DE3347123A1 - TYPE Y FAUJASITE WITH A HIGH SILICON DIOXIDE / ALUMINUM OXIDE RATIO - Google Patents

Description

The invention relates to the production of a type Y zeolite with a high silica / alumina ratio -JO ratio and the resulting unique zeolite.

US Pat. No. 3,130,007 is the basic patent for zeolite Y; then the zeolite is based on the oxide moles as

15 0.9 + 0.2 Na ₂ O: Al ₃ O ₃ : w SiO ₃ : χ H ₂ O

where w is a value greater than 3 up to about 6 and χ can be a value up to about 9. According to patent the zeolite Y is used as an adsorbent.

Two types of silica sources are disclosed in US Pat. No. 3,130,007 discussed. If the main source of silica is a cheaper source of silica such as sodium silicate, Silica gel or silica, the zeolite Y composition produced usually has a silicon dioxide / aluminum oxide Molar ratio (SiO "/ Al" O ^,) of greater than 3 up to about 3.9. Examples are given in Tables III and IV. The least used Amount of sodium oxide is in range 5. By multiplying the lowest Na "O / Al" O -. ratio, which is 0.6 is, with the lowest SiOp / Al-O ^ ratio of 8 results in the lowest possible Na_O content 4.8 moles, which, as discussed below, is located above line A in Figure 1.

Are zeolite Y compositions with silicon dioxide / If alumina molar ratios above about 3.9 are desired, US Pat. No. 3,130,007 describes a as being preferred Main sources of silica, more expensive sources of silica such as aqueous, colloidal silica sols and reactive, amorphous, solid silicas are used. There .these .- 'colloidal silica sols and reactive, amorphous, solid silicon dioxide ^ in front of M 1 ο i.ol \. ". υ sodium silicate are expensive materials, US Pat. No. 3,130,007 does not teach the Y-type zeolites high silica can be made from cheaper reactants.

According to US Pat. No. 3,130,007, a first digestion -15 at ambient or room temperature is also required. the Table V shows the critical importance of this cold aging for the entire production process. · '... .

GB-PS 1 044 983 describes the preparation of type Y zeolites having a silica / alumina ratio of 3 to 7, the reactants having low ratios of sodium oxide to silicon dioxide and water to silicon dioxide. As in U.S. Patent '3,130,007, the preferred source of silica and the material used in all examples is to provide a well crystallized NaY form with a SiQ ₂ / Al ₂ O ^ ratio of 5 .5 to 6.8 is claimed, · Silicic acid sol-, which is

30 is an expensive material.

U.S. Patent 3,8.08,326 describes the use of inoculants, or nucleation centers, with an average Size · below 0.1 in order to produce Type Y zeolites. According to Example II, the resulting

BATH ORIGINAL

Animal zeolite particles are described which have a silica / alumina ratio from about 5.0 to 6.0, but no individual values are given. The SiO “/ Al 0, ratio varies from 9.5 to 14.5 and the amount of Na "O added is called an amount indicated, which in each case is greater than the amount used according to the invention.

U.S. Patent 3,671,191 describes the preparation of a synthetic high silica faujasite by using seeds and a silica / alumina ratio of reactants of about 16: 1 at this preferred silica / alumina synthesis ratio of 16: 1 is the sodium oxide / aluminum oxide ratio shown in the example 6.6. This is indicated as point G in FIG. Among the manufactured products there is one with a ratio of 5.2 in Example 2 and 5.4 in

Example 3.

20 ". - ■

US Pat. No. 3,639,099 describes the preparation of a faujasite having a silica / alumina ratio greater than 4 using crystal seeds. The advance made with this patent has been the use of a lower silica / alumina ratio. A range of 8 to 12 SiO "to 1 Al_O- is given, with a silica to alumina ratio of about 9: 1 in the reaction slurry being preferred. In this case, in the preferred reactant mixture, there is 3.5 + 0.4 Na O for each Al-O. The lowest level at a silica / alumina ratio of 9: 1 would be 3.1 moles of Na ₁₂ O. This point is indicated as point F in FIG. Among those prepared according to Table 1 with a ratio of 10: 1

Products the lowest _{amount of free Na 2} O used was 3.5 and this yielded a zeolite with a SiCl / A ^ C ^ ratio of only 5.47.

U.S. Patent 4,016,246 describes the manufacture of Zeolite Y having a silica / alumina molar ratio of greater than 3 up to about 6.2. The procedure " requires the use of an "active" sodium meta- .. silicate hydrate derived from conventional sodium metasilicates is distinguishable. This particular hydrate is made by three processes described in the patent. Since this starting raw material is difficult to obtain ·. hold is because it requires special manufacturing techniques, the process according to US Pat. No. 5,4016,246 also appears to be expensive to carry out.

U.S. Patent 4,178,352 describes a synthesis of Y-type zeolites using a minimal excess of reactants. It is a general reference

2 "is present that the resulting zeolites can have a silica / alumina ratio of about 4 to 5.5. However, the highest ratio shown for the products in the examples is 5.1 in Example 6. In the finished reactant mixtures, for each Moles Al-O ^ from 4 to 7.5 moles SiO ₂ and from 1.2 to 3 moles Na ^ O. In most of the examples reactant solutions are used in which the silica / alumina ratio is from 6 to 1 and 1.8 or .1.9 moles of Na "O" are present * In Figure 1, point E represents this process, the silica / alumina ratio being 6 and 1.8 ". moles of Na", 0 per mole Alumina are present.

The US-PS 3,574,538 describes the use of - kaolin and in the preferred embodiment meta-

Kaolin and sodium silicate in the form of water glass for making faujasite materials with a silica / alumina ratio above 4.5 from inexpensive raw materials. In the examples, the production of products whose highest silicon dioxide / aluminum oxide ratio Is 5.90 and 5.95. In industrial practice, however, it is difficult to obtain kaolin and / or metakaolin which can has desired chemical and physical properties that optimize this process.

GB-PS 1 431 944. describes how to make a crystalline aluminosilicate zeolites having a silica / alumina molar ratio in the range from 5.5 to 8.0. The procedure requires a series of successive ones Process steps for adding the reactants. First is a faujasite precursor solution formed and heated. Then a sodium silicate solution is added to the SiO ^ / Al-G ^ molar ratio

ⁿ i ^{s to} increase. Subsequently, as a critical step, an aqueous aluminum chloride solution is added to form a gel slurry. Additional process steps require heating, separating the gel from the slurry, and adding more water to the gel with further heating to promote crystallization. The process of GB-PS 1,431,944 does not relate to a synthetic process in which all of the reactants are mixed together essentially at the same time.

It is an object of the invention to provide a type Y zeolite having a high silica / alumina ratio of greater than 5.0.

It is a further object of the invention to provide a zeolite of type Y. having a high silica / alumina ratio. a high degree of crystallinity and without entrapped silica.

Another object of the invention is to provide a high silica type Y zeolite derived from alumina sources other than 'Metakaolin or kaolin is made.

10. .

Furthermore, according to the invention, a zeolite of the Y type is to be included high silica content can be created, which is useful for catalytic purposes, by inexpensive

. Silica sources such as sodium silicate, silica gel

15 or silica can be used.

It is a further object of the invention to lower the content of active sodium oxide in the reaction mixture, a high silica type Y zeolite to accomplish.

It is also an object of the invention to provide an aluminum

. sulfate gelled mother liquor from a previous one To use synthesis as a starting material in order to

.25 stop at 'active sodium oxide and a To prepare high silica zeolite Y.

High Silica / Alu- 'Type Y Sodium Faujasite Minium oxide content (High silica / alumina sodium Y type faujasite, "HSAY") is produced by the content of active sodium oxide is carefully regulated to a level below the amounts conventionally used will. . Of the' . Type Y faujasite is made from a different source of alumina than metakaolin or kaolin produced while the silica source is a

inexpensive source such as sodium silicate, silica gel, silica, or mixtures thereof. The sodium oxide content can be determined by one of two different methods or reduced after a combination of the two. The first concerns the addition of a regulating agent, for the active sodium oxide such as an acid and / or an aluminum salt solution formed from aluminum and an acid that reduces the amount of active sodium oxide in the zeolite synthesis slurry. Preferred Materials are a dilute acid or a dilute aluminum sulfate solution. After another Process is used as the starting reactant. . a combined source of reactive silica and alumina used with low active sodium oxide content.

