JPS59121114A - High silica/alumina rate faujasite and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of type Y zeolites with a silica to alumina ratio and the resulting unique zeolites obtained.

Brec) l) U.S. Patent No. 3,130,007 is the basic patent for zeolite Y, and this patent describes the zeolite as having the formula % in moles of oxide: It is defined that W can have a value greater than 3.0 and up to about 6, and X can have a value up to about 9. A disclosed use for zeolite) Y is as an adsorbent.

Break considers two types of silica sources. When the main silica source is a lower cost silica source, such as sodium silicate, silica gel and silicic acid,
The produced zeolite) Y is usually larger than 3 and about 3.9
Silica/alumina (S j 02 /A
0 examples with a molar ratio of l 20a ) are shown in Tables ■ and ■
It is described in.

The lowest amount of soda used is in range 5. Na2O vs A1
5iOz/ to the lowest ratio of 20a (which is 0.6)
By multiplying by the lowest AltO* ratio of 8', the lowest possible Na2O content is 4.8 moles, which lies above line A in Figure 81 below.

When it is desired to obtain a zeolite product composition with a silica/alumina molar ratio greater than about 3.9, Break is preferred as the predominant source of silica, although the more expensive silica sources, such as colloidal silica and It uses amorphous solid silica. Since these colloidal silicas and amorphous solid silicas are expensive materials compared to sodium silicate, Break does not teach how to make high silica zeolites (Y) from lower cost reactants.

Break also requires initial aging at ambient or room temperature. The importance of this cold aging for all manufacturing processes is shown in Table V.

British Patent No. 1,044,983 to Es5o discloses the production of Y-type zeolites with silica to alumina ratios of 3 to 7, with reactive components having low soda to silica and water to silica ratios. Similar to the Break patent, 5.5 to 6.8 in the well-crystallized NaY form.
The preferred silica source and materials used in all of the examples, resulting in the i02/Al2O3 ratio, are expensive legacy materials.

McDaniel et alc7) U.S. Patent No. 3
．． No. 808,326 discloses making Y-type zeolites using nuclei or nucleation centers with an average particle size of about 0.1 microns. In Example IT, the resulting zeolite particles have a silica to alumina ratio of about 5.0 to
6.0, but the individual values are not listed. The 5i02 to Al2O3 ratio varies between 9.5 and 14.5, and the amount of Na2O sifted is listed, which in each case is greater than the amount used in the present invention.

Maher et al U.S. Patent No. 3,671.1
No. 91 discloses the production of high silica synthetic faujasite by using a core and a silica to alumina reactant ratio of about 16=1. At this preferred 16:1 silica to alumina synthesis ratio, the Na2O to alumina ratio shown in the examples is 6.6. This is identified as point G in FIG. Some of the products produced have ratios of 5.2 in Example 2 and 5.4 in Example 3.

Elliott et al U.S. Patent No. 3,639
．． No. 099 uses a core with a silica to alumina ratio of 4.
Discloses manufacturing larger faujasites. 8-12 5i02 vs. At20. A preferred silica to alumina ratio in the reaction slurry is about 9:1. In that case, the preferred reaction mixture is 35±0.4 Na2 for each Al□0:I
It has O. The lowest level at a 9:1 silica to alumina ratio would be 3.1 moles Na2O. This point is identified as point F in the figure above. In Table 1, lOO12
The lowest free Na used among the products made from
, 0 was 3.5, and it produced a 5i02/Al2O, ratio of only 5.47.

Whiiam et al U.S. Pat. No. 4,016.
No. 246 discloses the production of zeolite Y in which the molar ratio of silica to alumina is greater than 3 and up to about 6.2. This method requires the use of "active" sodium metasilicate hydrate, which can be distinguished from conventional sodium metasilicate. This unique hydrate is produced by three methods described in this patent. Whittam's method is also expensive to implement, since this starting material is difficult to obtain, requiring special manufacturing techniques.

Vaughan et al U.S. Pat. No. 4,178
．． No. 352 discloses the synthesis of Y-type zeolites using minimal excess of reactants. There is a general statement that the resulting zeolite can have a silica to alumina ratio of about 4 to 5.5. However, the highest product ratio shown in the examples is 5,1 in Example 6. The final reaction mixture is A l 20 a
4 to 7.5 moles of SiO□ and 1.2 per liter of
~3 moles of Na2O. Most of the examples use solutions of reactants with a silica to alumina ratio of 6 to 1 and 1.8 or 1.9 moles of Na2O. At point E in the drawing, the silica to alumina molar ratio is 6 and there are 1.8 moles of Na2O for every mole of alumina. represents this technology.

McDanel U.S. Pat. No. 3,547,538 uses kaolin, in a preferred embodiment metakaolin aged sodium silicate in the form of water glass, from inexpensive raw materials with a silica to alumina ratio of greater than 4.5. Discloses manufacturing faujasite materials. In an example, the highest silica to alumina ratio is 5.
．． 90 and 5.95 have been produced.

However, in industrial implementation this method is optimized. It is difficult to obtain kaolin and/or metakaolin that satisfy the desired chemical and physical properties.

Wilso'n British Patent No. 1,431,944 discloses the production of crystalline alumino-silicate zeolites with silica to alumina ratios ranging from 5.5 to 8.0. This method requires a series of sequential steps for the addition of one reactive acid. first.

A solution of faujasite precursor is formed and heated.

Then add sodium silicate solution to 5i02/Al
Increase the molar ratio of 2O3. Next, as an essential 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 more water to the gel and further heating to promote crystallization. Wilson's method does not involve a synthetic procedure in which all of the reaction components are mixed together lignically at the same time.

One objective of the present invention is to produce a Y-type zeolite with a high silica to alumina ratio greater than 5.0.

Another objective is to produce a Y-type zeolite with a high silica to alumina ratio and a high degree of crystallinity and free of occluded silica.

Another object of the invention is alumina made from metakaolin or a source other than kaolin. The objective is to obtain a high silica Y-type zeolite.

Another object of the invention is to obtain high-silica Y-type zeolites which can be used for catalytic purposes by using inexpensive silica sources such as sodium silicate, silica gel or silicic acid.

Another objective is to reduce the active soda content in the reaction mixture to obtain a high silica Y-type zeolite.

- Another objective is to use the light ogelation mother liquor from the previous synthesis as starting material when reducing the active soda content to make high silica Y-type zeolites.

These and other objects will become apparent from the detailed description of the invention.

A high silica/alumina sodium type Y faujasite, H5AY, is prepared by carefully adjusting the active soda content to lower levels than those conventionally used. Type Y faujasite is made from metakaolin or an alumina source other than kaolin, while the silica source is an inexpensive source such as sodium silicate, silica, silicic acid or mixtures thereof. The soda content can be reduced by two different techniques or a combination of the two techniques. The first technology is an activated soda regulator;
For example, it includes adding an acid and/or an aluminira 1.111 solution obtained from aluminum and acid, which reduces the amount of active sodium in the zeolite synthesis slurry. Preferred materials are dilute acids or dilute aluminum sulfate solutions.

