JPH0596174A - Catalysis composition for catalytic decomposition of hydrocarbon and its production - Google Patents

Abstract

PURPOSE:To provide a novel catalysis composition for catalytic decomposition of hydrocarbons having a high decomposition ability in using for hydrocarbon oils, especially heavy hydrocarbon oils such as residual oil hydrogenated at normal pressure, etc., and being small in generation of coke and gas, and its production. CONSTITUTION:In a catalysis composition for catalytic decomposition of hydrocarbons consisting of faujasite type zeolite and a porous inorg. oxide matrix, the faujasite type zeolite is a modefied type having >=6molar ratio of silica/alumina and >=0.70 ammonium ion exchanging ratio without having been a heating history of >=150 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst composition for catalytic cracking of hydrocarbon oil and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a catalyst composition for catalytic cracking of hydrocarbon oil, a faujasite type zeolite mainly having high thermal stability, for example, ultra stable Y type zeolite (US-Y) is used.
Etc. have been used (JP-A-51-107294, JP-A-63-107748). However, when a catalytic composition for catalytic cracking using a conventional zeolite is catalytically cracked for a low-grade heavy hydrocarbon oil, it is poor in stability against metal contaminants and does not necessarily have sufficient decomposing ability, and coke and There was a problem that the production of gas was not kept at a sufficient level.

[0003]

OBJECTS OF THE INVENTION The object of the present invention is to use hydrocarbon oils, especially heavy hydrocarbon oils such as hydrotreated normal pressure residual oils, to obtain a high residual oil decomposing ability, a high gasoline yield, a coke and It is an object of the present invention to provide a novel catalyst composition for catalytic cracking of hydrocarbons which produces less gas and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention provides a catalyst composition for catalytic cracking of hydrocarbons comprising a faujasite type zeolite and a porous inorganic oxide matrix, wherein the faujasite type zeolite is not subjected to a heat history of 150 ° C. or higher. Relates to a catalyst composition for catalytic cracking of hydrocarbons characterized by being a modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in the state, and a method for producing the same. ..

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The modified faujasite-type zeolite in the hydrocracking catalyst composition of the present invention has an ammonium ion exchange ratio (NH
₄ Z) shows a high ion exchange rate of 0.70 or more, preferably 0.72 or more, a silica / alumina molar ratio of 6 or more, preferably in the range of 7 to 30, and a unit lattice constant of 24.65Å. Below, preferably 24.55 to 24.30
It is in the range of Å and has excellent acid resistance and heat resistance. In the present invention, the state that the starting material and the modified faujasite-type zeolite have not been subjected to a heat history of 150 ° C. or higher does not have a history of being calcined at a temperature of 150 ° C. or higher, or the modified faujasite-type zeolite is 150
If calcined at a temperature of ℃ or above, the silica / modified faujasite zeolite before calcining /
It defines the alumina molar ratio and the ammonium ion exchange rate.

Such a modified faujasite-type zeolite is disclosed, for example, in Japanese Patent Application No. 3-993 filed by the present applicant earlier.
No. 90, that is, a faujasite-type zeolite that has not been subjected to a heat history of 150 ° C. or higher is treated with a dealuminating agent and p in the presence of soluble silica in the aqueous phase.
It can be produced by contacting with H4 or less.

The modified faujasite-type zeolite obtained by the above-mentioned production method is obtained by subjecting the faujasite-type zeolite which has not been subjected to heat history to an aqueous phase of sulfuric acid, nitric acid in the presence of soluble silica such as silicic acid or silicate. By contacting an acid such as hydrochloric acid at a pH of 4 or less, aluminum in the unit cell forming the hexagonal prism of the faujasite type zeolite skeleton is preferentially dealuminated, and silicon is inserted at the dealuminated position. Therefore, the aluminum content in the unit cell forming the hexagonal prism is lower than that of conventional faujasite-type zeolite with respect to the total aluminum content in the skeleton structure, and the ion exchange rate is high and the acid resistance is high. It is also presumed to have excellent heat resistance.