- | 5 These can be used in conjunction with those discussed above individual sources of silica and alumina can be used. A preferred combined source is a mother liquor from a previous synthesis which has been treated with an aluminum salt to obtain a mother liquor with a low soda content gelled with aluminum salt. A preferred aluminum salt according to this embodiment is aluminum sulfate, which is also known as alum.

By lowering the sodium content, it is possible unique, well crystallized NaY zeolites with a silica / alumina ratio of 5.0 and higher and in particular 5.8 and higher. These unique high silica / alumina ratio products can also be an ion exchange with rare earth or ammonium cations up to are subjected to even lower Na_O contents, about thermally and steam-stable zeolitic promoters for petroleum cracking catalysts, petroleum hydrocracking catalysts

- ^ Cj ren etc manufacture.

ORlRlMAl

The faujasites of type Y prepared according to the invention have a high degree of crystallinity. These materials are discussed in more detail below becomes, by magic angle spinning nuclear magnetic resonance, "MAS NMR"), .so the peaks for Si (I Al) and Si (O Al) are sharper than. with comparable .commercial samples. By · Darn to I I on dor HohäVfo tin Ratio to the Si (2 Al) peak and multiply by .10 a sharpness index, S.L, - is obtained. The S.I. for the Si (I Al) peak is at least 6 and preferably at least 7, while the S.I. for the Si (O Al) peak at least about 2.2, and preferably at least 2.5

amounts to.

Figure 1 shows the composition of the slurries for the production of the faujasite Y products, expressed as the ratio of Na-O and SiO "to Al" O_., in graphic Depiction.

20 ■ "■ '■

FIG. 2 shows the developed (deconvoluted) MAS NMR spectra for the zeolite Y according to the invention with a high silicon dioxide content and for commercially available NaY.

FIG. 3 shows the SiO ₂ / Al O ^ ratio versus the length of the unit cell in faujasites of the NaY type. high silicon dioxide / aluminum oxide ratio in graphical representation.

The sodium faujasites of type Y with a high silica / alumina ratio are made from aluminum oxide, silicon dioxide, sodium oxide sources, crystal nuclei or nucleation centers and a further reactant produced that had a reduced concentration of active sodium oxide in the reaction mixture allowed. · ■ ·

BATH ORIGINAL

The more preferred sources of alumina can be either alumina trihydrate, alumina monohydrate, one Sodium aluminate solution or an aluminum sulfate solution (Alum) be. Other aluminum oxide sources are aluminum oxide gel, Aluminum hydroxide, aluminum chloride, aluminum nitrate or other salts of aluminum and acids possible. It is particularly desirable not to use kaolin or metakaolin because it is used in industrial applications It is difficult in practice to procure these two materials in a form that has the desired chemical and has physical properties that optimize this process.

The preferred sources of silica are inexpensive - | 5 sources such as sodium silicate, silica gel, or silica Mixtures of these materials. For industrial use it is particularly desirable, not the more expensive ones Silica sources such as aqueous colloidal silica sols or the more expensive forms of the reactive, amorphous, solid Siliciumdioxi.de to use. Another possible source of silica is one with aluminum sulfate gelled mother liquor, which is discussed in more detail below.

The preferred source of sodium oxide is obtained from the sodium form of the compounds used to supply the Silica and alumina can be used, namely sodium silicate and sodium aluminate. More possible Sodium oxide sources are sodium hydroxide and sodium

3Q trium carbonate, but it must be noted that it The aim of the present invention is to reduce the amounts of sodium oxide in the reaction mixture.

The crystal nuclei or nucleation sites can _{manufacturer; i} - kömmliches Y zeolite seed material or the mother liquor

. - 15 -

from the production of zeolites A j X or Y or with Aluminum sulphate can be gelled mother liquors. A preferred one. Process for producing crystal seeds is in U.S. Patent 3,808,326 and is described in Example 1 below.

The additional reactant, which allows a reduced concentration of active sodium oxide 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 regarded as a regulating agent for the active sodium oxide, since it is with the excess of active Sodium oxide reacts and binds this so that it does not adversely affect the synthesis of zeolite Y. with a high silicon dioxide content. Examples of materials that increase the concentration of active sodium oxide are acids, salts from the reaction of aluminum with an acid and mixtures of these both materials. The acid is preferably added in dilute form and is a preferred acid Sulfuric acid. In a preferred embodiment of the invention, these added regulating agents are for the active sodium oxide is added to the slurry at the time of mixing or they are added within Added 3 hours from the time the slurry was heated to give the most effective results obtain. . . ■

The other form of the ■ additional reactant is used for creation a combined source of reactive silica and alumina with a low content of active sodium oxide. This can be done by adding an aluminum salt to the mother liquor containing silicon dioxide from a previous production, around a silica / alumina hydrogel with a

low active sodium oxide content. Examples of aluminum salts are aluminum sulfate, aluminum chloride, aluminum nitrate or mixtures thereof. The preferred salt is aluminum sulfate (alum).
A preferred example of this recycling method is shown in. US Pat. No. 4,164,551 in which alum, ie aluminum sulfate, is added to the filtered mother liquor to precipitate a silica / alumina hydrogel. This hydrogel is referred to as mother liquor gelled with aluminum sulfate, AGML, and this or other mother liquors gelled with aluminum salt can, according to the invention, be used directly as starting material for the production of the high silica faujasite.

15 '. .

According to the invention, the content of active sodium oxide is reduced below the levels conventionally used. In FIG. 1, line A shows conventional formulations which contain an NaY faujasite with an SiO ₂ / Al ₂ O ₃ ~

Deliver ratio of 5.0. In a reaction slurry according to point G, the 16 moles of SiO "for each mole of Al" 0_. contains, it is common to use a 0 Na ₉ / Al ₉ 0 ^ -Verhaltnis of about 6.6. In a reaction slurry according to point F which contains 9 moles of SiO2 for every mole of Al ₃ O ₃ , the lowest value for the Na ₂ O / Al ₂ O ₃ ratio is about 3.1, while in a reaction slurry according to point E with 6 moles of SiO for each mole of Al O _3, the Na ₂ O / Al “O ratio is about 1.7. Line A is accordingly based on at least the following points indicating the ratio values in the synthesis slurry:.

SiO ₂ / Al ₂ O : 1 relationship : 1 16 : 1 9 6th

Na ₂ O / Al ₃ ratio 6.6: 1
3.1: 1
1.8: 1.

. . According to the invention, the sodium oxide contents are set to contents lowered below line A by regulating means for the active sodium oxide, such as an acid and / or a

ΊΟ Salt of aluminum and an acid can be added. The salt can be added as a solution. The preferred Forms of the acid or salt are dilute. Solutions, and a preferred salt form is dilute Aluminum sulfate solution (alum). With the more preferred

-15 Embodiments of the invention will reduce the level of active sodium to levels that are illustrated by the line B in Figure 1, wherein in a Reaktionsauf slurry with 16 moles of SiO "for each mole of Al 0, the Na ₂ 0 / Al 0 ., - ratio is about 5.0 and in a reaction slurry with 9 moles of SiO "for .each mole of Al ₀ O-. about 2.4. If this 2 - ' 2 3

Starting composition used, NaY-faujasite are obtained with a SiO "/ Al" _i O_ ratio of .5,8 to 6.0. ·. . '

Line B is accordingly based at least on the following, the ratio values in the synthesis slurry specifying points: '

₂ / Al ₃ O ₃ ^Na 2 ° / ^A1 2 ° 3

Ratio ratio

- 16.: 1 5: 1

9: 1 '2.4: 1

If these materials are put into the reaction vessel,

so care must be taken that there are no gels

BATH ORIGINAL

which are then difficult to disperse or dissolve. If the materials are added one after the other, a sequence is preferred, first diluted sodium silicate, then slowly while stirring the dilute acid, then slowly, with continued stirring, the dilute sodium aluminate and Finally, the crystal seeds are added »According to a further preferred method for acceleration Upon addition of the reactants, the reactants are fed in three streams into a high speed mixer fed that. a soft gel forms that can be transferred directly to the crystallization reactor can. One stream contains sodium silicate and seed crystals, the second stream consists of a dilute acid

"15 and the third stream of dilute sodium aluminate.