The other technique involves using a combined source of reactive silica and low activated soda alumina as starting reaction components, which can be used in combination with the individual silica and alumina sources described above. . A preferred combination source was treated with aluminum lamb salt to obtain a low soda aluminum salt gelling mother liquor. This is the mother liquor from before. The preferred aluminum salt in this embodiment is aluminum sulfate, also known as Ming Qing.

By reducing the level of soda, the silica/alumina ratio is above 5.0, especially at levels above 5.8H. A unique well-crystallized NaY zeolite can be produced. This unique high silica/alumina product can also be ion-exchanged with rare earth or ammonium cations to further lower Na2O levels, making it more thermal and hydrophilic for petroleum cracking catalysts, petroleum hydrogenation catalysts, etc. Air-stable zeolite promoters can be produced.

Y-type faujasite obtained by this method has a high degree of crystallinity. These materials are detailed below in the magic angle spinning section.
le spinning) nuclear magnetic co-vJ (m, a, s
, n, m, r,), Si [lA
The peaks for Ico and St[OAI are sharper than comparable commercial samples. By expressing the sharpness for the S i [2A l] peak and multiplying by lO, we obtain the sharpness index, S .

■4 is obtained. This S for the Sf[lAI] peak, 1. is at least 6. Preferably at least 7
However, S, I for the Si[0-AI] peak
, is at least about 2.2, preferably at least 2.5
It is.

High silica/alumina sodium Y-type faujasite can be used as an alumina source, a silica source, a soda source, a nucleus or nucleation center, and a reduced active soda concentration in the reaction mixture for further reactions. Made from ingredients.

More preferred alumina sources may be alumina trihydrate, alumina-aquarite, sodium aluminate solution, and aluminum sulfate (Meiji) solution. Other possible alumina sources are alumina gel, aluminum hydroxide,
It could be aluminum chloride, aluminum nitrate or other salts of aluminum and acids. Since it is difficult in industrial practice to obtain kaolin or metakaolin in a form that satisfies the desired chemical and physical properties that optimize this method, the use of these two materials is particularly would be undesirable.

Preferred silica sources are inexpensive sources such as sodium silicate, silica gel, silicic acid or mixtures of these materials. The use of more expensive silica sources, such as aqueous colloidal silica sols or more expensive forms of reactive amorphous solid silica, is particularly undesirable for industrial applications. Other 6f-capable silica sources are the light percent gelling liquids detailed below.

Preferred sources of soda are obtained from the compounds in the form of sodium salts used to supply silica and alumina, namely sodium silicate and sodium alumina. Other possible sources of soda are sodium hydroxide and sodium carbonate, but it must be remembered that the purpose of the invention is to reduce the amount of sorta in the reaction mixture. It can be a normal Y zeola, a mother liquor from the production of A, X or Y or an o11 hot gelling mother liquor. Making the nucleus 1
One preferred method is as described by McDante et a
No. 3,808,326, and illustrated in Example 1 below.

Further reaction components, which allow a reduced concentration of active soda 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 an active soda moderator. Because it reacts with excess activated soda and binds it to the synthesis of high silica Y zeolite! This is because J. has no influence. Examples of materials that adjust the concentration of activated soda include acid, alumina L,
and mixtures of these two materials. The acid is preferably added in diluted form and the preferred acid is sulfuric acid. In a preferred embodiment, these added active soda modifiers are added at the time of mixing the slurry, or within about 3 hours of heating the slurry for most effective results.

Another form of more reactive component is a combined source of reactive silica and alumina with low active soda. This can be done as follows. That is, add 3 liters of fluoride to the silica-containing HJ solution from the previous preparation to precipitate a solica/alumina hydrogel with low active soda content. Examples of aluminum salts are aluminum sulphate, aluminum chloride, aluminum nitrate or mixtures thereof. Aluminum sulfate (Mei 7) is preferred i
It is n. This preferred recirculation technique is described in U.S. Patent No. 4.1.
64,551 (Elliott), in which aluminum sulfate is added to the filtered mother liquor to precipitate a silica/aluminum hydrigel. This hydrogel is called AGML or Alternative Gelling Mother Liquor, and it can be used with other Aluminum 1! The gelling mother liquor can be used directly as a starting material when making high silica faujasite according to the present invention.

According to the present invention, the active soda content is reduced below levels previously used. See Figure 1! When ζing, the straight line A is 5.0 5i02 to At20, the ratio is 1! A conventional formulation is shown to produce NaY forager (1.
It has traditionally been the Na2O to A1209 ratio of about 6.6. 9 moles of 5 for each mole of Al2O,
For the reaction slurry at point F using i02, N
The a2O:Al2O3 ratio has a minimum ip of about 3.1, but 6 moles cy) St for every nuclear mole of Al2O3,
, the point E using Na2O:Al2O'r, Ll; is about 1.7. Thus, straight line A is based on at least the following points in the ratio in the synthetic slurry: 5i02 :Al20g Na2O:Al2O3 ratio
Ratio 16:l 6.6:19:1
3.1:1 6:1 1.8:1, according to the invention, the sorter is prepared by addition of active soda moderator, e.g. acid and/or aluminium, and acid. is reduced to a level lower than straight line A. This salt can be added as a solution. The preferred form of the acid or salt is a dilute solution, and the preferred form of the salt is dilute T1! Aluminum acid solution. In a more preferred embodiment, the activated soda line is aligned with straight line B in the drawing.
is lowered below 1/bel, where Al2O
For a reaction slurry using 16 moles for each mole of 3, the N A20 :A I20a ratio is about 5. −
0, and using 9 moles for each mole of Al2O, for the voice reaction slurry, Na2O:At, 0. The ratio is approximately 2.4. Using this starting composition, 5.8
A NaY faujasite is obtained with a 5i02 to Al2O3 ratio of ~6.0. Thus, straight line B is based on at least the following points for the ratio in the composite slurry:
5i02:Al2O3Na2O:A120g ratio
-Rue 16: -15,0 9:1 2.4 When adding materials to the reactor, avoid gel formation? 1. Must be conscious. This gel is difficult to subsequently disperse or dissolve. When adding the ingredients sequentially - the preferred order is to first add the dilute sodium silicate, then slowly add the dilute acid with stirring, then slowly add the dilute sodium aluminate with continuous stirring, and finally add the nuclei. be. A preferred method for accelerating the addition of the reaction components is to feed the reaction components in three streams into the high speed reactor, thereby forming a soft gel, which can be fed directly to the crystallization reactor. One stream contains sodium silicate and nuclei, the second stream is a dilute acid stream, and the third stream is a dilute sodium aluminate stream.

