JPH08173816A - Catalyst composition for fluidized catalytic cracking of hydrocarbon and its production - Google Patents

Abstract

PURPOSE: To produce a catalyst compsn. excellent in bottom oil cracking ability, producing small amts. of hydrogen and coke and giving gasoline, kerosene and light oil fractions in large quantities when the catalyst compsn. is used for catalytic cracking of hydrocarbon, especially heavy hydrocarbon. CONSTITUTION: This catalyst compsn. contains alumina, crystalline aluminosilicate zeolite and an inorg. oxide matrix other than alumina and each of the components contains phosphorus atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons and a method for producing the same, and more particularly to hydrocarbons, especially heavy hydrocarbons containing metal contaminants such as nickel and vanadium. TECHNICAL FIELD The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons, which can be used for fluid catalytic cracking and has a low production amount of hydrogen and coke, and can enhance the yield of gasoline and kerosene gas oil fraction, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Catalytic cracking of hydrocarbons is intended primarily for the production of gasoline, and the catalysts used therein must naturally have high cracking activity and high gasoline selectivity. Furthermore, it is required that the yield of kerosene gas oil fraction (LCO) is also high. The deterioration of petroleum conditions in recent years has caused a situation in which low-grade crude oil must be applied to an atmospheric distillation unit (topper), resulting in an increase in the proportion of residual oil generated from the topper, which is usually 650 ° F or higher. . In recent years, such residual oil has been unavoidably used as a raw material for catalytic cracking, and therefore catalytic cracking catalysts are increasingly required to have the ability to crack heavy fractions. In order to efficiently decompose heavy fractions, the matrix part of the catalyst is made active and the extralattice aluminum of zeolite is effectively used to contribute to the decomposition activity. While these methods are excellent for cracking heavy fractions, they are also responsible for increasing the production of hydrogen and coke.
Therefore, as a catalyst for catalytic cracking of heavy hydrocarbons, the present applicant previously modified Y-type faujasite zeolite with phosphorus, and a fluid catalytic cracking catalyst using this catalyst (Japanese Patent Laid-Open No. 63-
197549), or a fluidized catalytic cracking catalyst (JP-B5-33102) in which alumina particles have been modified with phosphorus in advance and dispersed in a matrix together with zeolite to improve the selectivity by reducing the generation of hydrogen and coke. did. However, since these catalysts are methods of previously modifying the faujasite-type zeolite or alumina particles with phosphorus and incorporating it into the catalyst, the phosphorus component is not supported on all of the components constituting the catalyst. However, the effect of the phosphorus component is not sufficiently exerted, and the phosphorus component modified at the time of catalyst preparation is redissolved in the aqueous slurry again, and phosphorus escapes to the outside of the system when the catalyst is washed in the subsequent step. There was room for further improvement.

[0003]

[Objective] The object of the present invention is to use for catalytic cracking of hydrocarbons, especially heavy hydrocarbons, with excellent bottom (bottom oil) resolution, low hydrogen and coke production, and gasoline and kerosene oil distillate. It is another object of the present invention to provide a catalyst composition for fluid catalytic cracking of hydrocarbons, which has a large content, and a method for producing the same.

[0004]

According to the present invention, a mixed slurry of alumina, a crystalline aluminosilicate zeolite and a precursor of an inorganic oxide matrix other than alumina is spray-dried, and the obtained fine spherical particles are brought into contact with a phosphate ion-containing aqueous solution, particularly p
A method for producing a catalyst composition for fluid catalytic cracking of hydrocarbons, which comprises contacting with a phosphate ion-containing aqueous solution within a range of H2 to 6, and a catalyst composition for fluid catalytic cracking of hydrocarbons obtained by the production method. Regarding things. The present invention will be specifically described below. The catalyst composition for fluid catalytic cracking of hydrocarbons of the present invention comprises 1 to 30% by weight of alumina, preferably 3 to 20% by weight, 5 to 50% by weight of crystalline aluminosilicate zeolite, preferably 5 to 40% by weight. , Containing 20 to 94% by weight, preferably 35 to 92% by weight, of an inorganic oxide matrix other than alumina,
Moreover, each of the above-mentioned respective components is characterized by containing a phosphorus atom.

In the present invention, the crystalline aluminosilicate zeolite (zeolite) used in the present invention may be the zeolite used in the catalytic cracking catalyst composition of hydrocarbons, such as X-type zeolite, Y-type zeolite, mordenite,
Synthetic zeolite such as ZSM type zeolite or natural zeolite can be used, and the zeolite is at least one cation selected from the group consisting of hydrogen, ammonium and polyvalent metal as in the case of the conventional catalytic catalyst for catalytic cracking. Used in the ion-exchanged form. Y-type zeolite, particularly ultra-stable Y-type zeolite, is preferable because it has excellent hydrothermal resistance. The alumina in the present invention includes alumina and / or alumina hydrate, and
Alternatively, examples of the alumina hydrate include activated alumina, α-alumina, boehmite, pseudo-boehmite, bayerite, gypsite, and amorphous alumina hydrate.
In particular, 3 to 7 obtained by airflow firing of aluminum hydroxide
0 μm of ρ and / or χ-alumina is preferable because it has an excellent ability to capture the metal contained in the heavy fraction. Further, the inorganic oxide matrix in the present invention is a conventional matrix component used in a catalyst for ordinary catalytic cracking which acts as a binder such as silica, silica alumina, silica magnesia, alumina magnesia, silica zirconia, and silica magnesia alumina. is there. Such matrix components also include kaolin, halloysite, montmorillonite and the like. Further, the catalyst composition for fluid catalytic cracking of hydrocarbons obtained in the present invention may contain a conventional metal scavenger together. In the method of the present invention, the above-mentioned zeolite, alumina and / or alumina hydrate and the precursor of the inorganic oxide matrix other than alumina are uniformly mixed at a predetermined ratio, and the resulting mixed slurry is spray-dried to form a fine powder. It is preferred to produce spherical particles.