According to a further embodiment, after an initial Heating the reaction mixture reduces the liquid volume of the slurry by decanting be, so that the subsequent crystallization that carried out over a relatively long period of time " becomes, due to the removal of the excess liquid, with a significantly reduced volume of reactant, such as a volume reduced by 2/3 can be made. The duration of the initial Warming can range from a relatively short period of time, such as 15 minutes, to longer periods of time, such as a day, vary. Since the reaction is carried out in a completely aqueous system, the mixture can reach temperatures of about 100 ° C can be heated without the need for a printing device.

When using a reaction slurry with a 3b ratio of 16 SiO ₂ to 1 Al ₃ O ₃ , sodium

BAD ORJGJNAl

Type Y jasites having a SiO./Al-O ratio of about 5.4 to about 6.0 are obtained, depending on the present. reduced amount of active sodium oxide. If a reaction slurry is used in which a Ver. ratio of 9 SiOp to 1 Al ₃ O ^ is present, then sodium faujasites of type Y with an SiO "/ Al" O -, - ratio of about 5.3 to about 5.8 are obtained, depending on the reduced amount of active sodium oxide.

The HSAY zeolite can, like conventional zeolites of the Type NaY, an ion exchange with solutions of salts of rare earths or salts of other metals or ammonium salts or a combination of these

-15 den to lower the Na ion content in the zeolite and . a thermally and hydrothermally stable accelerator for producing catalysts for the treatment of petroleum fractions. Such an ion exchange can be performed by using the HSAY, which is synthesized has a Na "O content of about 10 to 15%, with an aqueous solution of any of the above salts for 1 minute to 100 hours at temperatures' .Contacted from 0 to 100 ° C, the mass filtered and the zeolite filter cake washes. The exchange can-with or without calcination of the exchanged Zeolites are repeated several times in order to reduce the Na ion content of the exchanged zeolite to 0.1 up to 5% NaO, depending on the intended use for the exchanged HSAY accelerator

3Q purpose. Such ion exchange processes are known to those skilled in the art known. Alternatively, the ion exchange can be done after the HSAY accelerator becomes one Catalyst has been processed.

The high silica type Ύ zeolites of the present invention are believed to be unique and are characterized by their high degree of crystallinity as measured by the sharpness index of their NMR spectra, as discussed below, and by the absence of entrapped silica. With an increasing SiO-ZAl ^ O -.- ratio, the nature of the chemical bond concerned changes. S. Ramdas et al describe in "Ordering of Aluminum and Silicon in Synthetic Faujasites", Nature ,. Volume 292, 16. 7. 1981, pages 228-230, that zeolites can have 5 types of bonds from silicon to silicon or aluminum. These 5 bond types are described by a designation system that indicates the number of aluminum atoms

Ί5 ■ the silicon is bound via oxygen atoms. Each silicon atom is bound to 4 oxygen atoms - which in turn are bound to silicon or aluminum. The 5 bond types are Si (4 Al), Si (3 Al), Si (2 Al), Si (I Al) and Si (O Al). Accordingly, if silicon is bound to 4 aluminum atoms via the 4 oxygen atoms, the designation is Si (4 Al). See also Klinowski et al "A Re-examination of Si, Al Ordering in Zeolites NaX an NaY", J. Chem. Soc, Faraday. Trans. 2, T8_ _f 1025-1050 (198.2). ·

25th .

Ramdas et al identified the 5 bond types by nuclear magnetic resonance measurement, in Table 1 below is the distribution of the 5 bond types for a conventional NaY faujasite with a SiO ^ / Al-O ^ -Ver-. ratio of 4.8 and the theoretical distribution for an HSAY material with an SiO ₂ / Al ₂ O ₃ ratio of 6.0 is shown. For comparison, the idealized possible binding for faujasite of the NaX type is also given in the table.

BATH ORIGINAL

Table 1

F aujasite type

NaX NaY HgAY SiO ₂ / Al ₂ O ₃ ratio. 2.4 4.8 6.0

Bond distribution (idealized)

16 • 0 0 8 ■ 4- ■ 0 0 16 ■ 16 0 12th 16 2 ' 2 4th

. 'Si (4 Al) Si (3 Al)

• Si (2 Al)

¹⁰ ■ Si (I Al) Si (O Al) '

Is the material of the type HSAY according to the .inventive - | If a process is not produced, it has more Si (I Al) and Si (O Al) bonds than conventional zeolites of the NaY type and less Si (3 Al) bonds. .

For the experimental measurement of these 5 binding types,

29
a high-resolution Si-NMR spectrum, as shown by Ramdas et al in FIG. 3, and from this a computer-simulated curve is created on the basis of Gaussian peak shapes. The area under the curves shows the relative occupancy of the 5 possible arrangements. This new analytical method was also used to determine the actual SiO ^ / Al-CU ratio. used in the crystal lattice to identify entrapped silica, if any, and to determine how well the sample was crystallized. In the process. Nuclear magnetic resonance spectra, (NMR)., of silicon-29, an isotope of silicon which is present in an amount of 4.7% of all silicon atoms, are used. The spectra are obtained at 79.45 MHz using magic angle spinning

J ₁ I _} . MAS) is used, a technique that significantly improves the resolution of the NMR spectra. Two with A and B

designated HSAY samples, produced according to the method according to the invention, and a commercially available NaY sample, produced according to the method of US Pat. No. 3,639,099, were examined according to this NMR method using MAS. Sample A was prepared according to the method described in Example 15 below, and Sample B was prepared according to the method described in Example 5. The NMR results showed that the HSAY in the lattice had a SiO _o / Al _o O ^ ratio of 5.6 + 0.4, that it had no entrapped silica, and that it was very well crystallized. For the present purposes the SiO ₉ / Al_O -.- ratio is determined according to the conventional wet chemical method. The ratio determined from the NMR data has been shown since this value accurately expresses the amounts of silica and alumina in the crystal structure. If any entrapped silicon dioxide is present, this is not taken into account in the ratio determined by NMR. However, the NMR data are less accurate, as can be seen from the greater spread of the values as shown in Table 2.

The MAS spectra were obtained at 79.45 MHz and related to tetramethylsilane by using external HMDS (hexamethyldisiloxane) as reference standard and assuming δ HMDS to be +6.7 ppm related to TMS (tetramethylsilane). The spectra show 5 peaks which are characteristic of the 5 possible environments that silicon can have in the tetrahedral arrangement of the zeolite structures, as the spectra shown in FIG. 2 show. The scale in FIG. 2 is based on TMS, the TMS peak appearing at 0.

The spectra were entered into the separate components keys (developed) assuming that

these are Gaussian in nature. The entire assignment of the spectra is shown below in Table 2 together with the peak areas corrected by sideband corrections with regard to minor differential effects. ■ These small differences between the displacement values in the table compared with those in the spectrum are zurückzü- on the overlaps between the ^peaks. to lead. The area of each peak was chosen so that the sum of the areas of the 5 peaks was 100. The width w of each peak at 1/2 peak height was also calculated. The Si (I Al) and Si (0 Al) peaks of the HSAY-Pro. . be in Figure 2 are sharper than the comparable, - peaks of the commercially available NaY. This sharpness can be mathematically defined as follows: ·. . ; If the <> area of the Si (2 Al) peak of each -Y sample is used as: reference, a dimensionless sharpness factor S for each peak is defined as. ''

_ Peak area A

(Half width) w

The sharpness index S.I. for any other than the Si (2 Al) peak can then be defined as

s.r. =

^{10 S} Si [nAl] ^S Si [2 Al]

These 'values are for η = 0 and 1 in the table below. Ie 2 reproduced.

