Hubert kitchen mixer. After
turning on the Hubert mixer the remainder of the sodium
acuminate solution was slowly added. Then the aluminum
sulfate (alum) solution which had 7.8~ AYE was
slowly added while mixing was continued. The thick, pasty
gel was put into 250 ml. or 500 ml. polypropylene bottles
and capped loosely. The remaining heating and analysis
procedure was the same as Examples 2-5. The resulting Nay
type faujasite products, described in Tables 4 and 5 were
crystallized prom the slurries ox Examples 6-9, and the
had a high Sue ratio, especially Examples
and 9.
- 26 -
I
Jo I
or .
run o o
I r
I m N I
o
h
a) I
.,
I I o o
rod us D I I
no I
to So m
Jo
rod m
O l
rl a sly O oil to
rod -
I m
I O
up I
I o
I I o rod rod o us
O to to o
,1 0 rn Jo n Jo
run I
Jo
aye
Pi
O I:; . UP n In
G) ~;~ us I to
a I 1-
, rJ~
m o
I .
a) I
rye O row
O O O
id Jo I I to
Z
a)
.
Z rho us
id
X
-- 27 --
~5~6
a
.,.
us or or
I
a
ox
Pi ox
a o I, I Lo
En o
on o E ", o
o
-1 o o o o
Us
TV I
d o
In Al O ED O
h O I
I
-- 2g --
I
Example 10
This example illustrates the synthesis using a reduced
volume of slurry after an initial heated reaction so that
the crystallization step which is carried out for a
relatively long period of time can be done with a
significant reduction in the volume required.
A 16:1 silica to alumina slurry was prepared having a
composition according to Example 5. The slurry was heated
in a bottle without stirring for 24 hours at 100C.
During this period the solids settled to the bottom of the
bottle. After the 24-hour heating period the mother
liquor was decanted off so there was about 2/3 reduction
in volume. The remaining solids surrounded by mother
liquor were then heated at 100C for 131 hours to obtain a
good product having a surface area of 897 mug a
crystallinity of 94% with a unit cell size of 24.59
Angstrom units. This corresponds to a Sue
ratio of 5.9. as seen in Table 3.
Example if
This example illustrates the production of the Y
zealot using a reduced volume of slurry with a shorter
period of initial heating.
A procedure similar to that used in Example lo was
followed except that instead of heating the slurry for 24
25 hours at 100C it was only heated at 100C for 15
minutes. The solids were filtered on a Buchner filter.
The solids were then returned to the bottle and only
enough mother liquor was added to just cover the solids.
Since these solids were fluffier than those produced in
Example lo a greater amount of liquor was required. The
volume reduction was about 55-60% which is slightly less
than the volume reduction obtained in Example lo
- 29 -
~2~3~i
After crystallizing the mixture at 100C for 144 hours
the product had 107~ crystallinity, the unit cell a
dimension was 24.61 angstrom units and the wet chemical
analysis of the Sue was 5.80
This example also shows obtaining a good product at
reduced crystallization volumes with the recovery of
excess mother liquor which can be recycled or used for
other purposes.
Example 12
This example also illustrates the synthesis using a
reduced volume of slurry with a slightly longer initial
period of heating.
In this example the exact procedure of Example 11 was
followed except that instead of initially heating the
slurry at 100C for 15 minutes, it was heated for 1 hour.
The solids were filtered as in the procedure of Example 11
an just enough mother liquor was added to cover the
solids. After heating at 100C for 93 hours the prevent
crystallinity ways 109~, the unit cell a dimension was
2~.60, and the Sue ratio by wet chemical
analysis was 5.8.
Example 13
This example illustrates the use of alum golfed mother
liquor, AGML, to supply some of the silica and alumina
reactant materials when using a slurry with a 16:1
silica/alumina ratio.
From a previous production of a sodium Y zealot made
by the process according to the McDaniel et at US. Patent
No. 3,639,099, the typical filtrate of mother liquor
filtered off from the fully crystallized Nay batch
contains:
4.9% Sue and
4.0~ NATO.
- 30 -
;36
Aluminum sulfate (alum) solution is added and the silica
alumina gel, AGML, precipitates and is recovered by
filtration. The gel contains:
12.6~ Sue
3.4% NATO
2.8~ AYE
2.6~ SO, and
balance water
A slurry for the synthesis of a high silica faujasite
according to the present invention was made by mixing in a
blender 300 grams AGML with 200 grams water and 517 grams
sodium silicate solution (41.2Bé containing silica and
soda in the ratio of 3.22 Sue: 1.0 NATO). Then 54
grams of sodium acuminate solution (18.2% NATO; 21.4%
AYE) which was diluted with 185 grams water was
added and mixed well. Finally 47 grams of a seed slurry
as made in Example 1 was mixed in the blender. The
effective slurry ratio was 5.2 NATO: 1.0 AYE: 16
Sue: 280 HO.