In other embodiments, after initially heating the reaction mixture, the liquid volume of the slurry can be reduced by decantation, whereby reliable crystallization carried out over a relatively long period of time can be achieved by removing excess liquid. Significantly reduced volume of reaction components, e.g. 2. This can be done with a volume reduction of /3. The initial heating time can range from a relatively short period of time, e.g., about 15 minutes, to a longer period of time, e.g.
It is possible to convert up to B to ψ. Since the reaction is carried out in a completely aqueous system, the mixture is heated to approximately 100°C.
can be heated to a temperature of

Using a reaction slurry with a ratio of 5i02 to Al2O3 of 16.1, a Y-shaped fork with a S i02 /A 120g ratio ranging from about 5.4 to about 6.0 depending on the amount of active soda reduction present is used. Jasite is obtained. Using anti-ψ, Nislery, where the ratio of 5i02 to A l 20 a is 9=1, 5i02. A Y-type faujasite is obtained where the /Al2O3 ratio ranges from about 5.3 to about 5.8 depending on the amount of active soda reduction present.

H5AY zeolite, like conventional NaY zeolite, is ion-exchanged with a solution of rare salts or other metal salts or ammonium salts or combinations thereof.
The Na" ion content in zeolites can be reduced to create a thermally and hydrothermally stable promoter for catalysts treating oil fractions. Such ion exchange H5 with Na+φ% of about io~15% when synthesized
AY with an aqueous solution of any of the salts mentioned above for 1 minute to 1 minute.
00 hours at 0°c-ioo°C.

This can be done by filtering the mass and washing the zeolite filter cake. Repeated exchanges with or without calcination of the exchanged zeolite can increase the Na+ content of the exchanged zeolite, depending on the application of the ion-exchanged H3AY promoter.
This can be done by reducing Na2O to as low as 0.1-5%. These ion exchange f orders are:
Well known in this field. Alternatively, ion exchange is H3AYOi! This can be carried out after preparing the promoter as a catalyst.

The high phosphoric Y zeolite made by this method is believed to be unique, and is due to the high degree of crystallinity and the absence of occluded silica, as determined by the NMR spectral sharpness index described below. characterized. As the S i O2/A I 203 ratio increases, the nature of the chemical bonds involved changes. S,
Ramdas eL at their paper, Ord.
ering of aluminum and
5ilicon in 5ynthetic
Faujasites”, Nature, Vol. 2
92. JuJy 16° 1981, pages 228-230 states that zeotites can have five types of silicon to silicon or aluminium bonds. These five types of bonds are expressed in a notation that gives the number of aluminum atoms to which silicon is bonded through oxygen atoms. Each silicon bonds to four oxygen atoms,
Each of these oxygen atoms is bonded to silicon or aluminium-11. The five types of bonds are Si (4AI),
Si (3AI), Si (2AI), St (IAI
) and 5i (OAI). In this way, silicon becomes 4
When bonded to four aluminum atoms through one oxygen atom, the notation is 3i (4AI). K1
1n.

wski et al, “A Re-exami
nation of St, AI Orderi
ng-ir+ Zeolites NaX an
dN a Y ”, J , Chem, Soc, , Far
day Trans, 2,78.1025-1゜5
0 (1982).

Ramdas et al. (7) FiPi et al. identified five types of bonds through the use of nuclear magnetism. Table 1 below shows the distribution for conventional NaY with a Si02/A I203 ratio of 4.8 and the Si027A 'l, 0
The theoretical distribution of H3AY type material rice grains with 3 liters is 6.0 is shown. For comparison, this table also includes an idealized row for NaY-type faujasite.

Al2O3 ratio 2.44.8 to 6.0 class and female'1
Decimal upper si (, tAl) 16 0 0
Si (3Al) 8 4 0S
i(2AI) 0 16 16Si(I
AI) 0 12 16Si(OAI)
2 2 4H5AY type materials when made according to the present invention.

It has more 5i (IAI) and 5ilAI) bonds and less 5i (3Al) bonds than conventional NaY zeolites.

To experimentally measure these five types of bonds, high-resolution “Si NMR spectra were collected using Ra+ndas
el alc7) Obtained as shown in Figure 3 of the literature, and using a computer to calculate
, a curve is generated based on the shape of the gown's peak. The area of the curve represents the relative population of the five 0f-capable rnn-ordered modes.

This new analytical technique was also used to determine the actual S i02 ,/A 1203 ratio in the crystal lattice r;
We identified occluded silica when it was present and determined how well the sample was crystallized. This technique uses silicon-29 nuclear magnetic resonance (N M'R). Silicon-29 is an isotope of silicon present in approximately 4.7% of all silicon atoms. The spectrum was generated at 79.45MH using MAS, a technique that significantly improves the resolution of NMR spectra.
Obtained at z. HS made by the method of the present invention
Two trials of AY: MA and B and U.S. Patent No. 3.63
No. 9,099 made by the method taught by
A commercial sample of Y was studied by this NMR technique using MAS. Sample A was made by a method similar to that described in Example 15 of F, and sample B was made by a method similar to that described in Example 5. NMR results show that SiC with HSAY of 5.6±0.4 in the lattice
2,/Al2O3 ratio, it was shown to be free of occluded silica, and it was very well crystallized. For purposes of this case, the S i02 /A 1203 ratio will be determined by the Jintong wet chemical method. The ratios determined by NMR theta are stated because the values are strictly representative of the silica and alumina in the crystalline structure. The presence of occluded silica would not be included in the ratio determined by NMR.9 However, the NMR data are shown in Table 2.
They appear to be less accurate due to greater uncertainty about their values, as reported in

MAS spectra were performed using an external HMDS (hexamethyldisiloxane) reference standard and TMS (
δHMDS=+6.7p for tetramethylsilane)
, p, m. The spectrum is
As shown in the spectrum of FIG. 2, there are five peaks characteristic of the five possible environments for silicon in the tetrahedral framework in the zeolite structure. The scale in FIG. 2 relates to TMS, with the TMS peak occurring at zero.

Assuming that these spectra have crow-like properties, we decompose these spectra into separate components.
(deconvolute). The complete assignment of spectra is shown in Table 2 below, along with the peak areas corrected for the small differential effects of sideband correction. The small difference in shift values in this table compared to that of spectrum L is due to the overlap between the peaks. The area of each peak was adjusted so that 11'' is equal to 100 for the sum of the areas of the five peaks.The width of each peak, W, at the I7/2 peak height was also extended by 1. HSAY trial i in the figure
-1 no s i [lA l] oyohi s i [O
A l] The peak is the quotient! II N a Y's gc is sharper than its rival peak. This sharpness can be defined mathematically as first order. S f [2A
I] When using the area of the peak as ij; H@,
The orderless optical sharpness, S, for each peak is defined as (width in l/2 height) 2 w2 . Next, the sharpness index of each peak other than the Si[2AI] peak, S, 1. , is defined as. These sets for n=0 and 1 are expressed as 1. Table 2
Describe it in

Dimensions - ■ Dimensions Oshi Coco
・-Ka＼L1′)
.

