JPS61278353A - Novel cracking catalyst of hydrocarbon stock material - 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 Field of the Invention The present invention relates to a new catalyst for the conversion of petroleum heavy distillates which contains as a basic component at least one specially modified Y-type acidic zeolite.

Cracking of petroleum heavy fractions is a very important refining process by which lighter fractions such as gasoline, jet fuel and light diesel oil are produced from excess, low-value heavy feedstocks. Refiners will be able to match their production to the demand structure.

The present invention relates to novel catalysts that can be used in cracking reactions, including in particular (a) a matrix and (b) a special zeolite.

The present invention contains 2 to 80% by weight, preferably 3 to 50%, of zeolites with specially modified physical properties and acidity, which is significantly improved compared to other prior art systems based on zeolites. The present invention relates to a new type of catalyst that exhibits high activity and selectivity towards middle distillates.

Structure of the Invention The zeolite used in the catalyst of the present invention is acidic zeolite HY, which is characterized by the following various uses, and its measurement method will be described later: 3! 02
/A120a molar ratio of about 8 to 701, preferably about 1
It is 2-40. The sodium content was measured on thick zeolite at 1100°C and was 0.15f2ff.
1% or less, crystal parameter aO of unit cell is 24.55
x10m ~24.24x10m, preferably 24
．． Between 38x10 m and 24.26x10 m. The sodium ion trapping capacity cN, expressed as the Na q number per 1000 zeolites that has been modified, neutralized, and further calcined, is approximately 0.85 or more (the sodium ion trapping capacity CN8 will be discussed in more detail later). ). The specific surface area measured by the B, E, T method is about 400 m2-g-' or more, preferably 550 m
2/g or more, temperature of 25℃, 2゜6Torr
The water vapor adsorption capacity at a partial pressure of (346,6 Pa) is approximately 6
% or more, and the pore distribution is such that the pore volume contained in pores with a diameter between 20 and 80 m (i.e., 20 to 80 × 10 m) is 1 to 20%, preferably 3 to 20 m. 15%, and the remainder of the pore volume is contained in pores with a diameter of 20×10 m or less.

Various properties are measured based on the methods disclosed below.

- SiO2/Al2O3 molar ratio is determined by chemical analysis. When the amount of aluminum is low, for example below 2%, it is suitable to use the atomic absorption spectrometry method of determination in order to increase the precision.

・Parameter of unit cell is ASTM D3.942
- Calculated from the X-ray diffraction diagram by the method described on the card No. 80. Obviously, for this calculation to be accurate it is necessary that the product has sufficient crystallinity.

・The specific surface area is measured by crosstalk measurement of nitrogen adsorption at the temperature of liquid nitrogen, and is determined by the classical method E.

■, Calculate by law. The samples are purged with dry nitrogen and pretreated at 500°C before measurement.

・The pore distribution was determined by Barrett JOVner and Alenda in the Journal of America.
an ChemicalS0City, No. 73
B, J, H described in Vol. 373 (1951)
Measured by method 6. This method is based on numerical calculations of nitrogen desorption and crosstalk. Measured by Carlo
Erba type 3 orptomatic series 18
00 equipment. The results are expressed as the value of pore volume V as a function of pore diameter. The induced curve is also D
dV/dD as a function of dV/dD. The total pore volume is here defined as the volume of nitrogen adsorbed at the saturated vapor pressure, more precisely at the partial pressure corresponding to the ratio P/Pa of partial pressure and saturated vapor pressure equal to 0.99. stipulated.

-Water absorption (or water vapor adsorption capacity) is measured with a classical gravimetric device. The sample is first pretreated in vacuum at 400°C and then brought to a stable temperature of 25°C. Next 346.
A water pressure of 6 Pa is applied, which is approximately 0.10 P/Pa.
(the ratio of the partial pressure of water introduced into the device to the saturated vapor pressure of water at a temperature of 25°C).