The completely mixed slurry was put into a 1.0 liter
polypropylene bottle which was placed into an oven at 100
lo After 61 hours the slurry made a well crystallized
Nay faujasite, of the high silica type according to the
present invention, having a nitrogen surface area of 952
mug This was measured on a Digisorb instrument
manufactured by Micromeritics Inc., Nor cross, GA. The
HAY faujasite had the following chemical analysis
10.7~ NATO 19.8% AYE 69.5% Sue
with a Sue ratio = 6.0 and a crystallinity of
102%.
This is an efficient use of a waste stream.
V~6
Example 14
This example illustrates the use of alum veiled mother
liquor to supply some of the silica and alumina reactant
materials when using a slurry with a 9:1 silica/alumina
ratio.
1,080 grams of AGML made as described in Example 13
was put into the bowl of a mixer and 319 grams 41.2Bé
silicate was added and mixed in the mixer. Then I grams
of sodium acuminate solution was slowly added and mixed.
The slurry became stiff, but softened after mixing for 1-2
minutes. Finally, 93 grams of seed slurry made according
to Example 1 were added. The slurry was transferred to a
1.0 liter polypropylene bottle and heated in an oven at
100+1C. The effective slurry oxide ratio was 2.4 NATO:
1.0 OWE: g Sue: 140 HO.
After 44 hours a high silica Y faujasite crystallized
which had a nitrogen surface area of 937 m go and a good
crystallinity which measured as 101~ when compared to a
commercial Nay standard. Chemical analysis of the
composition on a dry basis was as follows:
10.9% NATO 20.4% AYE 68.7% Sue
Lowe Sue ratio was 5.7.
Example 15
This example demonstrates the scale-up of the process
to a 15 gallon batch which yields nearly 6.0 kg. of dry
product.
40.0 kg. of commercial sodium silicate (Philadelphia
Quartz "N" Brand, 40.8 Be gravity) was placed into a
mixing tank and diluted with 11.5 kg. water. The mixer
was turned on and kept on throughout the addition of
chemicals. A solution of 1,531 grams concentrated
sulfuric gravity 1.84) diluted with 11.4 kg. water was
very slowly added over a 15 minute period. Mixing was
continued for 1/2 hour more
- 32 -
I
Then a diluted solution of sodium acuminate made from
5,226 grams concentrated sodium acuminate solution (18.2%
NATO; 21.4~ AYE) mixed with 5.9 kg. water was
slowly added over a 1/2 hour.
Finally, 2,631 grams seeds or nucleation centers
(described in Example 1) was added. The slurry was pumped
to a 20 gallon steam-jacketed reaction tank and heated to
100 + 1C to crystallize the Nay The slurry was sampled
from time to time to monitor the progress of the
crystallization. After 105 hours at temperature the run
was stopped. The slurry was filtered and the filter cake
washed free of excess mother liquor.
The product was a well crystallized HAY with a
Sue ratio of 6.0 and a crystallinity of 96%.
Example 16
This example demonstrates both scale-up to a 15 gallon
slurry batch and the use of another type of sodium
silicate. The mixing and crystallization procedures were
the same as in Example 13.
Mixed together were 41.5 kg. Diamond Shamrock DO 34
sodium silicate (25.6~ Sue; 6.6% NATO) and 14.6 kg.
water. A solution of 696 grams concentrated sulfuric acid
diluted with 4.5 kg. water was added. The 5,253 grams ox
sodium acuminate of the same concentration as in Example
13 diluted with 4.5 kg. water was added. Lastly, 2,192
grams seeds were added of the type described in Example 1.
The crystallization at 100 + 1C yielded HEY with a
Sue ratio of 5.3 and a crystallinity of 104%
in 72 hours.
- 33 -
1?,31 I
Example 17
This example illustrates the production ox a large
batch using the simultaneous addition of the reactants.
Three solutions were prepared. In a first tank was
added 36.7 kg. ox 41.0Bé sodium silicate, 12.2 kg. water
and 2,633 g. of seeds of the type described in Example 1.
The materials were mixed and heated to 60C.
In a second tank a dilute acid solution was prepared
by mixing 1,537 g. of concentrated sulfuric acid with
9,100 g. water.