The soluble silica is a silicic acid contained in the aqueous solution, which is in a state of producing yellow molybdosilicic acid by adding an ammonium molybdate solution by acidifying the aqueous solution with sulfuric acid. Sources of soluble silica include orthosilicic acid, metasilicic acid, etc. xSiO ₂ · y
Silicic acid represented as H ₂ O; silicates such as metasilicate, orthosilicate, disilicate, trisilicate, etc .; silica sol in which silicic acid is highly polymerized; silane compounds, etc. it can. The amount of soluble silica present in the aqueous solution is preferably 130 ppm or more. The amount of soluble silica present in the aqueous solution is 130
If it is less than ppm, the crystal structure of zeolite is destroyed by the acid treatment, which is not desirable.

Examples of the dealumination agent include mineral acids such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as acetic acid, and EDTA.
A dealuminating agent usually used for dealumination of zeolite such as a chelating agent can be used, but sulfuric acid, nitric acid and hydrochloric acid are particularly preferable.

The ammonium ion exchange rate (NH ₄ Z) of a conventional faujasite type zeolite (zeolite Y) which has not been subjected to a heat history of 150 ° C. or higher is usually about 0.68. In general, a zeolite having a low silica / alumina molar ratio tends to have a high ammonium ion exchange rate (NH ₄ Z), but a zeolite having a silica / alumina molar ratio of 5 or more has an ammonium ion exchange rate of 0.70 by the above method. No more. Therefore, in order to increase the ammonium ion exchange rate, NH ₄ —Na-faujasite-type zeolite once subjected to ammonium ion exchange is repeatedly ion-exchanged to increase the ion exchange rate, or the zeolite is calcined at a temperature of 400 to 700 ° C. After that, a method of further exchanging ammonium ions is being carried out.

The ammonium ion exchange rate in the present invention is described by DONALD W, BRECK, “Zeolite Molecular Sieve”.
Chapter of s ”A WILEY-INTERSCIENCE PUBLICATION (1974)
er Seven; values displayed by the method described in Ion Exchenge Reactions in Zeolites and measured as follows. That is, a sample of faujasite-type zeolite that has not been subjected to a heat history of 150 ° C. or higher is suspended in 10 times the amount of pure water (ion-exchanged water). In this suspension, the number of moles of alumina (m) previously determined from the composition analysis of the sample zeolite
10 times as much salt (NaCl) is added, and the mixture is stirred at 80
Heat to ℃. Next, 3.0 wt% N at a temperature of 80 ° C.
Adjust the pH of the suspension to 8.5 by adding aOH solution to 1
After stirring for an hour, the temperature is further raised to 90 ° C. and the mixture is stirred for 30 minutes. Then, this suspension is filtered and washed thoroughly with hot water at 80 ° C. to obtain Na (+) exchanged zeolite. By this operation, a sodium ion-exchanged zeolite is obtained. Ammonium ion exchange is performed as follows using the Na (+) exchanged zeolite obtained by the above operation.
That is, Na (+)-exchanged zeolite was suspended in 10 times the amount of pure water (ion-exchanged water), and the amount of ammonium sulfate was 5 times the number of moles (m) of alumina obtained in advance from the composition analysis of the sample zeolite. And warm to 80 ° C. with stirring. Then, this suspension was maintained at a temperature of 80 ° C. for 1 hour while stirring, then filtered, washed thoroughly with 80 ° C. warm water, and
An ammonium ion-exchanged zeolite is obtained by drying overnight at 20 ° C. Similarly, ammonium ion exchange of Na (+) exchanged zeolite is performed using 10 times of ammonium sulfate. Ammonium ion exchange rate (NH ₄ Z) in the present invention
Is an ion exchange equilibrium diagram showing the results of these two NH ₄ (+) exchanges obtained from the analytical values of Na (+) exchanged zeolite and NH ₄ (+) exchanged zeolite and the amount of ammonium sulfate used for ammonium ion exchange. The NH ₄ + equilibrium fraction in the solution is 0.9, and the ammonium ion exchange rate (N
H ₄ Z).

The porous inorganic oxide matrix in the present invention acts as a binder such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. Porous inorganic oxides can be used as long as they can be formed into a desired shape by mixing with a conventional matrix component used for a usual catalytic cracking catalyst obtained from a sol or gel precursor, or by mixing with other catalyst composition components. The thing itself can also be used.