- Sodium ion exchange capacity CNa (or sodium ion collection capacity) is measured as follows. 1q of zeolite is exchanged three times in succession in 100 cm of 0.2 M NaC/solution at 20°C for 1 hour with good stirring. The solution is kept at the same pH during the exchange. In fact, a small amount of sodium carbonate is In addition, if the pH is readjusted to a value close to 7, the proportion of sodium exchanged should be large.
It is expressed as the Q number of sodium per 100 g of zeolite calcined at 1100°C.

It has been discovered in the present invention that stabilized zeolite Y corresponding to the above specifications has remarkable properties.

These zeolites are generally produced from the zeolide Y-Na by a suitable combination of two basic processes. (a) a hydrothermal treatment involving the temperature and partial pressure of steam; and (b) an acid treatment, preferably with a strong, deep mineral acid.

In general, zeolite Y-Na, which is the raw material for producing the zeolite according to the present invention, has an S i 02 /A of about 4 to 6.
It has a molar ratio of 1203. It is advantageous to reduce the sodium content (by weight) in advance to about 1-3%, preferably below 2.5%. Furthermore, zeolite Y-Na generally has a specific surface area of between about 750 and 750 m2/Q.

There are a number of production process variants, all of which involve hydrothermal treatment of the zeolite followed by acid treatment. Hydrothermal treatment is an operation known in the prior art and makes it possible to obtain so-called stabilized or ultra-stabilized zeolites.

For example Mac [) aniel and M aher
, in U.S. Pat. No. 3,293,192, claimed the production of so-called ultra-stabilized zeolites, which were obtained by a combination of hydrothermal treatment and cation exchange with ammonium salt solutions, 24 .45-24.2
crystalline parameters and low sodium content.

Kerr et al. also selectively extracted aluminum using chelating agents such as ethylenediaminetetraacetic acid to obtain silica-rich zeolite Y (U.S. Pat. No. 3,442).
, No. 795).

Combining these two last techniques, Eberly et al. attempted to obtain dealuminated zeolites in US Pat.
506,400 and 3°591.488). They show that hydrothermal treatment consists of selectively extracting tetracoordinated aluminum from the aluminosilicate framework. They claim this procedure as well as post-treatment with solutions containing various cations. One example shows that with post-extraction with 0.1NHC/, faujasite is obtained which no longer contains aluminum.

Ward describes the preparation of zeolite catalysts for producing intermediate extracts (U.S. Pat. No. 3.853.74).
No. 2), the zeolite is stabilized but not subjected to acid treatment at the end of the series of treatments, so the crystal parameters are 24.40X1Q-10m ~ 24.50X10 10m
It is.

3 Ezman and Rabo used a relatively strongly stabilized zeolite as the substrate for the hydrocracking catalyst, but its crystalline parameters varied between 24.20×10−m and 24.4.5×10−10rr1. (European Patent No. 28938). This type of zeolite has 0.
It is particularly characterized by an ion exchange capacity ff1 (IEC) of 0.07 or less. The exchange capacity is defined in this specification as follows: IEC: (ion exchange capacity) [Na2O] moles IEC = to □ [8!02] moles where k is measured before back-exchange to the ions Na+ 5
The molar ratio is i07/A/203.

S! 02 /A/203 molar ratio is equal to k and IE
Zeolites with C equal to 0.07 correspond approximately to the following formula: HNa A/ 02 (S ! 02 ) k/
20.93 0.07 The sodium ion collection capacity of such a product is 100
Expressed as q per 0, 23X0.07 C= x100a (23x O,07)+ 0.93 +59+ (60
xk/2) When k=4.8 CNa= 0.78h=
When 10, CNa= 0.45 therefore 0.07
For smaller or equal IEC values, the sodium ion collection volume I CNa is in all cases 0.8
smaller (for stabilized zeolite Y, k is greater than 4°8).

The ultrastabilized zeolites according to the method of Bezman and Rabo are also characterized by hydrophobicity, such that the adsorption capacity for water at 25 °C and a value of P/Po of 0.1 is less than 5%.