In a third tank a dilute sodium acuminate solution was
prepared by mixing 5,232 g. of sodium acuminate (18.2
NATO and 21.4% OWE) with 6,800 g. water.
The three tanks were connected by lines to a reactor
having a high speed mixing pump and the line from the
first tank was opened first. After the three streams were
mixed by the high speed mixing pump they formed a soft gel
which was fed to a reactor with further stirring. The
reactor was closed and the gel was heated gradually to
100C while stirring continued. After the 100C
temperature was reached, the stirrer was turned off and
the mixture was maintained at this temperature for 70-80
hours to crystallize the HAY. The slurry was then
quenched with cold water and filtered with subsequent
washings with hot water. The material was dried and
yielded 6 kg. of well-crystallized HAY having a
Sue ratio of 5.9 and a percent crystallinity
as 103%. The unit cell size was 24.60 Angstrom units and
the nitrogen surface area measured by the BET method using
a Micromeritics Digisorb was 875 m. go The chemical
analysis was 11.0% NATO, 19.6~ AYE and 68.4%
Sue .
- 34 --
I
Example 18
HAY zealot was rare earth exchanged and calcined to
obtain a "CRUSOE" that comprised 14.0 percent REDO
2.45 percent NATO and a silica to alumina ratio of
5.9:1.0 by the following procedure.
A 4,444 9 portion of HAY filter cake (45% solids)
obtained in Example 17 was slurries in 9 1 of deionized
water The ISSUE slurry was then blended into a solution
of 4,444 ml commercial mixed rare earth chloride solution
(51% WRECK OWE by weight) diluted with 7.5 1 of
deionized water. The resulting mixture was heated to 90C
- 100C end held at that temperature for one hour. The
slurry was filtered and the filter cake was washed twice
with 3 1 of boiling deionized water. The washed filter
cake was slurries into a solution of 4,444 ml commercial
rare earth solution diluted with 16.5 liters of deionized
water. The mixture was again heated to 90-100C and held
at temperature for one hour. Then the slurry was filtered
and resulting filter cake was washed three times with 3 1
of boiling deionized water. The filter cake was then oven
dried at 150C for 4-8 hours. Finally, the dried zealot
was calcined at 538C for tree hours. The product
CRUSOE had the following properties:
Loss on Ignition LOWE) 2.1 wt. %
ROY 14.0 wt. %
NATO 2.5 wt. %
Ratio Sue + 0.1
Nitrogen Surface Area 768 m2/gm
(by BET method)
- 35 -
TV
Example 19
(a) The CRUSOE of Example 18 was used to prepare
a FCC catalyst according to the teachings of US.
Patent 3,957,689. An acid-alum-silica sol was made by
mixing two solutions A and B through a high speed
mixer. Solution A was 11.5 kg of 12.5% Sue sodium
silicate (NATO: 3.2 Sue). Solution B was 3.60 1
of a solution made from 20 weight percent sulfuric acid
(2.2 1) and dilute aluminum sulfate solution, 77 g
AYE per liter (1.4 liters). The ratio of the
flows of solutions A and B through the mixer is
approximately 1.5 1 solution A to 0.5 1 solution B.
The ratio of the flows is adjusted to produce an
acid-alum-silica sol having a pi of 2.9-3.2. To 14.4
kg of acid-alum-silica sol is added a slurry composed
of 2,860 g kaolin clay and 2,145 g CRUSOE from Example
18 mixed into 6 1 water. The mixture of the
acid-alum-silica sol and the slurry of CRUSOE and
kaolin in water was blended and spray dried using an
inlet temperature of 316C and an outlet temperature of
149C. 3,000 g portion of the spray dried product
was slurries in 11.3 1 of water at 60-71C and
filtered. The filter cake was washed three times with
3 1 of 3 percent ammonium sulfate solution. Then the
cake was reslurried in 9 1 of hot water, filtered, and,
finally, rinsed three times with 3 1 of hot water. The
catalyst was then oven dried at 149C.
(b) A catalyst having the same proportions of
ingredients was made in the same manner from calcined
rare earth exchanged conventional Nay having a silica
to alumina ratio of about I - 0.1
The results of comparison tests are shown below in
Table 6. The micro activity test used a modification of
the test procedure published by F. G. Ciapetta and D.
- 36 -
I
S. Henderson entitled "Micro activity Test For Cracking
Catalysts", Oil And Gas Journal, Vol. 65, pages 88-93,
October 16, 1967. Micro activity tests are routinely
used in the petroleum industry to evaluate cracking
catalysts in the laboratory. The petroleum fraction
which was cracked over these catalysts was a West Texas
Heavy Gas Oil (WTHGO) using the following test
conditions:
Temperature 499C;
Weight Hourly Space Velocity (WHSV) 16;
Catalyst to oil ratio 3.