BATH ORIGINAL

. - 24 -

Table 2

Commercial HSAY

Sample A B

SiO ₂ / Al ₂ O ₃ ratio

according to NMR 5.2 + 0.4 5.6 + 0.4 6.0 + 0.4 according to chemical
analysis 5.0 + 0.1 5.9 + 0.1 6.0 + 0.1 Peak types Si (2 Al). Area A. 36.0 34.5 33.7 Width w at 1/2 height 3.1 3.35 3.2 2
Sharpness, A / w 3.75 ■ 3.07 3.29 Si (I Al) Area A 42.4 47.5 47.1 Width w at 1/2 height 5.1 4.6 4.0 2
Sharpness, A / w
*
Sharpness index 1.63
4.3 2.24
7.3 2.94
8.9 Si (O Al) Area A 9.0 9.3 13.6 Width w at 1/2 height 3.6, Z, 8 4.0 2
Sharpness, A / w
* ■
Sharpness index 0.69,.
i, 8 ': 1.19
3.9 ■ 0.85
2.6

Sharpness index = sharpness of the Si (I Al) or Si (O Al) peaks x 10 /

Sharpness of the Si (2 Al) peak.

The data in Table 2 show that the Si (I Al) and Si (O Al) peaks from HSAY are much sharper than the same peaks from commercially available NaY. The Si (I Al) peak has a sharpness index S.I. of at least 6 and preferably at least 7, while the Si (O Al) peak has a sharpness index of about 2.2, and preferably at least 2.5. This sharpness of the Si (I Al) - and Si (O Al) peaks of the HSAY of the invention show this high SiO ^ / Al-O -.- ratio in the crystal lattice and the high degree of crystallinity of the HSAY.

As described above, entrapped silica can be detected from the magic angle NMR spectra because there is then a characteristic, separate peak for silicon dioxide, which is caused by silicon atoms is characterized, which are only bound to such oxygen atoms, which in turn are not to others are bonded as silicon atoms.

ZZ The presence of entrapped silica can also be determined from the unit cell lengths. E. Dempsey et al, Journal of 'Physical Chemistry, 7 ^ 3 (2), 387-390, (1969) compared the chemical analysis values with the unit cell lengths of various samples of NaX and. NäY faujasites. She. found that the lowest unit cell length of their NaY samples was 24, -66 R for a NaY whose SiO / Al-O, ratio was 5.32 according to chemical analysis. When the unit cell length was plotted against the number of aluminum atoms per unit line (FIG. 1 of their publication), however, it was found that the lowest number of aluminum atoms per unit cell is 53, which corresponds to a cell size or unit cell length of 24.665 R. Although they examined various other NaY samples for which chemical analysis had ratio values

up to 5.83 showed none of the NaY sample had a unit cell, the length was less than 24.665 R. They therefore suspect that the samples with a high SiO ~ / Al "O" ratio contain amorphous silicon dioxide. -

If an NaY sample contains amorphous silicon dioxide intimately mixed with crystalline NaY, the ratio determined by quantitative chemical analysis will be higher than the actual ratio in the crystal lattice. Their data, which are taken from their table 1, were plotted in FIG. 3 as a unit cell size against the SiO ^ / Al-O ^ ratio. The open squares in Figure 3 show your data for well crystallized NaY samples; the unit cell length is inversely proportional to the SiO ^ / Al-O ^ ratio. The triangles in FIG. 3 show that the NaY samples which, according to the chemical analysis, had a high ratio, show no progressive cell length shrinkage with increasing ratio; these triangular samples presumably contain entrapped amorphous silica. For these high ratio samples, the cell length remains. at 24.66 to 24.67 Å, although the ratio increases from 5.4 to 5.8. It can be concluded from this that the highest ratio in the crystal lattices of the NaY samples examined by them was about 5.3. The filled squares in FIG. 3 are plots of the unit cell length versus the SiO ^ / Al ^ CK ratio in the faujasites of the NaY type according to the invention with a high silicon dioxide / aluminum oxide ratio. The filled squares appear to essentially continue the line of the open squares and they show that the HSAY samples according to the invention have a unit cell length which is proportional to the SiO 2 / Al ₇ O., - ratio according to chemical analysis.

τκ The filled squares are closed down to the bottom

a unit cell length of 24.58 A, which corresponds to a ratio of 6.0. Accordingly, the HSAY samples according to the invention contain no enclosed, amorphous silicon dioxide in intimate admixture with the paujasite. In addition, the ratio determined by chemical analysis in each sample gives the actual SiO ₂ / Al _? O - ratio in; dom crystal filter again.

The unique Y type zeolites of the present invention high silica, with their high degree of crystallinity and the absence of entrapped Silicon dioxide is very suitable as a catalyst material. These catalysts can by known methods getting produced. The HSAY faujasite is subjected to an ion exchange to reduce the alkali metal content to lower and stabilizing, catalytically active ions to add. Usually the HSAY is filled with rare earth ions and / or ammonium and hydrogen ions.

2ü exchanged. The HSAY faujasite can do ion exchange either before or after being incorporated into an inorganic oxide matrix. Furthermore, the ion-exchanged HSAY are calcined, i.e. either before or after incorporation into a catalyst matrix be heated to temperatures of about 200 to 700 C. The HSAY faujasite is used as a hydrocarbon cracking catalyst used, it preferably has an alkali metal content, usually as sodium oxide, Na "0, expressed by painful than about. 6% by weight -.

The conversion of the HSAY zeolite into a usable one particulate catalyst is achieved by converting the finely divided HSAY zeolite into an inorganic Dispersed oxide matrix. The inorganic oxide matrix

Tij can be made of silica-alumina, alumina,

BATH ORIGINAL

Silica sols or hydrogels in combination with additives such as clay, preferably kaolin, and other zeolites such as zeolites of the ZSM type exist or contain them.
5

The catalyst compositions can be prepared according to the teaching of US Pat. No. 3,957,689, according to which finely divided Zeolites and clay are combined with an aqueous slurry that is spray dried and an ion exchange is subjected to obtain a highly active hydrocarbon conversion catalyst. Further the catalyst preparation can be carried out according to the general teaching of CA-PS 967 136, according to which Zeolite and clay. with an acidic alumina solbine agent be combined. Will producing a Desired catalyst is a silica-alumina hydrogel binder contains, so.can the manufacturing process U.S. Patent 3,912,619 can be used.

As mentioned above, the HSAY zeolite is particularly stable to hydrothermal deactivation conditions, which normally occur when regenerating cracking catalysts. Regeneration closes high temperature oxidation (Burning) in to burn off the accumulated carbon deposits at temperatures of up to 1000 ° C remove. In addition, it has been found that catalysts which contain the "· according to the invention .HSAY, especially resistant to the deactivating

3Q effects of metal impurities such as nickel and vanadium which are rapidly deposited on the catalyst during the cracking of residual hydrocarbons.

Although the exact cause that the invention Tc moderate HSAY and the invention, ■ these contain-

BATHROOM ORIGINAL.

the catalysts are particularly active and stable, is not fully known, it is assumed that the particularly high catalytic activity and stability after steam deactivation and in the presence of contaminating metals is due to its special structure, as by S. Ramdas et al in "Ordering of Aluminum / And Silicon In Synthetic Faujasites ", Nature, Volume J ¹ ). ¹ , July 16, 1981, pages 228-230.

When 'using' the catalyst according to the invention. Ren for catalytic cracking combined with hydrocarbon feedstocks, which are usually hydrocarbon fractions. of the residual oil type containing up to about 1000 ppm nickel and vanadium and up to about 10 wt% sulfur and 2 wt% nitrogen. The cracking reaction is usually carried out at temperatures of about 200 to 600 ^° C., a catalyst / oil ratio of the order of 1 to 30 being used. During the cracking reaction, the catalyst usually accumulates from about 0.5 to 10 weight percent carbon which is then oxidized as the catalyst is regenerated. It has been shown that these catalysts are able to have a certain

25 degree of viability.