The content of the modified faujasite-type zeolite in the catalytic composition for catalytic cracking of the present invention is 5 to 50 w.
It is desirable that it is in the range of t%, preferably 10 to 40 wt%.

Further, in the catalyst composition for catalytic cracking of hydrocarbons of the present invention, in addition to the modified faujasite-type zeolite and the above-mentioned porous inorganic oxide matrix, alumina or alumina hydrate, phosphorus-containing alumina particles, alkaline earth are used. A metal scavenger component such as a refractory oxide containing a metal oxide, a clay substance such as kaolin, halloysite, and montmorillonite may also be contained.

The catalyst composition of the present invention comprises a precursor of the above-mentioned porous inorganic oxide matrix, for example, silica hydrosol, silica-alumina hydrogel and the like, and a modified faujasite type zeolite, and if desired, a clay material such as kaolin. In addition, it is uniformly dispersed, and the obtained mixture slurry is produced by a conventional method, for example, by spray drying. The catalyst composition of fine spherical particles obtained by spray drying is washed if necessary, and after washing, dried or dried and calcined again. It is also possible to introduce components such as phosphorus and rare earths into the catalyst composition of fine spherical particles by a usual method. The catalytic cracking catalyst composition of the present invention can be used under normal catalytic cracking conditions and is composed of a specific modified faujasite-type zeolite, so that when used for hydrocarbon oils, particularly heavy hydrocarbon oils, It is stable against heat and metal contaminants, and has a characteristic that it produces a small amount of coke and gas in spite of showing high resolution. Hereinafter, the present invention will be specifically described with reference to examples.

[0016]

【Example】

Reference Example 1 Production of modified faujasite-type zeolite NaY zeolite (molar composition Na ₂ O.Al ₂ O ₃ .5Si
1392 g of O ₂ ) was suspended in 13.9 liters of warm water at 80 ° C. Separately, No. 3 water glass diluted to a silica concentration of 1% was neutralized with sulfuric acid to prepare 13.5 kg of a silicic acid solution having a pH of 2.0. After adding 930 g of this silicic acid solution to the suspension while stirring, the temperature was raised to 95 ° C., and then 251.4 g each of the remaining silicic acid solution 12.57 kg and 2.5% sulfuric acid 26.5 kg. / HR, a pH of 2.0 was continuously added at a rate of 529.2 g / HR. After the addition of the silicic acid solution and sulfuric acid was completed, the zeolite was separated, washed and dried to obtain a modified zeolite. The composition of this modified zeolite was determined by chemical analysis, and the crystallinity and lattice constant were measured by X-ray diffraction. The modified zeolite obtained as described above is called SAI-1. The properties are shown in Table 1. The modified zeolite (SAI-1) and the starting material NaY
Ammonium ion exchange properties of some of the zeolites were investigated. Ammonium ion exchange method, according to the method described above, after Na (+) exchanged zeolite,
The ion exchange rate at 80 ° C. was determined by changing the amount of ammonium sulfate. The results are shown in Fig. 1 (ion exchange equilibrium diagram).
Shown in. The vertical axis (NH ₄ Z) in FIG. 1 is the equilibrium fraction (ion exchange rate) of NH ₄ (+) with respect to all cations in the zeolite.
And is a value represented by the following equation. The horizontal axis (NH ₄ S) is the equilibrium fraction of NH ₄ (+) in the solution and is a value represented by the following equation. As can be seen from FIG. 1, the modified zeolite of the present invention (SAI-
1) shows ion exchange characteristics with a high exchange rate as compared with conventional NaY zeolite.