The WTHGO (1.67g) is passed through 5.0 g of
catalyst in 1.3 minutes. The products are collected
and the percent conversion of gas oil into hydrogen,
light gases, gasoline range hydrocarbons, etc. are
determined by gas chromatography.
The catalysts were impregnated with No and V as
naphthenates dissolved in WTHGO; next the hydrocarbons
were burned off by slowly raising the temperature to
677C. Then the metals impregnated catalysts were
steam deactivated by the S-13.5 procedure before
testing for cracking micro activity.
- 37 -
TABLE 6
Catalyst Composition (wt. %) Example lo Example aye
Zealot 35 35
Sue 24 24
Clay 41 41
NATO 0.49 0~37
ROY 4.94 5.08
Aye 26.5 26.0
Microactiv-ty (Vol.% Con.) After Indicated Deactivation
S-13.5(1)
0% petals 82 86
I (Navaho)
1500(3) 81 80
1550(4) 20 I
Partial Chemical Analysis of Zealot CRY HSACREY
Swahili (Ratio) 4.9-+0.1 5.8-+0.1
ROY (Wt.%) 15.0+-1 14.0-+1
NATO (Wt.%) 3.2-+0.2 2.4-+0.2
( ) Steam deactivation: 8 hours at 732C, 100% steam at 1.1
kg/cm gauge pressure.
( ) No = V
( ) Steam deactivation: 5 hours at 816C, 100~ steam at 0
kg/cm2 gauge pressure.
( ) Steam deactivation: 5 hours at 843C, 100% steam at 0
kg/cm gauge pressure.
- 38 -
I
Example 20
(a) A slurry was made from 2,576 g HAY filter
cake (45~ solids) from a batch of HEY synthesized as
in Example 17 and 4,186 g of kaolin in I 1 of water.
This slurry was thoroughly blended with 13.8 kg of
acid-alum~silica sol, the preparation of which was
described in Example 19. The mixture was spray dried
using the conditions described in Example 19. The then
spray dried material was washed with water and ion
exchanged with mixed rare earth chloride solution as
follows: A 3,000 g portion of spray dried material was
slurries in 11.3 1 of hot deionized water at 60-71C
and filtered. The filter cake was rinsed three times
with 3 1 of hot water. Then the cake was reslurried in
9 1 of hot water and filtered again. The cake was
rinsed three times with 3 1 portions of hot water. The
filter cake was next reslurried in 10 1 of hot water
and 215 ml of mixed rare earth chloride solution (60
wt.% WRECK OWE) were mixed into the slurry. The
slurry was gently stirred for 20 minutes and kept at a
temperature of 60-71C, and the pi was kept at
4.7-5.2. Lastly the slurry was filtered again and
rinsed with three 3 1 portions of hot water.
(b) A similar catalyst was prepared using a
conventional Nay zealot that has a Sue
ratio of about 4.9 + 0.1
The finished catalyst was then oven dried at
149C. The finished catalyst made from HAY was
compared in the tests given below in Table 7 with the
catalyst made in a similar manner from conventional
Nay West Texas Heavy Gas Oil was cracked in the
micro activity test using the test conditions given in
Example 19.
- 3g -
I
TABLE 7
Catalyst Composition (wt. I) Example 20(b) Example aye
Zealot 17 17
Sue 23 23
Clay 60 60
NATO 0.74 0~70
ROY 3.68 3.83
Sue ratio of zealot 4.9 + 0.1 5.8 t O .
Micro activity (Vol.% Con.)
S-13.5 Deactivation
As Is 73 82
0% Metals 68 72
0.5~ (Navaho) 28 54
1500 Deactivation 48 62
Steam deactivation: 5 hours at ~16C, 100% steam at 0
kg/cm2 gauge pressure.
For each of the catalysts described above in Examples
lo and 20 the catalyst made with the HAY type zealot
demonstrates better resistance to hydrothermal
deactivation than the same formulation of catalyst made
with an equal amount of conventional Y type zealot. The
two catalysts in Examples lo and 20 made with HAY also
show greater resistance to deactivation by vanadium and
nickel contamination (heavy metals poisoning) than the
equivalent catalysts made from conventional Y type zealot.
The above catalyst examples clearly indicate that
valuable cracking catalysts may be obtained using the HAY
according to the present invention.
- 40 -
~5~3~
It is understood that the foregoing detailed
description is given merely by way of illustration and
that many variations may be made therein without departing
from the spirit of the invention.
- 41 -