. . The catalysts can advantageously with Other additives or components such as platinum can be combined to improve the CO / SO characteristics of the catalyst improved. Preferably will. Platinum in the total catalyst composition in amounts of about 2 incorporated up to 10 ppm. Furthermore, the catalyst

■ ren in an advantageous manner with traps for SOx such as Lanthanum / alumina compositions are combined that are on the order of about 20 wt.% Lanthanum oxide contain..

BATH ORIGINAL

The invention is illustrated below with the aid of examples.

Example '1 5. ".

This example shows the production of nucleation centers or crystal nuclei according to the teaching of the US-PS 3 808 326.

A solution of 919 g of sodium hydroxide in 2000 ml of water was heated to dissolve 156 g of aluminum trihydrate (Al ₂ O- .. 3H “O) and then cooled to room temperature. It is referred to as solution A. A second solution B was prepared by mixing 3126 g of a 41.2 Be sodium silicate (weight ratio 1.9 Na ₂ O: 3.22 SiO ₃ ) in 1555 ml of water. Solution A was then mixed into solution B with rapid stirring. The mixture was aged at room temperature for about 24 hours; then the slurry, nucleation centers or seeds were ready to use.

Examples 2-5

These examples demonstrate the production of high silica / alumina-type sodium faujasite, wherein the seeded slurry has a silica / alumina ratio of 16: 1.

30 - -

The reactant solutions were prepared as follows.

A dilute acid solution was made by adding various amounts of concentrated sulfuric acid with a specific gravity of 1.84 as indicated in Tabel-> t, Ie 1, made to 100 ml of water, and the Mixture was stirred well.

A dilute sodium aluminate solution was prepared

by adding 91 g of sodium aluminate solution with a content of 17.2% by weight of Na ₂ O and 21.8% by weight of Al ^ O-, to 214 g of water

were given.
5 -

A dilute sodium silicate solution was prepared

by placing 648 g of a 41.2 ° Be sodium silicate solution with • a ratio of 1.0 Na ₉ O: 3.22 SiO ₂ in a 1.2 l mixing cup of a Hamilton Beach mixer and adding 200 ml of water; the water was mixed thoroughly with the sodium silicate in the mixer.

During the mixing process, the diluted silicate dilute acid and then the dilute aluminate

added.

15 · '' "■■ ■ · ■ ■ '-

Finally, 47 g of seed slurry was added to the Mixture given.

The slurry was poured into polypropylene bottles ^and capped loosely. The bottles were heated in a water bath until the slurry reached 85 ° C; at this point the bottles were transferred to an oven heated to 100.degree. Samples of the slurry were taken from time to time by stirring the contents well and withdrawing 50 ml of the slurry. The samples were filtered, washed to a pH of 10 to 10.5 and dried in an oven at 100 ° C.

The percentage. Crystallinity of each sample, as determined by powder x-ray diffraction photographs, would be compared to a well crystallized, commercial sample of Y sodium faujasite. The nitrogen surface area of the sample was 1-hour after degassing the sample at 538 ° C -3 ^ _{chromatography:} on a Perkin-Elmer shell 212D

Sorbtometer or according to the BET method on a Aminco-Adsorptomat measured.

The unit cell size of the cubic unit cell of the HSAY, in which all three axes have the same length (a = b = c), was measured as follows: About 1 g of HSAY powder, which was left overnight in a desiccator in an atmosphere with 33 % relative humidity was equilibrated with about 1 g of silicon metal powder. The silicon served as an internal standard for a powder X-ray diffraction diagram, which was produced using copper radiation filtered through nickel foil. The diffraction pattern was recorded from about 52 ° 23 to 6Ο ° 2Θ. The position of the reflection from the 997 plane (h = 9, k = 9 and 1 = 7) and the 999 plane were measured in degrees 20. The first appeared at about 54.0 to 54.2 ° 23 and. the second at about 58.7 to 58.9 20. The internal silicon standard has a theoretical reflectance at 56.12 ° 20. The measured for the two levels HSAY 23 was by the amount ^r kc igiert, deviated by which the Silici-umpeak of 56.12 °. The unit cell was then calculated using Bragg's equation:

25 a = 4 * "γ * h ² + k ² + l * ²

sin θ

in the L the wavelength of the copper K radiation of 1.54718 Å. The unit cell was the mean of the value of a for the 997 and 999 levels.

The results described in Table 3 below Type Y sodium faujasite products which crystallize from the slurries of Examples 2-5 had a high SiC ^ / A ^ O ^ ratio; in particular those of Examples 4 and 5.

Tabel

2 mole ; i; 0. Synthesis of sodium faujasites of type Y with high hours Crystal - ' 16 SiO ₂ : 1.0 Al ₂ O ₃ Unitary 1
LO
LO <<! 3 Na ₂ Q Silica / alumina ratio at linearity% nitrogen SiO / Al O cellular I. ΓΟ 4th A1 "O inoculated on sole immunizations with 100 + 1 ⁰ C surface relationship size LO example 5 6th Concentrated 104 m / g .. according to chemical No. ^- ' 5, 4th . sulfuric acid 36 102 analysis 24.61 '5, 2 G. 40 97 . 854 5.4 '■ ■ 24.60 5, 0 64 99 838 5.7 24.59 5, 16.7 108 853 5.9 24.58 20.9 802 6.0 24.9 29.1.

Examples 6-9

These examples illustrate the preparation of a type Y high silica / aluminum-5 sodium faujasite oxide ratio, the inoculated slurry being a Silica / alumina ratio. of 9: 1.

The sodium silicate and sodium aluminate solutions had the same concentrations as in Examples 2 to 5. The sodium silicate and half of the water were in the 1.2 liter mixing cup of a Hamilton Beach Mixer mixed. The crystal seeds prepared according to Example 1 were given in Table 4

The sodium aluminate solution was mixed with the other half of the water. The mixture became very viscous until the gel point was reached and the mixer was turned off. The gel was carefully and completely scraped out of the mixing cup and into the bowl of a Hobart After switching on the Hobart mixer, the remaining sodium aluminate solution was slowly metered in. Then the aluminum sulfate solution (alum), which contained 7.8% Al ^ O-, was slowly added with mixing. The thick, pasty gel was in 250 or 500 ml polypropylene bottles filled and loosely capped The further heating and analysis procedures were carried out as in Examples 2 to 5. The resulting faujasites of the NaY type, which are described in Tables 4 and 5, were prepared from the slurries of Examples 6 to 9. crystallized and had a high SiO ₂ / Al 0., - ratio, in particular those according to Examples 8 and 9 .

Table, 4

Synthesis of faujasites of the NaY type with high • silica / alumina ratio

inoculated slurries with 9 SiO

Mole.
Na ₂ OrI, 0
Al ₂ O ₃ crystal
germs
• g Reactants 235 sodium
silicate
. G Al ₂ (SO ₄ ) ₃
solution
G- Example.
No.: ■. 3.0. 194 Sodium aluminate water
solution g
9 ■ 220 .860 230 6.: '■ 2.8 194 ■ 140 184 860 260 7 ■ 2.6 175 129 169 774 262 8th 2.4 175 106 774 289 9 96

LO (Jl

Tabel

Synthesis of faujasites of the NaY type with high

Silica / alumina ratio inoculated slurries with 9 SiO "

1.0 Al ₃ O ₃

Response time and product analysis

example
No. hours
at 100 + 1 ° C 6 '..' 12th 7th 20, 8th . '36 9 60

Crystallinity % nitrogen
surface m ² / g 108 859 109 884 104 910 103 897

Ratio according to
chemical analysis

5.3
5.4
5.6
5.8

Unit cell size, a

24.64 24.62 24, -61 24.60

OJ CTl

- ". · Example 10

This example illustrates the synthesis using a reduced slurry volume after initial. Preferably heating, so that the crystallization that occurs during carried out over a relatively long period of time is, with a significant reduction in the required. such volume, can be made.