As the data in Table 2 shows, Si[IAI,
] and S i IOA 1] peaks are commercially available NaY
much sharper than the same peak in . St [IA1] peak is at least 6. IJI or sharpness index of at least 7, S, 1. , and the Si[OAl] peak has a sharpness index of about 2.2, preferably at least 2.5, S, 1. , has. The Si[IAI] and Si[OAI] peaks of the present invention are derived from the high 5
It clearly shows the i02/A1201 ratio and the high degree of crystallinity of HSAY.

(As mentioned above, the magic angle NMR spectrum can be used to determine whether or not occluded silica is present. This is because the oxygen atom is not bonded to any other atom other than silicon. If not, there would be another characteristic peak for silicon, characterized by silicon atoms bonded only to # atoms.

The presence of occluded silica also increases the unit cell length un
it call length)c7) can be determined by data. E, Dempsey e.
tal, Journey of, Physic
al Chemistry, 73, 387-390.
(1969) j,:,F-++,'T, Nax and N
Chemical analysis versus unit cell length of various samples of aY fu+-jasite are compared. They have the lowest unit cell length among the NaY samples, S i 02 /' of 5.32.
A was found to be 24.66A for NaY with a 120g ratio. However, a plot of unit cell length versus number of aluminum atoms per unit cell (Figure 1 in the paper) shows that the lowest number of aluminum atoms per unit cell is 53, which is 24.665A
corresponds to the pitch size, that is, the unit cell length, where A
is in angstroms. They tested several other NaY samples, and chemical analysis showed ratios up to 5.83, but none of the NaY samples, +1, had a ratio of 24.665.
It did not have a unit cell shorter than A. therefore,
They suggest that samples with high 5102/A+203 ratios contain amorphous silica.

When the NaY sample contains 11 crystalline silica homogeneously mixed with crystalline NaY, the apparent ratio j by bulk chemical analysis will be larger than the actual ratio in the crystal lattice. The jin-yu taken from their table is S i 02
The unit cell length versus the /A +203 ratio is plotted in FIG. The open rectangle in Figure 3 represents Na
Data are shown for a crystallized sample of Y. The unit cell length is inversely proportional to the 5iO7/A120a ratio. The triangles in Figure 3 demonstrate that the NaY test viewed at higher ratios by chemical analysis does not show progressive cell length contraction with increasing ratio. These samples, pro-sothoted as triangles, likely contain occluded amorphous silica. For these high ratio samples, the ratio is between 5.4 and 5.
．． Even with the increase to 8, Cell I Committee Saba 24.66-24.
Stay at 67A.

It is concluded that the highest ratio in the crystal lattice of the NaY samples they studied was approximately 5.3. The solid rectangle in FIG. 3 shows the unit cell length vs.
This is a plot of the i02/AI203 ratio. The solid squares generally appear to be an extension of the open squares, and the H5AY sample of the tree invention has a unit cell length proportional to the S+02,/AI□03 ratio obtained by chemical analysis. It proves that. The full square is 6
The unit cell length is 24.58A, which corresponds to a ratio of 0.degree. Therefore, Wood's H5AY sample does not contain occluded amorphous silica homogeneously mixed with faujasite. Moreover, the ratio obtained by chemical analysis of each sample is the actual S r 027 in the π real crystal lattice.
'A I 2 Oa ratio.

Presence of occluded silica with high crystallinity 1. The unique high silica Y zeolite made in accordance with the present invention is very useful as a catalyst. This catalyst can be created using the f-order of the preceding branch technique. The HSAY is ion-exchanged to reduce its alkali metal content and added with stabilizing, catalytically active ions. Typically, HSAY is ion-exchanged with Ri-like ions and/or ammonium ions and hydrogen ions. H.S.
AY can be ion-exchanged before or after incorporation into the inorganic oxide matrix. Additionally, the ion-exchanged HSAY may be incorporated into the catalyst 7 trix before or after.

Calcinate, i.e. heat to a temperature of about 200-700°C. Preferably, when HSAY is used as a hydrocarbon cracking catalyst, the alkali content is lower than the sorb impregnation, Na
Expressed as 2O, it will be about 6% by weight or more.

Conversion of HSAY into useful particulate catalysts is possible with finely divided) TSA
This is achieved by dispersing Y zeolite in an inorganic oxide matrix. The inorganic oxide matrix is composed of silica-alumina, alumina, silica-nol or hydrogel in combination with additives, such as Visco-1-1 preferably kaolin, and other zeolites, such as ZSM type zeolite i. It's okay to include it.

The catalyst composition can be prepared according to the teachings of US Pat. No. 3,957,689. That is, fine zeolites and clays are combined with a jet-dried and ion-exchanged aqueous slurry to form a highly active hydrocarbon conversion catalyst. Additionally, catalysts are generally made of zeolites and ζ, as shown in Canadian Patent No. 967.136. - can be prepared by combining with an acidic alumina binder. When attempting to obtain a catalyst containing a silica-alumina hydrogel, the method of US Pat. No. 3,912,619 can be utilized.

1-, the N5AY zeolite is particularly resistant to hydrothermal deactivation conditions normally encountered during cracking catalyst regeneration. Regeneration involves high temperature oxidation (combustion) at temperatures up to about 1000° C. to remove accumulated L'j +: buildup.

Further (2) Catalyst containing HSAY described here
It is particularly resistant to the deactivation effect of contaminating metals, such as nickel and vanadium, which rapidly precipitate on the catalyst during the decomposition of residual hydrocarbons.

The exact reasons why the HSAY of the present invention and the catalysts containing the HSAY described herein are particularly active and stable are not completely understood, but after steam deactivation and The particularly high degree of activity and stability of this existing catalyst has been demonstrated by S. Ramdas, et al.
alc7) Paper No.'Ordering Of
Alutninum AndSiliconInSy
nthetic F a u j a sit e
s”, N a ture, V.

1.292. July 16.1981.228-2
As discussed on page 30.

This is because of its unique structure.

During use, the catalytic cracking catalyst of the present invention is combined with a hydrocarbon feedstock (approximately 1.000 p.p.
nickel and l<nadium up to pm, about 10 Tohaya%
It also consists of a hydrogen-burning fraction (residual petroleum) containing up to sulfur and up to about 2% nitrogen. The cracking reaction is typically carried out at a temperature range of 200-600°C using a catalyst to oil ratio on the order of 1-30. During the cracking reaction, catalysts typically accumulate about 0.5-10% carbon, which is then oxidized during catalyst regeneration. The activity can be maintained even after accumulating contaminating metals.