Scherzer (Journal of Ca.
taxis, Vol. 54, p. 285 (1978))
is highly silica-rich (S) by a combination of hydrothermal treatment and acid.
! 02/Al2O3 molar ratio > 100) Zeolite is synthesized and its properties are determined by X-ray diffraction. At the same time, Bo
Sacek et al. conducted a similar process to obtain S! 02/A
An ultrastable zeolite with a l2O3 molar ratio of about 75 is obtained.

These products are very heavily dealuminated.

Zeolites suitable as components of cracking catalysts have moderate acidity, i.e. a SiO2/Al2O3 molar ratio of approximately 8 to 70. It has now been established that the preferred value is 12-40.

The crystallinity is maintained at least 45%, corresponding to a specific surface area of 400 m2/cx, preferably 60%, corresponding to a specific surface area of 550 m2/g, and the pore distribution is maintained at a diameter of 2
The pore volume contained in the 0x 10-10 m to 80x10-"m pores is 1 to 20%, preferably 3 to 15%,
The remainder of the pore volume is essentially contained in pores smaller than 20 x 10-'' m in diameter.

Generation of secondary microporosity targeting pore diameters from 20X10-m to 80X10-10 m as well as 80X10-m
- No intermediate porosity exceeding 10 m is one of the features of the present invention.
These are two characteristics.

Zeolites whose characteristics satisfy the criteria specified above can be selected from alumina, silica, silica-alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia,
Based on titanium oxide, or on a combination of at least two of the abovementioned oxides, or even on clay, or on a combination of the abovementioned oxides and clay, generally Distributed in an amorphous matrix. This matrix essentially helps to shape the zeolite (in other words, to form the product into nodules, globules, extrudates, pellets, etc., so that it can be placed into industrial reactors). have a role'. The proportion of matrix in the catalyst is approximately 50-95% by weight.

Various manufacturing methods are possible depending on the type of product desired. There are two main variations depending on the number of hydrothermal treatments required. For products that are on average strongly stabilized, ie products that are on average strongly dealuminated at the level of the aluminosilicate framework, only one treatment is sufficient. It can be seen that two treatments are necessary for very strongly stabilized products. Conventional techniques generally use the values of crystal parameters to position the level of stabilization.

The crystal parameters measured at the end of a series of manufacturing steps were 24
．． It is economically advantageous to carry out only one hydrothermal treatment in order to obtain a product (strongly stabilized on average) between 27.times.10@-10 m and 24.55.times.10@-10 m. The raw material zeolite NaY was originally S f 02 / A
1203 molar ratio is 4-6, crystal parameter is 24.
60X10'-m ~ 24.80x10-10m, more generally: 24.65, X10-'°m ~ 24.75
It is X1010m. Before carrying out the hydrothermal treatment, it is necessary to reduce the proportion of sodium to below 3% by weight, preferably below 2.5% by weight. This is generally acknowledged;
It is carried out in a solution of ionizable ammonium salts, such as nitrates, chlorides, and sulfates, with repeated exchanges. The zeolite NH4NaY thus obtained can now be heated under the following conditions. That is, about 500℃~
A temperature of 850°C, preferably 600°C to 800°C, about 0.
05 bar to 10 bar, preferably 0.1 bar to
The conditions are at a water vapor partial pressure of 5 bar for at least 20 minutes, preferably for more than 1 hour.

The thus stabilized zeolite is treated with hydrochloric acid, nitric acid, sulfuric acid,
Treatment with dilute solutions of organic or inorganic acids such as phosphoric, acetic, oxalic, or formic acids.