Reference Example 2 Production of Modified Faujasite Type Zeolite NaY zeolite (molar composition Na ₂ O.Al ₂ O ₃ .5Si)
Ion exchange was repeated without firing 1392 g of O ₂ ) by a usual method to prepare an ammonium exchanged zeolite having a Na residual ratio of 25%. This ammonium-exchanged zeolite was suspended as it was in 13.9 liters of warm water at 80 ° C. Separately, 14.4 kg of a silicic acid solution of pH 2.0 obtained by neutralizing No. 3 water glass diluted to a silica concentration of 1% with sulfuric acid was prepared. 930 g of this silicic acid solution was added to the suspension with stirring. Next, the temperature is raised to 95 ° C., and 23.52 kg of 2.5% strength sulfuric acid and the remaining silicic acid solution 1
3.47 kg was continuously added at a rate of 981 g / HR and 561 g / HR, respectively. 24 hours after the start of addition, the slurry was collected, the zeolite was separated, washed and dried to obtain modified zeolite SAI-2. The properties of this modified zeolite are shown in Table 1.

Reference Example 3 Production of NH ₄ -Y zeolite NaY zeolite (molar composition Na ₂ O.Al ₂ O ₃ .5Si)
O ₂₎ 1392g performed repeating the ion exchange by an ordinary method to prepare Na remaining 25% of the ammonium-exchanged zeolite. After washing and drying this zeolite, it was calcined at 550 ° C. for 3 hours. Next, the calcined zeolite was further ion-exchanged with ammonium sulfate to prepare NH ₄ —Y zeolite (Na ₂ O content 1.33 wt%) having an ammonium exchange rate of 91%. This NH ₄ -Y zeolite was designated as Z-1, and its properties are shown in Table 1.

Reference Example 4 Ultra-stable Y-type zeolite (US
Y) Production NaY zeolite (molar composition Na ₂ O.Al ₂ O ₃ .5Si)
1392 g of O ₂ ) was repeatedly ion-exchanged by a usual method to prepare an ammonium-exchanged zeolite having a Na (+) residual rate of 25%. After the zeolite was calcined at 550 ° C for 3 hours, the Na (+) residual ratio of 10 was again obtained by ion exchange.
A% ammonium exchange rate zeolite was prepared. After washing this zeolite, the zeolite was hydrothermally treated in a steam atmosphere at 650 ° C. for 3 hours to obtain ultra-stable Y-type zeolite (USY). The crystallinity of this USY zeolite is 80% with respect to the starting NaY, and the lattice constant is 24.54.
It was Å. This USY is Z-2, and its properties are shown in the table.
Shown in 1.

Example 1 (Production of catalytic composition for catalytic cracking) Commercially available No. 3 water glass was diluted to a SiO ₂ concentration of 12.73%.
An aqueous solution of water glass was prepared. Separately, sulfuric acid having a concentration of 25% was prepared. 2 parts each of this aqueous solution of water glass and sulfuric acid
A silica hydrosol (binder) was prepared by continuously mixing at a rate of 0 liter / minute and 5.6 liter / minute for 10 minutes. With an appropriate amount of silica hydrosol prepared in this way,
An appropriate amount of the hydrogel of pseudo-boehmite alumina obtained by the neutralization reaction of an appropriate amount of kaolin and sodium aluminate aqueous solution with an aqueous solution of aluminum sulfate (these are used in such amounts that the composition of the catalyst composition will be the ratio described below). A)), and then the samples SAI-1 and SAI-2 of Reference Examples 1 and 2 and the sample Z of Reference Examples 3 and 4 previously prepared.
The respective zeolites of -1 and Z-2 were mixed and then spray-dried. Each of the obtained dry particles was washed, then immersed in an aqueous solution of rare earth chloride, washed and dried to obtain catalytic compositions A, B and C, D for catalytic cracking, respectively.
Was prepared. Each catalyst composition is 35 wt%
Zeolite and 10 wt% pseudo-boehmite alumina, 35w
It was composed of t% kaolin and 20 wt% silica as a binder, and further contained 0.9 wt% rare earth as RE ₂ O ₃ .