A slurry with a ratio of Silica to alumina of 16: 1 and one •. Composition according to Example 5 produced. The slurry was 'heated to 100 ° C' in a bottle without stirring for 24 hours. During this period

- | 5 · the solids settled on the bottom of the bottle 'away. After heating for 24 hours, the mother liquor was decanted so that the volume was reduced by about 2/3 became. The remaining solids surrounded by mother liquor were then heated to 100-C for 131 hours,

2
^{to obtain} a good product with a surface area of 897 m / g, a crystallinity of 94% and a unit time size of 24.59 Å. As Table 3 shows, this corresponds to an SiO ₂ / Al O_ ratio of 5.9.

25 Example 11

This example illustrates the preparation of the zeolite type Y using a reduced volume of slurry with a shorter initial heating time. '.

The procedure according to Example 10 was repeated with the difference that the slurry is not 24 hours

heated to 100 ° C for a long time but only 15 minutes to 100 ° C

c- was. The solids were on a Buchner filter

filtered off. The solids were then returned to the bottle and only enough mother liquor was added to just cover the solids. Since these solids were more fluffy than those prepared according to Example 10, a greater amount of liquid was required. The volume reduction was about 55-60%, which is slightly less than the volume reduction according to Example 10.

After the mixture had crystallized at 100 ° C. for 144 hours, the crystallinity of the product was 10 7%, the unit cell size was 24.61 Å and the wet chemical analysis showed a SiO ^ / Al "O, ratio of 5.8.

1-5 This example also shows that a good product is obtained with a reduced crystallization volume, the excess mother liquor being recovered and recycled or used for other purposes can.

20 ·

Example 12 . .

This example also illustrates the synthesis using a reduced slurry volume with a slightly longer initial warming period.

The procedure of Example 11 was repeated exactly, with the difference that the slurry was initially heated to 100 ° C. for 1 hour instead of 15 minutes. The solids were filtered off as described in Example 11 and just enough mother liquor was added to cover the solids. After 93 hours of heating at 100 ^° C., the degree of crystallinity was 109%, the unit cell size was 24.60 and the SiO / Al-O -

35 ratio according to wet chemical analysis 5.8.

Example 13

This example illustrates the use of mother liquor gelled with aluminum sulfate, AGML, as a source for a portion of the silica and alumina reactants when a slurry containing a silica / 16: 1 alumina ratio is used.

From a previous production of a sodium zeolite Type Y, prepared by the process of US Pat. No. 3,639,099, contained a typical mother liquor filtrate, filtered off from a completely crystallized NaY batch,

15th 4.9% SiO ₂ and 4.0% Na ₂ O.

Aluminum sulfate solution (alum) was added and the silica-alumina gel, AGML, precipitated and was collected by filtration. The gel contained:

12.6% SiO _2. 3.4% Na ₂ O

. .2.8% Al ₂ O ₃ 25 * 2.6% SO and.

in the rest of the water.

A slurry for synthesizing one of the present invention • Faujasites with high silica content have been

30- represents by mixing 300 g of AGML in a mixer with 200 g of water and .517 g of sodium silicate solution (41.2 ° Be with a content of silicon dioxide and sodium oxide in a ratio of 3.22 SiO ": 1.0 Na" O) were mixed. Then 54 g of sodium aluminate solution (18.2% Na ₂ O, 21.4 % Al ₂ O ₃ ), which were mixed with 185 g of water

was thinned, added and mixed well. Finally, 47 g of seed crystal slurry according to Example. 1 mixed into the mixer. In the slurry the effective ratio was 5.2 Na 'O : 1.0 Al ₂ O ₃ : 16 SiO ₃ : 280 H ₃ O.

The completely mixed slurry was placed in a 1.0 1 polypropylene bottle, which was transferred to an oven at 100 + 1 ⁰ C. After 61 hours the

ΊΟ Slurry a well crystallized sodium faujasite of type Y, which had the high silica content of the invention and a nitrogen surface of 952 m / g as measured by a Digisorb device from Micromeritics Inc., Norcross, GA.

-j 5 According to chemical analysis, the HSAY faujasite had the the following composition:

10.7% Na ₃ O, 19.8% ^Al ₂ ° 3 ^{and 69} ' ^{5% Si0} 2'

where the SiO _? / Al "O ^ ratio 6.0 and the crystalline

efficiency was 102%.

This example shows an effective use for a waste liquid as possible. .

Example 14

This example illustrates the use of "with aluminum sulfate gelled mother liquor as a source of some of the silica and alumina reactants when using a slurry with a SiIi-

3Q. cium dioxide / alumina ratio of 9: 1.

1080 g AGML according to Example 13 were in a mixer

o '

bowl introduced and 319 g 41.2 Be silicate added and mixed in the mixer. Subsequently was 69 g sodium aluminate solution slowly added and

mixes. The slurry set, softened after 1 to 2 minutes of mixing. Finally, 93 g of seed crystal slurry, prepared according to Example 1, were added. The slurry was transferred to a 1.0 L polypropylene bottle and heated to 1.00 + 1 ° C in an oven. The effective oxide ratio in the slurry was 2.4 Na 2 O: 1.0 Al ₉ O ₁ : 9 SiO ;, ■: ... 140 H ₃ O. - ■

"IG After 44 hours there was a Type Y faujasite with high Silicon dioxide content crystallizes out, its .stick-

2 ' '

. fabric surface was 937 m / g and the one good one

. Possessed a degree of crystallinity compared to a commercial NäY standard. Was 101%. The che-15 ' Mixed analysis of the composition on a dry matter basis gave the following values:

10.9% Na ₂ O, 20.4% Al ₃ O ₃ and -68.7% SiO ₃ . The SiO ₂ / AluO ₃ ratio was 5.7.

20 Example 15

This example shows the extension of the procedure. ^: on a scale to a 56.8 liter batch which yielded almost 6.0 kg of dry product.

40.0 kg commercial sodium silicate: (Philadephia Quartz "N" Brand, 4 0.8 Be density) was placed in a mixing tank and diluted with 11.5 kg of water. Of the The mixer was switched on and kept in operation while the chemicals were being metered in. 1531 g concentrated Sulfuric acid solution (density 1.84) -, diluted with 11.4 kg of water was added very slowly over a period of 15 minutes. The mixing process became another continued for half an hour.

Then a dilute sodium aluminate solution, made from 5226 g concentrated sodium aluminate solution (18.2% Na 0, 21.4% Al OJ, mixed with 5.9 kg of water, added slowly over a period of 1/2 hour.

Finally, 2631 g of crystal nuclei or nucleation centers (according to Example 1) were added. The slurry was pumped into a 75.7 1 reaction tank with a steam jacket and heated to 100 + 1 C to achieve the To bring about crystallization of the NaY. The slurry samples were taken from time to time to monitor progression monitor crystallization. After 105 hours at the specified temperature, the experiment was canceled. The slurry was filtered and the filter cake was washed free of excess mother liquor.

The product was a well crystallized HSAY with a SiOp / Al-O ^ ratio of 6.0 and a degree of crystallinity of 96%.

Example 16 '

This example shows both the scale expansion to a 56.8 liter batch of slurry as well as use another type of sodium silicate. The mixing and crystallization procedures were the same. how in example 13.

41.5 kg of Diamont Shamrock DS 34 were mixed together

Sodium silicate (25.6% SiO ₂ , 6.6% Na ₃ O) and 14.6 kg of water. A solution of 696 g of concentrated sulfuric acid diluted with 4.5 kg of water was added. The T ₅ 5253 g of sodium aluminate of the concentration according to

game 13, diluted with 4.5 kg of water, was added. Finally, 2192 g of seed crystals according to Example 1 were added.

The crystallization at 100 + 1 ° C gave a HSAY faujasite with a S.iO ^ / Äl ^ O -.- ratio in 72 hours of 5.8 and a degree of crystallinity of 104%.