The catalyst may optionally be combined with additional additives or components, such as platinum, which enhance the CO/SOx properties of the catalyst. Preferably, the total catalyst composition contains 1 O of platinum at about 2 to 1 O ppm. moreover,
The catalyst advantageously comprises a SOx acquisition fraction of 1, for example about 20
It can be combined with a lanthanum/'alumina composite containing about % by weight of lanthanum oxide.

Having explained the basic aspects of the invention, the following
Embodiments of the special features of the present invention will be described by way of a fourth example.

1 - This - ← pole side is disclosed in U.S. Patent No. 3,808,326 (M
The production of nuclear centers or nuclei is described as disclosed in Daniel et al.

A solution of 919 g of sodium hydroxide in 2.000 ml of water was heated to produce 156 g of alumina trihydrate (A120
．． and 3H20) was dissolved, and then the solution was cooled to room temperature. This solution is mixed with solution A. 3.126 g of 41.2°B6 storium silicate (1,0:3.22
(7) Na20:5i02 gravity ψ ratio) is 1,555 m1
A second solution B was prepared by mixing the solution in water.

Then add solution A into solution B while stirring rapidly.
Mixed. The mixture was heated at room temperature for about 24 hours to form a V% solution, and then the core cores or core slats were ready for use.

Examples 2-5 These examples show that the nucleated slurry was 16:J S
High 5i02 that increases iO2/A l 203 ratio by 1
/' Clarify the production of Al2O3 sodium Y-type faujasite.

Solutions of reaction components were prepared as follows. W3tm of various baskets with a specific gravity of 1.84 as listed in Table 1 is
A dilute acid solution was prepared by adding 00 ml of water and the mixture was stirred well.

91gc7) 17.2% by weight Na2O and 21.8
A Ri sodium aluminate solution was prepared by adding a sodium aluminate solution containing % Al2O3 by weight to 214 g of water.

648gc7)l, O: 3, 22c/)Na2
Pour the 41.2°Be sodium silicate solution with a 0:SiO7 ratio into a 40 oz. Prepare a sodium nonasilicate solution by combining sodium thorium and 414 1. 6
During blender mixing, the dilute acid was added to the dilute aluminate and then the dilute aluminate was added. Finally 47g of core slurry was added to this mixture.

The slurry was poured into a polypropylene bottle with a loose lid. The bottles were heated in a water bath to bring the slurry to 85°C, at which time the bottles were transferred to a heated L7 oven at 100°C.

Samples of the slurry were taken from time to time by stirring the contents well and taking 50 ml of slurry. The sample was filtered, washed to pH [O~10.5, and incubated at 100°C.
dried in an oven.

The crystallinity rate of each sample was determined by powder X-ray diffraction technique.

N, a Comparison was made with a crystallized commercial sample of Y-type faujasite. After incubating the sample for 1 hour at 1000 °C (538 °C),
by the chromatographic method of Kin-Elmer-3hell) 212D Sorptome-9-(Kin-Elmer-3hell) or by the chromatographic method of
Amic, o Adsorp t, o m a t
) The nitrogen surface area of the sample was measured by the BET method.

Let us define the magnificence cell size of the cubic single A cell of H3AY, where all three axes are equal and the length is a=b=c),
III was determined as follows. H5AY was equilibrated overnight in a 7F desiccator with relative humidity of 33%.
Approximately Ig of powder was mixed with about 1 g of Gaif metal powder. This silicon served as an internal standard for the X-ray diffraction pattern produced using copper radiation filtered through a Ninkel foil. The diffraction pattern was recorded from approximately 52°20 to 60620.

997 plane (h=9.=9, and 1=7) and 9
The 2° position of the reflection from the 99-plane was measured. , the first appears at about 54.0 to 54.2820, and the second appears at about 58.
Appeared at 7 to 58.9”20.The internal standard of silicon was
Theoretically it had a reflection at 56.12°20.

2 H5AY)! The 2θ measured on the three sides was corrected by the change from the silicon peak at 56.12°. Then, the median cell was calculated using the Bragg's law equation: % formula %. Here, the input is 1.54718A I
It is the wavelength of I Kα radiation. The unit cell was the average of a from the 997 and 999 planes.

The resulting NaY type faujasai) Jl crystallized from the slurries of Examples 2 to 5 and listed in Table 3 below
The 1ν material has a high S, especially in Examples 4 and 5.
i02/A I20. I got the ratio right.

-ULITO [two legs-] These examples show that the nucleus addition slurry is 9=1 silica/
'High silica/sodium alumina Y that controls the alumina ratio
Revealing the manufacture of type faujasite.

The solution of sodium silicate and sodium aluminium was prepared by adding 1/2 the same concentration of sodium silicate and water as in Examples 2 to 5 to 40 ounces of Hamilton Beach Burengoo. It was mixed inside. Nuclei prepared according to Example 1 were added with the groups listed in Table 4;
It was blended. Aluminum anti-sodium solution in another 1/2 of water
mixed with. The mixture became very viscous, to the point of gelling and stopping the blending. Carefully scrape the gel completely out of the Brengu cup and pour it into the bowl of the Hobart Fist Kitchen Mixer. After starting the Hobart mixer, the remainder of the sodium aluminate was slowly added. A solution of aluminum sulfate (male) with 7.8% Al2O, was added (while continuing to combine t, k, 4). Added 250 ml of a thick, base-like gel. 500 ml polypropylene bottle, loose container 1. Ta. The remaining heating and analysis procedures were the same as in Examples 2-5.

The resulting NaY-type faujasite product, listed as Table 4 and No. 4, was crystallized from the slurry of Examples 6-9. In particular, Examples 8 and 9 had a ratio of lb's+Q2/Al>0g.

- Yum This example shows that one culm of crystallization is carried out for a relatively long time.
We demonstrate synthesis using a reduced volume after an initial heated reaction so that the volume required can be significantly reduced.

''-i6 Example 5 A 16:1 silica to alumina slurry having a sidewall composition was prepared. The slurry was heated to 100 DEG C. for 24 hours without agitation.

During this period, the solids settled to the bottom of the bottle. After heating for 24 hours, the mother liquor was decanted to reduce the volume by about 2/3, and the remaining solids surrounded by liquid Iv were then reduced to 1
After heating to 00℃ for 131 hours, the surface! +'i 897x
n2/g, crystallinity 94% and unit cell size 24
．． 11 excellent products of 59 angstrom units
I was beaten. This is 5.9 as shown in Table 3.
SiO□/Al corresponds to 203 silicon.

This example demonstrates the production of Y zeolite using a reduced volume of slurry with a shorter initial heating step.