Example 2 (Evaluation of Catalyst Composition) A part of each of the catalysts A, B and C, D prepared in Example 1 was calcined in air at 600 ° C. for 2 hours, and then each of them was treated with nickel naphthenate. Nickel 170 was added to each catalyst by impregnating it with a benzene solution containing vanadium naphthenate, then removing benzene under reduced pressure and firing again.
0 ppm and vanadium 3300 ppm were deposited.
A catalytic cracking test was carried out on the cracking characteristics of each of the catalysts thus obtained, using hydrogenated atmospheric residual oil (DSAR) as a feedstock. Prior to the test, each catalyst was calcined at 600 ° C. for 2 hours, and then subjected to a test in which a pseudo-equilibrated sample was prepared by contacting with 100% steam at 770 ° C. for 6 hours for pretreatment. The evaluation results are shown in Table-2. Further, each catalyst on which nickel and vanadium had not been deposited was also steam-treated at 770 ° C. and 810 ° C. for 6 hours for pseudo-equilibrium and subjected to a catalytic cracking test. As the feedstock oil, hydrogenated vacuum gas oil (DSVGO) was used to evaluate the decomposition characteristics of each catalyst. The results are shown in Table-3. (The following margin)

[0022]

[Table 1] * 1 Crystallinity is a relative value when the starting material NaY is 100%. * 2 It is an ion exchange equilibrium diagram and is the ammonium ion exchange rate of zeolite when the equilibrium fraction of NH ₄ (+) in the solution is 0.9.

[0023]

[Table 2] * 1 Specific surface area when the catalyst is calcined at 600 ° C for 2 hours * 2 Boiling range: C _{5 to} 216 ° C * 3 Boiling range: 216 to 343 ° C (hereinafter blank space)

[0024]

[Table 3] * 1 Specific surface area when the catalyst is calcined at 600 ° C for 2 hours * 2 Boiling range: C _{5 to} 216 ° C * 3 Boiling range: 216 to 343 ° C

[0025]

[Effect] The catalyst composition for catalytic cracking of hydrocarbons of the present invention is
Used for catalytic cracking of hydrocarbon oils, especially heavy hydrocarbon oils such as atmospheric residue oil, has excellent metal resistance, high resolution, high gasoline yield, low production of coke and gas, Further, it has a feature of excellent hydrothermal stability.

[Brief description of drawings]

FIG. 1 is a graph showing a modified faujasite-type zeolite produced in Reference Example 1 and starting material ion exchange characteristics.

Front Page Continuation (72) Inventor Yusaku Arima 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Catalyst Kasei Kogyo Co., Ltd. Wakamatsu Factory (72) Inventor Takanori Ida 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka Kasei Industry Co., Ltd. Wakamatsu factory

Claims (5)

[Claims] 1. A catalyst composition for hydrocarbon catalytic cracking comprising a faujasite type zeolite and a porous inorganic oxide matrix, wherein the faujasite type zeolite is
Silica / with no heat history above 150 ° C
A catalyst composition for catalytic catalytic cracking of hydrocarbons, which is a modified faujasite-type zeolite having an alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more. 2. As a faujasite-type zeolite, 1
A modified faujasite-type zeolite produced by contacting a faujasite-type zeolite that has not been subjected to a heat history of 50 ° C. or higher with a dealuminating agent in the aqueous phase in the presence of soluble silica at a pH of 4 or less, or further this modified faujasite-type zeolite The catalyst composition for catalytic cracking of hydrocarbons according to claim 1, which is obtained by calcining site-type zeolite. 3. As a faujasite-type zeolite, 1
At least the residual alkali metal of the modified faujasite-type zeolite produced by contacting a faujasite-type zeolite that has not been subjected to a heat history of 50 ° C. or higher with a dealumination agent in the aqueous phase in the presence of soluble silica at a pH of 4 or less. Part of ammonium ion and /
2. The catalyst composition for catalytic cracking of hydrocarbons according to claim 1, which is substituted with a rare earth metal cation or is used after being calcined. 4. A modified faujasite-type zeolite and a porous inorganic oxide having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in the state of not being subjected to a heat history of 150 ° C. or more. 2. The method for producing a catalyst composition for catalytic cracking of hydrocarbon according to claim 1, wherein the precursor is mixed with the precursor, the mixture is molded into a desired shape, and then dried or dried and calcined. 5. A modified faujasite-type zeolite and a porous inorganic oxide having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in the state of not being subjected to a heat history of 150 ° C. or more. The precursor of the catalyst composition for catalytic cracking of hydrocarbons according to claim 1, which is obtained by mixing the precursor of (1) with the above (1) and molding the mixture into a desired shape.