Example 17

This example illustrates the preparation of a large batch with the addition of the reactants at the same time. It 3 solutions were made. In a first tank

• were 36.7 kg of 41.0 Be sodium silicate, 12.2 kg of water

-i'5 "and 2633 g of seed crystals according to Example 1 were introduced.

■ 'The. Materials were mixed and heated to 60C.

In a second tank, a dilute acid solution was prepared by adding 1537 g of concentrated sulfuric acid were mixed with 9100 g of water.

In a third tank, a dilute sodium aluminate solution was prepared by mixing 5232 g of sodium aluminate (18.2% Na ₂ O and 21.4% Al O) with 6800 g of water.

The three tanks were connected by pipes. a reaction vessel connected, which was equipped with a high-speed mixing pump. The line to that first tank was opened first. After the three reactant flows through the high speed mixing pump had been mixed, a soft gel formed, which with continued stirring in a reaction vessel was transferred. The reaction vessel was capped and the gel slowly with continued

Stirring heated to 100.degree. After the temperature of 100 ° C. had been reached, the stirrer was switched off and the mixture was kept at this temperature for 70 to 80 hours in order to bring about the crystallization of the HSAY. The slurry was then quenched with cold water, filtered, and subsequently washed with hot water. The material was dried and yielded 6 kg of a well crystallized HSAY faujasite with an SiO ₂ / Al ₂ O ₃ ratio of 5.9 and a degree of crystallinity of 103%. The unit cell size was 24.60 k and the nitrogen surface, measured by the BET method using a Micromeritics Digi-

2
sorb, was 875 m / g. The chemical analysis delivered

the following results: 11.0%. Na ₃ O, 19.6% Al “0_ and -15 68.4% SiO ₂ .

Example 18 ,

HSAY zeolite was subjected to a rare earth exchange and calcined to obtain a "CREHSAY" which was 14.0% SE ₃ O ₃ , 2.45% ^Na ₂ ° ^{and a} silica / alumina ratio of 5.9: 1.0 using the following procedure:
A 4444 g batch of HSAY filter cake (45% solids) obtained according to Example 17 was slurried in 9 liters of deionized water. The HSAY slurry was then mixed into a solution of 4444 ml of commercially available mixed rare earth chloride solution (61% by weight SECl ₃ .6H ₂ O) diluted with 7.5 liters of deionized water. The resulting mixture was heated to 90 to 100 ° C. and held at this temperature for 1 hour. The slurry was filtered and the filter cake washed twice with 3 liters of boiling, deionized water. The washed filter

, [. cake was in 4444 ml of commercially available rare earth

. - 45 -

solution, diluted with 16.5 liters of deionized water, slurried. The mixture was heated again to 90 to 100 ^° C. and kept at this temperature for 1 hour. The slurry was then filtered and the resulting filter cake washed three times with 1 boiling deionized water. The filter cake was then oven-dried at 150 ° C. for 4 to 8 hours. Finally, the dried zeolite was calcined at 538 ° C. for 3 hours. The "CREHSAY" product had the following properties:

Loss on ignition (LOI) 2.1% by weight

.4.0% by weight
2.5 wt.%
s
Nitrogen surface

SE ₃ O ₃ .14.0% by weight

Na ₂ O. 15 Si0 ₉ / Al ₉ 0, ratio 5.9 + 0.1

_ (according to the BET method) 7 68 m / g.

Example 19

a) The CREHSAY according to Example 18 was used to produce an FCC catalyst according to the teaching of US Pat. No. 3,957,689. An acid aluminum sulfate silica sol was prepared by adding two solutions. A · and B were mixed together using a high speed mixer. The 'solution A. consisted of 11.5 kg of sodium silicate with 12.5% SiO ₂ (Na 2 O: 3.2 SiO ₂ ). Solution B consisted of 3.60 1 of a solution prepared from 20 wt.% Sulfuric acid (2,2'1) 'and dilute aluminum sulfate solution, 11 g of A1 ₂ O _3/1 (1.4 to 1). Solutions A and B were left in one. Flow ratio of about 1.5 1 solution A to 0.5 1 solution B through the mixer. The ratio of the solutions flowing in was adjusted so that

an acid-aluminum sulfate-silica sol with 3?

a pH of 2.9 to 3.2 was obtained. to

BATH ORIGINAL

14.4 kg of acid-aluminum sulfate-silica sol were added a slurry of 2860 g of kaolin and 2145 g of CREHSAY according to Example 18, mixed in 6 l of water, given. The mixture of the acid-aluminum sulfate-silica sol and the slurry of CREHSAY and kaolin in water was mixed and spray-dried, an inlet temperature of 316 C and an outlet temperature of 149 C used became. A 3000 g batch of the spray dried product was placed in 11.3 1 "water at 60 to 71 ° C slurried and filtered. The filter cake was washed three times with 3 l of a 3% strength ammonium sulfate solution. The cake was then placed in 9 l of hot water slurried again, filtered and finally

-15 rinsed three times with 3 liters of hot water. The catalyst was then oven dried at 149C.

b) A catalyst, with the same ratio of the components to each other, was made in the same way from calcined, rare earth exchanged, conventional NaY with a silicon dioxide / aluminum

oxide ratio of about 4.9 + ^ 0.1.

The results of the comparative tests are shown below shown in Table 6. The microactivity was determined according to a modification of the method described by F.G. Ciapetta and D.S. Henderson in "Microactivity Test For Cracking Catalysts", Oil And Gas Journal, Volume 65, Pages 88-93, October 16, 1967, the procedure described. Microactivity tests are becoming routine in the petroleum industry used to evaluate the cracking catalysts in the laboratory. Those of the petroleum fraction that over these catalysts was cracked was a West Texas Heavy Gas Oil (WTHGO), the following test conditions ^ 5 conditions were applied:

Temperature 499 ° C,

hourly weight hourly space velocity (WHSV) 16, Catalyst / oil ratio 3. 5

The WTHGO (1.67 g) was replaced by 5.0 g in 1.3 minutes Catalyst passed. The products were collected and the percentage conversion of. Gas oil in hydrogen, light gas s.e, hydrocarbons in the gasoline range ect.

10 determined by gas chromatography.

The catalysts were impregnated with Ni and V as naphthenates dissolved in WTHGO; then the Burned off hydrocarbons by slowly increasing the temperature to 677 ° C. The metal impregnated Catalysts were steam deactivated by the S-13.5 procedure prior to their cracking microactivity were examined.

BATH ORIGINAL

Table 6 Catalyst Composition (wt%) Example 19 (b) Example 19 (a)

Zeolite 35 '35

SiO ₂ 24 24

Tone 41 .41

Na ₂ O '0.49 O ₇ 37

SE ₃ O ₃ 4.94 5.08

Al ₃ O ₃ 26.5 26.0

Microactivity (vol% conversion) after the specified deactivation

0% metals

1% ■ (Ni + V) ⁽²⁾ 1500 ⁽³⁾
1550 ⁽⁴⁾

Partial chemical analysis of zeolite CREY

SiO ₂ / Al ₂ O ₃ (ratio) SE O ₃ (% by weight)

Na_0 (wt%).

Steam deactivation: 8 hours at 732 ° C, 100% steam at

2 ·· 1.1 kg / cm overpressure.

82 86 HSACREY 8 + 0, 53 74 5, 0 + 1 81 80 14, 4 + 0, 20th 64 2, ,1 - CREY 4/9 + 0.1 ■ 2. 15.0 + 1 3.2 + 0.2

Steam deactivation: 5 hours at 816 ° C, 100% steam at 0 kg / cm overpressure.

Steam deactivation: 5 hours at 843 ° C, 100% steam at

2 ··· 0 kg / cm overpressure.