A procedure similar to that used in Example IO was followed, but instead of 24 hours at 100°C, the slurry was heated to 100°C for only 15 minutes. The solids were filtered through a Buchner filter.The solids were then added back to the bottle and just enough mother liquor was added to just cover the solids. These solids were fluffier than those produced in Example 10, so more serum was needed. The volume reduction was approximately 55-60%. This was slightly less than the volume reduction obtained in Example 10.

After crystallizing this mixture for 144 hours at 100 °C, the product has a crystallinity of 107%, the dimension a of the unit cell is 24.61 angstrom units, and Sl 02 /A Wet chemical analysis of the l203 ratio was 5.8.

Also, as shown from this example, excellent product was obtained with reduced crystallization volume and with excess! Il fluid is Ij
:jJ is collected and can be recycled or used for other purposes.

This example also demonstrates a synthesis using a reduced volume of slurry with a slightly shorter initial period of heating.

In this example, the exact procedure number two of Example 11 was followed, but instead of heating to 100° C. for 15 minutes, the slurry was heated for 1 hour. The solids were filtered according to the procedure of Example 11 and just enough mother liquor was added to cover the solids. After heating at 100 °C for 93 h, the crystallization rate is 109%, one dimension of unit cell is 24.60, and SiO□/Al by wet chemical analysis.
203 ratio was 5.8.

Ichijo Arashi Kaiun This example shows the reaction of silica and alumina using a slurry with a silica/alumina ratio of 16=1 using a sliding door gelling mother liquor, AGML. clarified that it will supply.

U.S. Patent No. 3,639,099 (McDaniei
Fully crystallized NaY from the previous preparation of sodium Y heptaolide made by the method according to et al.
A typical filtrate of mother liquor filtered from the batch contained the following components: 4.9% 5i02. and 4.0% Na2O.

Sodium aluminate solution is added and the silica, alumina gel, AGML precipitates and is recovered by filtration and dried. The gel contains the following ingredients: 12.6% S+02. 3.4% (7) Na20. 2.8% Al2O3° 2.6% S03 and balance water.

300 g of AGML in a blender with 200 g of water and 517 g of sodium silicate solution (41,2°B≦
Silica and sorter 3.22Si02: 1.0
A slurry for the synthesis of high silica phoridisesite according to the present invention was prepared by mixing with 54 g of sodium aluminate solution (18,296N a 20 ; 21 ,
4% A1203) was added diluted with 185 g of water and mixed well. Finally, 47 g of the core slurry prepared in Example 1 was mixed in a blender. Effective slurry ratio is 5.2N'a20:1.0A120t:16S
It was i02 280H2-0.

The thoroughly mixed slurry was placed in a 1.0 cross polypropylene cage and placed in a 100±1'C oven. 61
After an hour, the slurry formed a well-crystallized NaY faujasite with a surface area of 952 m2/H, of the high warp type according to the invention. This is Micromeritinx Co., Ltd. (
Micromeritics Inc., Norc
ross, GA) ￥J's Digisorp (Digisor)
p) Measured by instrument. HSAY faujasite had the following chemical analysis values: 10.7% Na2O19, 8% Al20369.5%5
i02 S i O2,/A 1203 ratio = 6.0 and crystallinity 102%.

This is an efficient use of waste.

- Disaster Season 14 - This example shows that when using a slurry with a silica/alumina ratio of 9:1, a clear gelled LzJ solution is used to supply a portion of the silica and alumina reaction component materials. reveal.

1.080 g of AGML prepared as described in Example 13 was placed in the bowl of a mixer and 319 g of 41
．． 2°B6 silicon salt resistant was added and mixed in the mixer.

Then 69 g of sodium aluminate solution was slowly added and combined IIi. The slurry became hard, but 1~
After 2 minutes of mixing, it became soft. After hl, 93 g of the core slurry prepared according to Example 1 was added. This slurry was placed in a polypropylene bottle of t.o.
1] The effective slurry oxide ratio placed in the furnace at ±J'C is 2.4Na20:1.0A1203:9SiO,:
It was 140H20.

After 44 hours, a high silica Y zeolite crystallized, with a nitrogen surface area of 937 m2/g and excellent crystallinity measured as 101% when compared to the Yamakawa NaY standard. The chemical analysis of the composition on a dry basis was as follows: 10.9% Na2O20, 4% A I 20368.7
The %5i02 sio2/A12o3 ratio was 5.7.

This stream reveals the process of the present invention to be scaled up to a 15 gallon (57L) bath yielding approximately 6.0 kg of dry product. .

40.0i<g commercial sodium silicate A, (Phi!a
Delphia Quartz N” Bran
d, 40.8B6 specific gravity) in the conditioning tank, LL, 5k
diluted with g of water. The mixer was started and allowed to run during the chemical addition. 1 diluted with 11.4 kg of water,
A solution of 531 g of concentrated sulfuric acid (specific gravity 184) was slowly added over 15 minutes and the reaction was continued for a further 12 hours.

5.226 g concentrated sodium aluminate solution nl (18.2% Na2O; 2
A dilute solution of 1.4% Al2O3) was added slowly over 1i2 hours.

After brewing, 2,631 g of nuclei or core centers (described in Example 1) were added. The slurry was pumped into a 20 gallon (76 gallon) steam jacketed reactor and lOO±l'C
was heated to crystallize NaY. The slurry was recently sampled to monitor the progress of crystallization. 105 at that temperature
After an hour, the experiment was stopped. The slurry was filtered and the filter cake was washed to remove excess RL liquid.

The product was H5AY which crystallized well, Si0
The 2/A 1203 ratio was 6.0 and the crystallinity was 96%.

- This example demonstrates both the 15 gallon (57Q) scale up and the use of other types of sodium silicate. The f order of mixing and crystallization was the same as the procedure in Example 13.

41.5kg Tiremond Jamrock (Dia
mond Shamrock-k) DS34 silicic acid!
25, 6% 3102; 6.6% Na20) and 14.6% water were mixed together. 4.5kg
A solution of 696 g of concentrated sulfuric acid diluted with 500 g of water was added. 4.
5 as in Example 13 diluted with 5 kg of water.
, 253 g of sodium aluminate were added. lastly,
2,192 g of cores of the type described in Example 1 were added.

Crystallization at 100±1°C is 5i02/A12'3
H whose ratio is 5.8 and crystallographic force <104%
5AY was produced in 72 hours.

- Husband 1 - This example demonstrates the production of large patches using simultaneous addition of the reactants.

Three solutions were prepared. 36.7 kg of 41.
0°B6 sodium silicate, 12.2 kg water and 2.633 g of the desired core described in Example 1 were added.

These materials were mixed and heated to 60°C.

In the 24th Pi, add 537g of concentrated sulfuric acid to 9°t.
A citric acid solution was prepared by mixing oog with water.