24, 24x10-10m ~24.35x10-
To obtain a zeolite with a parameter of 10 m, a two-stage hydrothermal treatment can be used. The first step is to produce a product with a relatively high proportion of sodium, in any case below 3.5%, preferably 2.8%, under very mild conditions, i.e. 5%.
Temperature from 00 to 700℃, 20 Torr (0,026b
ar) for at least 20 minutes, preferably at least 1 hour. The product is then subjected to one or more exchanges in an ionizable ammonium salt solution and then in a solution of an organic or inorganic acid, provided that the pH of the final solution does not fall below O05. It is also possible to use a combination of these two types of exchange, ie mixing the acid with a solution of the ammonium salt. In this case, the proportion of sodium is less than 1%, preferably 0.07%.
It is. Next, conditions that are stricter than the first treatment, namely 600
-880°C, preferably 660-830°C (the temperature of the second hydrothermal treatment is about 100°C-830°C lower than the temperature of the first treatment)
250°C, preferably 160-230°C higher), about 0.0
5 bar to 10 bar, preferably 0.1 bar to 5
A second hydrothermal treatment is applied at a water vapor partial pressure of bar (7) for a period of at least 30 minutes, preferably for a period of at least 1 hour.

One or two hydrothermal treatments are followed by one or more extraction treatments of organic or inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, phosphoric acid, acetic acid, oxalic acid, formic acid, etc. It is done in solution.

It is also possible to use complexing agents known in the prior art, such as ethylenediaminetetraacetic acid, acetylacetone.

However, the preferred treatment is 0.1% of hydrochloric or nitric acid.
It is carried out with a solution with a normality of N to 11N, preferably 0.5N to 3N. In order to take care of the crystallinity of zeolite, it is best to perform the treatment gently, that is, repeatedly in an acid solution with a small normality, multiple times under more severe conditions.
That is, rather than a single treatment in concentrated acid, a significant amount of aluminum and sodium can be removed. The acid treatment described herein can be carried out in any event subsequent to or prior to one or more exchanges commonly carried out with ammonium salts to further reduce the sodium content of the zeolite product. This ion exchange can be carried out simultaneously with the acid treatment without any inconvenience by adding an acid to the ammonium salt aqueous solution. These acid treatments can also be followed by exchange with Group IIA metal cations, rare earth cations, even chromium and zinc cations, or any other element useful for improving the catalyst.

The zeolite HY or N1-(4Y) thus obtained can be introduced at this stage into one of the amorphous matrices mentioned above. One method preferred in the present invention is to moisten the zeolite for several tens of minutes. The paste thus obtained is then passed through a die to obtain an extraction volume with a diameter of 0.4 to 4 Il m.

The hydrogenation agent function can be introduced into the catalyst in various ways at various stages of production.

The zeolite described above and produced by the method described above is
It has been found in the present invention to be particularly well suited as a catalyst for catalytic cracking, which catalyst comprises, by weight, (a) at least 50 to 95% of silica-alumina, silica-magnesia and clay; 1
(optionally with at least one other solid selected from the group consisting of alumina, silica, zirconia, alumina-boron oxide, magnesia, titanium oxide); b
) 5-50% zeolite (optionally containing one or more metal elements, especially rare earth metals, currently used in cracking catalysts). It should be noted that here the catalyst according to the invention is used in a small amount, for example ioooppm
rhenium or one of the noble metals of the platinum group (platinum, palladium, iridium, osmium, rhodium,
ruthenium) and/or iron, especially in the form of oxides,
Other metals such as cobalt, nickel, chromium and manganese (eg 0.01-15%) may also be suitably included.

The general conditions for catalytic cracking reactions are particularly well known and will not be repeated here within the scope of the present invention (e.g. U.S. Pat. Nos. 3,293°192; 3,449;
No. 070, No. 4,415.438, No. 3,518.0
51, No. 3.607.043).

The characteristics of the present invention will be clarified by the following examples.

Example Example 1 Zeolite 2.5 with formula Na AlO2 (S!03) Use NaY.