. ■ - 4 9 -

Example 20

a) A slurry was made from 2576 g of HSAY filter cake (45% "solids") of a batch of HSAY, synthesized according to Example 17, and. 4186 g of kaolin in 8.0 liters Water produced. The slurry became green. borrowed with 13.8 kg of acid aluminum sulfate silicon di- '. Oxide ^ Sol mixed according to Example 19. The mixture was, at. Spray-dried under the conditions of Example 19. The spray-dried material was washed with 100% water and an ion exchange with a mixed rare. Earth chloride solution as follows. Subjected: A 3000 g batch of the spray dried material was deionized in 11.3 liters of hot . Slurried water at 60 to 71 C and filtered, -j 5 The filter cake was washed three times with 3 l of hot water • rinsed. The filter cake was then in 9 1 reslurried in hot water and filtered again. The filter cake was three times with 3 1 rinsed with hot water. The filter cake was then reslurried in 10 liters of hot water; and 215 ml of a mixed rare earth chloride solution (60% by weight SECl-, 6H "Q) were added to the Slurry "mixed in. The slurry was 20 minutes . carefully stirred for a long time and at a temperature of "60 to 71 C and a pH of 4.7 held to 5.2. The final was the slurry . filtered again and washed three times with 3 liters of hot water each time.

b) A similar catalyst was prepared by using conventional NaY zeolite with an SiO "/ Al-O-. Ratio of about 4.9j ^ 0.1 was used.

The finished catalyst was then oven-dried at 149 ° C. The finished one out. HSAY produced catalysis

BATH ORIGINAL

tor was compared in the experiments shown in Table 7 below with the catalyst used in similarly made from conventional NaY. In the microactivity test, West Texas was Heavy Gas Oil cracked under the test conditions according to Example 19.

Table 7 Catalyst Composition (wt%) Example 20 (b) Example 20 (a)

Zeolite 17th 17th SiO ₂ 23 23 volume 60 60 Na ₂ O 0.74 '0.70 SE ₂ O ₃ 3.68 3.83 SiO / Al 0 ratio of the zeolite 4.9 + 0.1 5.8 + 0.1 Microactivity (volume conversion) S-13.5 deactivation As Is 73 82 0% metals 68 72 ■. ■ 0.5% (Ni + V) 28 54 1500 deactivation ^ 48 62

Steam deactivation: 5 hours at 816 ° C, 100% steam at 0 kg / cm overpressure.

3Q In the case of the above-described catalysts according to the examples 19 and '20 it was found that the catalyst prepared with the zeolite of the HSAY type was better Exhibited resistance to hydrothermal deactivation than the same catalyst formulation

. _jr those with the same amount of a conventional Zeo-

type Y was produced. The two catalysts prepared with HSAY according to Examples 19 and 20 also showed better resistance to deactivation by vanadium and nickel impurities (Heavy Metal Poisoning) than the corresponding catalysts made from conventional Y-type zeolite had been made. The above catalyst examples clearly show that when using the invention HSAY valuable cracking catalysts can be obtained.

SJ

- blank page -

Claims (1)

UEXKULL & STOLBERG PATENT LAWYERS BESELERSTRASSE 4 D -2000 HAMBURG 52 EUROPEAN PATENT ATTORNEYS DR J -D FRHR by UEXKULL DR ULRICH GRAF STOLBERG DIPL ING JÜRGEN SUCHANTKE DIPL ING ARNULF HUBER DR ALLARD by KAMEKE DR KARL HEINZ SCHULMEYER W.R. Grace & Co. 111-4 Avenue of the Americas New York, N .Y. 10 0.3 6 V.St.A. . (Prio .: December 27, 1982 US 45.3 604 - 19 888 / KA / VOE / wo) December 1983 Faujasite of the NaY type with high
Silica / alumina ^ ratio Claims 1.) Process for the preparation of zeolite Y of the formula ι expressed in moles of the oxides 0.9 + 0.2 Na ₂ O: Al ₃ O ₃ : WSiO ₃ : where w is a value greater than 5.0 and χ can have a value up to about 9, characterized in that, that he a) preparing a reaction slurry by one. Source of alumina, excluding metakapline or kaolin, ·. a silicon dioxide source selected from the group consisting of sodium silicate, silica gel, silica and mixtures thereof,
a source of sodium oxide, a source of nucleation or nucleation centers and
another reactant that is either (I) an active sodium oxide regulator selected from the group consisting of an acid, a solution of a salt obtained from aluminum and an acid, and mixtures thereof, or
(II) a combined source of reactive silica and alumina with low- - | 5 like content of active sodium oxide, or (III) is a mixture of (I) and (II),
mixed with one another, the sources mentioned and the further reactants being selected so that the concentration of active sodium oxide in the reaction slurry, measured as the molar ratio of Na 0 to Al-O. ,, is regulated below the value shown in FIG. 1 by the Line A is given for the corresponding molar ratio of silica to alumina in the reaction slurry, where line A is based on at least the following points indicating the ratios in the synthesis slurry: relationship relationship 16: 1 6.6: 1 9: 1 3.1: 1 6: 1 1.8: 1 and b) the reaction slurry from step a) is heated to allow the crystallization of zeolite Y to effect. 2. The method according to claim 1, characterized in that that w in the formula has a value equal to or greater than about 5.8 and that the concentration active sodium oxide in the reaction slurry - | 0 mung at or below the value that holds through the line B in Figure 1 for the corresponding Silica to alumina molar ratio is indicated in the reaction slurry, where line B is based at least on the following, the -) 5 specify ratios in the synthesis slurry based on the points: N / A 2 ° ^{: A1} 2 ° 3 , 0 : 1 relationship , 4 : 1. 5 2 relationship 20 16: 1 9: 1 3. The method according to claim 1, characterized in that that sulfuric acid is used as the acid in the agent for regulating the active sodium oxide. 4. The method according to claim 1, characterized in that that . as a salt of aluminum and an acid in the agent for regulating the active content of sodium oxide Aluminum sulfate used. 5. The method according to claim 1, characterized in that there is used as a combined source of silicon dioxide and aluminum oxide uses a mother liquor gelled with aluminum salt. 6. The method according to claim 5, characterized in that that a salt is used as the aluminum salt for gelling the mother liquor, which is selected from the group consisting of aluminum sulfate, aluminum chloride, Aluminum nitrate and mixtures thereof ben. 7. The method according to claim 6, characterized in that that aluminum sulfate is used. 10. . . 8th.' Method according to claim 1, characterized in that that the reaction suspension 'heated and the excess mother liquor decanted before allows the reaction product to crystallize. 9. The method according to claim 1, characterized in that the sources of aluminum oxide and silicon dioxide and the regulating agent for the active sodium oxide in each case in separate streams feeds a mixer, the source for the crystal nuclei. or nucleation centers being one of the Streams are metered into a reaction slurry produce, which is then heated in stage b). ...... 25 ■ .- ■ ■ '' '. ■ -. 10. The method according to claim 9, characterized in that that the individual streams are fed into the mixer at the same time. ( ^LA - · / Well crystallized zeolite Y with high silica content and low content of entrapped amorphous silica of the formula expressed in moles of oxide in the crystallized state ₃₅ 0.9 + 0.2 Na ₃ O: Al ₃ O ₃ : WSiO ₃ where w. in the crystal lattice of the zeolite Y is a value greater than 5.0, χ a value up to about 9 and the sharpness index, S.L ·, for | the Si (I: Al) peak at least 6 and for the Si (O Al) peak is at least about 2.2, with the sharpness index on the formula ^10S Si [n Al] S.I. = 10 ■ -. ^S Si [2 Al] where η is 0 or '1 and where S is defined as · ·. 'Peak area -15 S = _: ■ =. ■ (half width), and the peak area and width based on disaggregated Magic angle spinning nuclear magnetic 29
resonance MAS NMR), measured by-silicon. 12. Zeolite according to claim 11, characterized in that that the sharpness index for the Si (I Al) peak is at least 7 and .at least 2.5 'for the Si (O Al) peak amounts to. '· - 13. Zeolite according to claim 11, characterized -characterized, that w has a value greater than 5.4 .. 30. ■ 14. Zeolite according to claim 11, characterized in that that w has a value greater than 5.8.