In a third tank, a dilute sodium aluminate solution was prepared by mixing 5.232 g of sodium aluminate (1B, 2% Na2O and 21.4% Al, O,) with 6.800 g of water.

Transfer the three vessels to a reactor with a high-speed mixing pump〉'
and the line from the first tank was first opened. After mixing the three streams with a high speed mixing pump, these streams formed a soft gel, which was fed into the reactor with further agitation. The reactor was closed and the gel was gradually heated to 100°C with continued stirring. After reaching a temperature of 100°C, the stirrer and strainer were stopped and the culm mixture was kept at this temperature for 70-80 hours. The temperature was maintained to crystallize H5AY. The slurry was then quenched with cold water, filtered, and subsequently washed with hot water.

When this material is dried, 6 kg of well-crystallized H
S A Y is obtained, which is 5.9 g of 5i02, /
It had an A I 20 = ratio and a crystallinity of 103%. The unit cell size is 24.60 angestrow 1, and the nitrogen surface area measured by the BET method using Micromeritinx Digisorb is 875 m
It was 2/g. Chemical analysis values are 11.0% Na2O,
It was 19.6% Al2O3 and 68.4% 5in2.

-Bunshi±11- The m5AY ceolite was exchanged with the rare 1-type according to the following procedure, and fired to obtain 14.0%RE20. ．． 2.45%
"CRE HS AY" was obtained consisting of Na2O and a silica to alumina ratio of 5.9:1.0.

HS obtained in Example 17 in a portion of 4.444 g
AY filter material (raw cake%) was slurried with 99% deionized water. The T(SAY) was then diluted with 7.5 grams of deionized water and 4,444 m
1 commercial mixed rare earth chloride solution fj, (61wt ¥% REC
1, 6H20). Heat the resulting mixture to 90-100"C and roll once to that temperature.
It lasted m. The slurry was filtered and the filter cake was washed twice with three passes of boiling water. This washed filter cake was diluted with 16.5 ml of deionized water.
1 in a commercial rare earth solution. This mixture was heated again to 90-100°C and the temperature was increased to 1
Time was maintained. The slurry was then filtered and the resulting filter cake was washed three times with three portions of boiling water. The filter cake was then oven dried at 150°C for 4-8 hours. Finally, the dried zeolite was calcined at 538°C for 3 hours to produce CREHSAY, which had the following properties: Loss on ignition (LOI) 2.1 % RE, 03
14.0 heavy φ% Na2O2,5 heavy % 5i02. /Al2O ratio 5.9±0.1 Nitrogen surface area (according to BET method) '798 m2/g--(a) Using CREHSAY of Example 18, U.S. Patent No. 3,957,689 F CCIll according to the teachings of No.
! Manufactured by h. The two solutions A and B are Ij'? +
JX and acid-male silica vines were prepared using a high-speed mixer. Solution A consists of 11.5 kg of 12.5% 5i0
2 sodium silicate (Na20:3.2Si02). Solution B contains 20% by weight of sulfur 19 (2,2 sentences) and 77 g/It of Al2O3. 3.609 of a solution prepared from dilute aluminum sulfate solution (14 sentences)
Met.

The ratio of solutions A and B flowing through the mixer is approximately 1.5
JJ's solution A vs. 0. ! This is solution B of l. The flow ratio was adjusted to produce an acid-light silica solution with a pH of 2.9 to 3.2. 14.4 kg of acid-Meishi silica,
2,860 g of kaolin and 2. ．． A slurry consisting of 145 g of CREHSAY from Example 18 and 6 parts water was added. A mixture of a slurry of +411 acid-clear-silica sol and CREHSAY in water was formulated and spray dried at an input temperature of 316°C and an exit temperature of 149°C. 3,000 of spray-dried product
A portion of g was slurried in 11.3 ml of water at 60-71'C. Filter party cake 3
Washed three times with 5 L of 3% ammonium sulfate solution. The cake was then reslurried in 9 liters of hot water, followed by
Finally, the catalyst was washed 3 times with hot water for 14 hours.
Oven dried at 9°C.

b) Catalysts with the same proportions of components were prepared in the same manner from rare earth exchanged conventional NaY with a silica to alumina ratio of about 4.9±0.1.

The results of the comparative test are listed in Table 6 below. Microactivity test (m
icroactivity test), F
, G., C4apetta and Ri.

S. Henderson, “Microact 1Vi.
ty Te5t For CrackingCa
talyst'', 0ils And Gas J
ournal, Vol-65, 88-93〆-ji, 19
The modified test procedure of October 16, 1967 was used. Microactivity tests are commonly used in the petroleum industry to evaluate the activity of cracking catalysts in the laboratory. Petroleum fractions cracked in the presence of these catalysts using the following test:
West Texas Heavy Cass Oil
・Texas Heavy Gas Of 1
) (WTHGO): Temperature: 499℃ Main hourly space velocity (WH3V): 16 Torque to oil ratio: 3゜WTHGO (1.67g) to 5.0g of catalyst 1.3
Pass within minutes. The product is collected and the conversion of gas oil to hydrogen, light gases, gasoline range hydrocarbons, etc. is determined by gas chromatography.

N as naphthenate with catalyst dissolved in WTHGO
Impregnated with i and v. The hydrocarbons were then combusted by slowly increasing the temperature to 677°C. The metal-impregnated catalyst was then deactivated by a 5-13.5 sequence and then tested for decomposition microactivation.

Table 6 Composition of catalyst Example Example, -(Heavy JJ
j%) 19(b) -1 and'11-heptaolite 35, 35Si02 2
4 24 viscosity (24141 Na20 0.49, 0.37RE
202 4, 94 5, 08AI, O
a 26.5 26.0-5 showed deactivation,
'High'f-(Turnover rate, 9' vertical %S-13,5 (1) 0% metal 82 86 1% (Ni +V) 53 74500 <3'l'81 80 550 (4) 20 5io2/' AlzOa of 64 zeolite -4,9±0.1 5.8±0.IRE
20 a (arbor%) 15.0±t 14.0±Ia
20 (weight ψ%) 3,2±0.2 2.4±0.2(1)
Water vapor deactivation near 32℃, 100% water vapor and 1.1
8 Gin in kg/cm2 gauge pressure.

(2) Ni=V/2° (3) Water vapor deactivation: 816°C, 100% water vapor and 0
kg70m2 Gauge pressure and N for 5 hours.

- (4) Percent deactivation of aquatic plants: 5 hours at 843°C, 100% steam and 0kg70m2 gauge pressure.

- Suzuma I Hikiotate - Ca) 2.576 g of H5AY filter cake (45% 1 mass) from the batch synthesized as in Example 17 and 4,186 g of kaolin and 8.0 parts water A slurry was made from this. 13.8k of this slurry
Example 19. This mixture was blown dry under the conditions described in Example 19. The spray-converted material was then washed with water and ion-exchanged with this mixed rare earth chloride solution as follows: A 3.000 g portion of the spray-dried 1-5 material was washed with 11.3 grams of 60-71"O of hot deionized water.