The characteristics of this zeolite 1- are S! 02/A/203 molar ratio 5
Crystal parameters 24.69 Xl0-10m
Water vapor adsorption capacity at 25°C (at P/Po = 0.1) 26% specific surface area
880II12/g This zeolide is subjected to 5 exchanges in 2M ammonium sulfate solution at a ratio of (volume of solution)/(weight of zeolite) 8 for 1.5 hours at a temperature of 95°C. . The percentage of sodium in the obtained zeolite NaNH4Y is 0.95%. The product is then quickly introduced into a furnace preheated to 770° C. and left in a static atmosphere for 4 hours. The zeolite is then exchanged twice with ammonium nitrate solution so that the sodium content falls to 0.2%. At this time 3 i 02
/A I 203 molar ratio is 6o3, crystal parameter is 24゜38x10-10m, specific surface area is 625m2/Q
, the water absorption capacity is 11°3% (at P/Pa-0,1), and the sodium collection capacity is 2. Example 2 Raw material Zelite N
aY is subjected to the same exchange and stabilizer treatment as in Example 1. After stabilization, instead of performing exchange with ammonium ions, acid treatment is performed under the following conditions. That is, (2N
The ratio of nitric acid volume)/(solid Shigenobu) is 6, and the temperature is 95°C.
, the time is 3 hours. Another treatment is then carried out under the same conditions as above, but in this case using an acid with a normality of 0.3N. In this case, the SiO2/A/203 molar ratio is 18,
Residual sodium percentage is 0.2%, crystal parameter is 2
4゜32X10-10m, specific surface area 805m2/g,
The water absorption capacity is 13.7%, and the sodium ion collection capacity is 1.8.

Example 3 The zeolite NaY is exchanged twice in ammonium chloride solution so that the proportion of sodium is 2.6%. The product is then placed in a cold oven and heated to 400°C in air. At this temperature, in the force potential atmosphere,
Upon evaporation, an amount of water corresponding to a partial pressure of 50.661 Pa is introduced. At this time, the temperature is maintained at 565°C for 2 hours.

This product was then subjected to one exchange with ammonium chloride solution, followed by a 3-hour exchange with the following conditions: , apply the acid treatment with great care.

In this case, the proportion of sodium increases to 0.6%, and S
The i 02 /A120a molar ratio is 7.2. Now this product is subjected to a coarse force position for 3 hours at 780°C in a static atmosphere and then (volume of solution) / (zeolite weight)
The mixture is returned to an acid solution using hydrochloric acid with a normality of 2 and a ratio of 10. The crystal parameters are 24.28 x 1 x 10 m, the specific surface area is 825 m2/g, the water absorption capacity is 11.7, and the sodium ion collection capacity is 1.0.

Example 4 Zeolite HY10Q obtained in Example 2 was dispersed in pulverized silica-alumina powder to obtain zeolite 25
% and 75% silica alumina is obtained. This mixture was then heated at 75'0°C for 17 hours at a water vapor partial pressure of 1 ba.
A hydrothermal treatment is performed at r (0, 1 M Pa) to reduce its activity. (Silica alumina contains 75% silica and 25% alumina by weight).

The performance of the catalyst thus obtained is evaluated in a vacuum fixed bed cracking test of diesel oil under the following conditions.

Catalyst amount 4. C1 Catalyst/raw material weight ratio = C10 = 3.0 WH8V = 15/hour Reaction time = 75 seconds Reactor temperature = 480°C Raw material: Density (15°C) = 0.904 Aniline point = 79°C S weight% = 1.3 N weight% <0.1 Conradson carbon weight% - ○, 32 Ni+V<11) I)m A S T M D 1160 Initial distillation = 202℃10
%=307°C 50%-402°C 90%=510°C End point The results obtained are as follows.

Conversion rate - 72% C5 + gasoline yield = 53% C4''''/C4 ratio = 1.2 Coke weight % relative to catalyst - 2.0% Example 5 The zeolite HY10C1 obtained in Example 2 was added to 0.5
Soak in an aqueous solution of M lanthanum sulfate for 2 hours at ambient temperature. The product was then washed with distilled water and dried at 150°C for 4 hours.
Next, it is heated at 500°C for 2 hours. As in Example 4, it is dispersed in silica-alumina powder in the same proportions and subjected to the same hydrothermal treatment as carried out in Example 4.

The performance of the catalyst thus obtained is evaluated under the same conditions as described in Example 6. The results are as follows.