The filter cake was rinsed three times with 3 KL of hot water and the cake was then reslurried with 9-bun wood and filtered again. The cake was rinsed three times with three drops of hot water each time.

The filter cake was then reslurried in 109ml of hot water and 215ml of 7+d combined chloride solution (6
0% by weight of RECI3.6H20) was incorporated into the slurry. Stir this mixture gently for 20 minutes, 6
Maintain the temperature at 0~7I°C, pH 4-7~5, 2
Nimt: I did. After bathing, rinse with hot water for 3 times.

(a) S i 02 , /A l 203 ratio is approximately 4.9
With conventional NaY zeolite, which is ±0.1.

A similar catalyst was prepared.

The exposed catalyst was then oven dried at 149°C. A catalyst made from H5AY was compared with a catalyst made from conventional NaY in a similar manner in the tests described in Table 7 below. Ware 1 - Chassas or Hebiecas oil was degraded in a microactivity test using the test conditions described in Example 19.

Person 1 - Composition of catalyst Example Example - Roro 10 -
-Falled to ζ--Fuyuzora'' 11-Theolite 17
17 Si02 23 23 Clay
60 6゜Na2O0,740,37 4RE2O33,685,08 Theolite 5i02/' 4.9+0.1 5.8fO,IA
1□0□Ratio' Inactivation 11: (Conversion rate, volume θ0 S-13,5 Deactivation As Is 73 820% of metal 68 72 Q, 5% of (', Ni+28 54 V) 1500 48 62 (1) (1) Water vapor deactivation: 816°C, 100% water vapor and O
5 hours at kg/cm2 gauge pressure.

For each of the catalysts listed under L in Examples 1g and 2o, the catalyst prepared using SAY-type zeolite had a higher concentration than the same formulation of catalyst prepared using 1 equivalent of conventional Y-type zeolite. , clearly exhibits excellent resistance to deactivation of hydrothermal water.

Examples 19 and 20 made using HS A Y
The two catalysts also exhibit greater resistance to deactivation by vanadium and Fuchel contaminants (inhibitory effects of heavy metals) than comparable catalysts made from conventional Y-type zeolites.

The catalyst examples clearly show that H5AY according to the invention can be used to obtain a valuable cracking catalyst.

It should be understood that the following detailed description is by way of example only and that many changes may be made without departing from the spirit of the invention.

[Brief explanation of the drawing]

Is the figure 1 Y-shaped? Na2O,i;7 and 5102 vs. A of Slurry Composition for Producing Su-jasite Product
This is a graph expressed as a ratio of 1203. 21; 4 Decomposed MAS for high solica Y heptaolide and commercial NaY according to the present invention
This is an NMR spectrum. :fS3 diagram is Tweet for Faujasite J%+j Na Y with high silica to alumina ratio (7) S i 02
/ A I'20 a[ is a graph of unit cell length versus unit cell length.

Claims (1)

[Claims] 1. Formula % expressed in moles of liquid: where W is greater than 5.0, and X is about 9
A method of producing zeolite Y, which can be up to (a)) an alumina source other than takaolin 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 nuclei or nucleation centers: and (I) salts obtained from acids, aluminum and alcohol; an activated soda moderator selected from the group consisting of a mixture of; (II) a combined source of reactive silica and alumina with low activity sorter; or (m) a mixture of (I) and (II); forming a reaction slurry by mixing the above reactants; Line A in FIG. 1 for the corresponding ratio of moles of silica to 1 mole of alumina in the reaction slurry.
5i02:Al2O3Na2O:Al. Oa ratio
Ratio 16:l 6.6:19:l
3.1:16:1
1.8:1 and (b) heating the reaction slurry product of (a) to crystallize zeolite) Y. 2. Maintain the concentration of active sodium across the reaction slurry at or below the value given by line B in Figure 1 for the corresponding ratio of moles of silica to moles of alumina in the reaction slurry. By this, W in equation 1
has a value equal to or greater than about 5.8, and said straight line B is based on at least the following points for the ratio in the composite slurry: 5i02 :Al2O3Na2O:Al2O3 ratio
-111-Luuuuuuuu 16:l
5.09: 1
2. A method for producing zeolite Y according to claim 1. 3. The method according to claim 1, wherein the acid in the regulator of activated soda is sulfuric acid. 4. The method according to claim 1, wherein the alumina and 7-sulfuric acid in the conditioner for activated soda are aluminum sulfate. 5. The method of claim 1, wherein the combined source of silica and alumina is an aluminum salt gelling mother liquor. 6. The method according to claim 5, wherein the aluminum salt for gelling the R1 liquid is selected from the group consisting of aluminum sulfate, aluminum chloride, aluminum sulfate, and mixtures thereof. 7. The method according to claim 56, wherein the aluminum salt is aluminum sulfate. 8. The method of claim 1, wherein the reaction product is crystallized after heating the reaction slurry and decanting excess mother liquor. 9. A source of alumina, a source of silica, and an active sorter modifier are fed into the mixer in separate streams, a source of nuclei or nucleation centers is added to one of said streams to form a reaction slurry, and then this A method according to claim 1, wherein the reaction slurry is heated in step (b). 10. The method of claim i9, wherein said separate streams are fed simultaneously to a mixer. 11. High silica zeolite Y which has been subjected to Ha treatment according to the method described in claim IF. 12. High silica zeolite Y produced by the method according to claim 2. 13. M l by the method described in claim 3
14. High silica zeolite Y produced by the method described in claim 4. 15. High silica zeolite Y produced by the method described in claim 5. 16. High silica zeolite Y produced by the method set forth in claim 6. 17. High silica zeolite Y produced by the method set forth in claim 7. 18. Claim 1. High silica zeolite Y produced by the method described in claim 8. 19. High silica zeolite Y produced by the method described in claim 9. 2. Manufactured by the method described in claim 1θ. High silica zeolite Y. 21, the amount of absorbed R of amorphous silica is small, and expressed in moles of oxide, formula % formula %: where W is zeolite) 5.0 in the crystal lattice of Y. (l /2 width at height)2, where the area and width of the peak are
9's deconvoluted magic angle spike/g
si[IA
l] for the peak at least 6 and Si[OAl
] a sharpness index S of at least about 2.2 for the peak;
1. a high silica well crystallized zeolite Y having;
. 22, the number of sharpness fringes is at least 7 for the S i '[1'A'l ] peak and at least 2.5 for the 91 [OA1] peak. Zeolite Y. 23. High silica zeolite Y according to claim 21, wherein w has a value greater than 5.4. 24. High silica zeolite Y according to claim 21, wherein w has a value greater than 5.8.