Conversion rate = 73% C5 + gasoline yield = 54% C4 = / C4 ratio = 1.0 Coke weight 1% to catalyst = 2.1% Example 6 (comparison) An industrial cracking catalyst exhibiting the following characteristics was prepared in a fluidized bed. Use with.

Matrix% near 5 heavy flow% (75% silica)
Alumina) Zeolite %: 25% Zeolite properties: Specific surface area = 148 m2 ・a-1 Pore volume = 0.310 m3-Q-' Rare earth weight % (as metal) = 1.9% F0203 weight % = 0.65% ABC<apparent density) = 0.75 g-cm3 Na20 (wt%) = 0.33% This catalyst was subjected to the same hydrothermal treatment as in Examples 4 and 5, and then the same hydrothermal treatment as in Examples 4 and 5 was performed. Do the same test. The results obtained are: Conversion = 68% Yield of C5+gasoline - 47% 04''''/C4 ratio = 0.6 % coke weight relative to catalyst - 2.7%.

Effects of the Invention Since the catalyst according to the present invention is configured as described above,
When used for cracking hydrocarbon feedstocks, it exhibits significantly improved activity and selectivity to intermediate effluents compared to other prior art systems based on zeolites.

The use of this catalyst in cracking petroleum heavy fractions therefore allows refiners to improve demand structure by producing lighter fractions such as gasoline, jet fuel and light diesel oil from excess, lower value heavy feedstocks. You will be able to adjust your own production to.

that's all

Claims (1)

[Claims] 1) Consisting of (a) a matrix and (b) a zeolite, the (b) zeolite: - having a SiO_2/Al_2O_3 molar ratio of about 8 to 70; - for the zeolite calcined at 1100°C. The measured sodium content is 0.15% by weight or less, and the unit cell parameter a_0 is 24.55×10^-
^1^0m ~ 24.24 x 10^-^1^0m, and the sodium ion collection capacity C_N_a expressed in grams of sodium per 100g of modified, neutralized, and calcined zeolite is approximately 0.85 or more, ・The specific surface area is about 400m^2・g^-^1 or more, ・The water vapor adsorption capacity at 25°C is 6% or more (when the P/P_0 ratio is 0.10),・Pore distribution is 20 x 10^-^1^0m to 80 x 10^ in diameter.
The pore volume contained in a pore of -^1^0m is 1 to 20%, and the remaining pore volume is 20 x 10^-^1^0m in diameter.
A catalyst characterized in that it is essentially contained in the pores of: 2) on a weight basis: (a) at least about 50-95% of a matrix selected from the group consisting of alumina, silica, silica-alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, clay; b) About 5-50% of the zeolite according to claim 1 further comprising at least one metal selected from the group consisting of rare earth metals, rhenium, noble metals of the platinum group, iron, cobalt, nickel, chromium and manganese. A catalyst consisting of. 3) on a weight basis: (a) at least about 50-95% of a matrix selected from the group consisting of alumina, silica, silica-alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, clay; b) about 5 to 50% of zeolite, (b) the zeolite: - has a SiO_2/Al_2O_3 molar ratio of about 12 to 40, and - has a sodium content of 0.5%, measured for the zeolite calcined at 1100°C. 15% by weight or less, ・Parameter a_0 of unit cell is 24.38×10^-
^1^0m ~ 24.26 x 10^-^1^0m, and the sodium ion collection capacity C_N_a expressed in grams of sodium per 100g of modified, neutralized, and calcined zeolite is approximately 0.85 or more, ・The specific surface area is about 550 m^2・g^-^1 or more, ・The water vapor adsorption capacity at 25°C is 6% or more (when the P/P_0 ratio is 0.10),・Pore distribution is 20 x 10^-^1^0m to 80 x 10^ in diameter.
The pore volume contained in the -^1^0m pore is 3-15%, and the remaining pore volume is 20 x 10^-^1^0m in diameter.
Catalyst according to claim 2, characterized in that it is contained in the following pores: 4) A method for producing a catalyst according to any one of claims 1 to 3, comprising mixing a matrix with zeolite, the zeolite being zeolite Y.
-Na is manufactured from zeolite Y-Na.
Generally, the SiO_2/Al_2O_3 molar ratio is about 4 to 6, and the crystal parameter is 24.60×10^-^1^0
m ~ 24.80 x 10^-^1^0 m, and the specific surface area is generally about 750 to 950 m^2/g, and the production of the zeolite includes at least one treatment with an ionizable ammonium salt solution. The proportion of sodium in the zeolite Y-Na is lowered to a value below 3% by weight by exchange of the zeolite NH_4NaY, with a temperature of about 500 to 850 °C and a water vapor partial pressure of about 0.05 to 10 bar. Calcining the zeolite NH_4NaY in at least one stage for at least 20 minutes under conditions (hydrothermal treatment) to obtain a so-called stabilized zeolite; A method comprising at least one step of treatment with at least one solution of. 5) The production of the zeolite is such that - the proportion of sodium in the zeolite Y-Na is reduced to a value below 2.5% by weight by at least one exchange with an ionizable ammonium salt solution, so that the zeolite NH_4NaY is obtained; Calcining the NH_4NaY zeolite in at least one stage (hydrothermal treatment) at a temperature of about 600-800 °C and under a water vapor partial pressure of about 0.1-5 bar for at least 1 hour to obtain a so-called stabilized zeolite. , ・So-called stabilized zeolite, 0.1 to 11N
5. A process according to claim 4, comprising at least one step of treatment with a solution of hydrochloric acid or nitric acid, preferably with a normality of 0.5 to 3N. 6) A method for producing a catalyst according to any one of claims 1 to 3, comprising mixing a matrix with zeolite, the zeolite being zeolite Y-
Manufactured from Na, generally SiO_2/Al_
The 2O_3 molar ratio is about 4-6, and the crystal parameter is 2.
4.69 x 10^-^1^0 m, and the specific surface area is generally about 800-900 m^2/g, and the production of zeolite consists of: At least one exchange with an ionizable ammonium salt solution The proportion of sodium in zeolite Y-Na is 3% by weight or less, preferably 2.8% by weight.
to obtain the zeolite NH_4NaY, at a temperature of about 500-700 °C, at least 0.026 ba
subjecting the zeolite NH_4NaY to at least one stage of first hydrothermal treatment for at least 20 minutes under a water vapor partial pressure of r; followed by at least one exchange with at least one solution of at least one ionizable ammonium salt; treatment with at least one solution of at least one organic or inorganic acid or exchange with at least one solution of at least one ionizable ammonium salt and at least one solution of at least one organic or inorganic acid. treatment with at least one solution or at the same time,
the proportion of sodium is reduced to a value below 1% by weight, preferably below 0.7% by weight; the zeolite thus obtained is then treated at a temperature of 600-880°C, preferably 660-830°C;
at least one stage of a second hydrothermal treatment, wherein the temperature of the second hydrothermal treatment is lower than the temperature of the first hydrothermal treatment;
the zeolite is then treated in at least one step with at least one solution of an organic or inorganic acid or a complexing agent. 7) By weight: (a) 50-95% of a matrix selected from the group consisting of silica-alumina, silica-magnesia and clay; (b) 5-50% of a zeolite as defined by claim 1; %. 8) The matrix is alumina, silica, zirconia,
A catalyst according to claim 7 further comprising at least one solid selected from the group consisting of alumina-boron oxide, magnesia, titanium oxide. 9) The catalyst according to claim 7 or 8, wherein the zeolite contains at least one rare earth metal. 10) Precious metals of the platinum group, rhenium, manganese, chromium,
A catalyst according to any one of claims 7 to 9, further comprising at least one metal selected from the group consisting of cobalt, nickel and iron. 11) According to any one of claims 1 to 3, or any one of claims 7 to 10, or according to claims 4 to 6 Application of the catalyst produced by any one of the above methods to the cracking of hydrocarbon raw materials.