In the present invention, the phosphate ion-containing aqueous solution used for introducing a phosphorus atom into the fine spherical particles includes phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and other water-soluble phosphoric acid. It can be prepared by dissolving a salt or the like in water at an arbitrary concentration. The phosphate ion-containing aqueous solution is spray-dried, washed if necessary, desalted and dealkalized to obtain fine spherical particles, and the resulting fine spherical particles have a pH of 2 to
The contact is carried out under the conditions of No. 6 at room temperature to about 100 ° C.
When the pH of the fine spherical particles in contact with the phosphate ion-containing aqueous solution is lower than 2, the crystalline aluminosilicate zeolite crystals in the fine spherical particles are broken, which is not preferable. Further, if the pH is higher than 6, the introduction property of phosphorus into the fine spherical particles is deteriorated, which is not preferable. The preferred pH for contact is in the range of 3-4. By the above-mentioned contact operation, the fine spherical particles into which phosphorus has been introduced are dried and, if desired, calcined to form a catalyst composition. It is desirable that the phosphorus content of the obtained catalyst composition is adjusted to a range of 0.1 to 3% by weight, preferably 0.1 to 1.5% by weight as P ₂ O ₅ . The amount of phosphorus atoms is 0.1
If it is less than 5% by weight, hydrogen and coke formation during the reaction cannot be sufficiently suppressed, while if it exceeds 3% by weight, the decomposition activity of the catalyst is lowered, which is not desirable.

In the method of the present invention, since the phosphorus atom is introduced into any of the crystalline aluminosilicate zeolite, alumina and the inorganic oxide matrix, the resulting catalyst composition contains a metal contaminant such as vanadium or nickel. It exhibits an excellent effect on catalytic cracking of heavy hydrocarbons.
In particular, it has a characteristic that the decomposition rate of the bottom is high. The catalyst composition obtained by the method of the present invention shows that the strong acid point is decreased and the weak acid point is increased as compared with the catalyst composition which is not subjected to phosphorus treatment from the measurement of the solid acid strength distribution by the ammonia adsorption method. It was. By reducing the strong acid point of the catalyst by phosphorus treatment, it is possible to reduce the generation of hydrogen and coke.Also, although the strong acid point is reduced by phosphorus treatment, the weak acid point amount increases, but the total acid amount hardly changes. However, the heavy oil fraction can still be efficiently decomposed, and the liquid yield does not decrease. Further, in the method of the present invention, not only can phosphorus be prevented from flowing out of the catalyst system, but since the inorganic oxide matrix also contains phosphorus, it exhibits an excellent effect on the decomposition of the bottom as described above. .

Example 1 Y-type crystalline aluminosilicate zeolite (NH ₄ Y zeolite) ammonium-exchanged with 20 kg of silica hydrosol containing 5 wt% of SiO ₂ prepared by adding sulfuric acid to water glass at an ion exchange rate of 95%. A mixed slurry was prepared by adding 1650 g (dry basis), 2100 g of kaolin clay (dry basis) and 250 g of alumina particles (dry basis) obtained by air-flow firing of gibbsite having an average particle diameter of 30 μm. This mixed slurry was spray-dried to obtain fine spherical particles. The microspheres were then washed. At the time of cleaning, an aqueous solution of RECl ₃ corresponding to 0.5 wt% (based on oxide) as rare earth metal (RE) was added to support RE, and then phosphorus was added as P ₂ O ₅ to H corresponding to 0.5 wt%. ₃ PO ₄ aqueous solution was added, and further hydrochloric acid aqueous solution was added to maintain the suspension pH at 3.5 for 60 minutes for 20 minutes.
Phosphorus was supported by stirring at ℃. This was dried to prepare a catalyst composition for fluid catalytic cracking of the present invention. This fluid catalytic cracking catalyst composition contains 33 wt% of NH ₄ Y zeolite.
%, Alumina particles 5 wt%, RE ₂ O ₃ 0.5 wt%
%, P ₂ O ₅ 0.5 wt% and the average particle size is 63
μm. This catalyst composition is referred to as catalyst B. In the same manner as the above-mentioned preparation method, catalysts were prepared with different amounts of phosphorus added. That is, the addition amount is 0, 1, 1.5, respectively.
The H ₃ PO ₄ aqueous solution was added so as to be wt% (based on oxide). 33 wt% of NH ₄ Y zeolite was used as the catalyst.
And 5% by weight of alumina particles. Let these catalysts be catalysts A, C, and D, respectively.

Comparative Example 1 To 250 g (dry basis) of alumina particles obtained by air-flow firing of gibbsite having an average particle diameter of 30 μm, an aqueous H ₃ PO ₄ solution was added so that the phosphorus content was 12 wt% as P ₂ O _5. It was left for 1 hour. 1 of these phosphoric acid-added alumina particles
It was dried at 10 ° C. for 17 hours and then baked at 600 ° C. for 2 hours to prepare phosphorus-containing alumina particles. The phosphorus-containing alumina particles were mixed with a mixed slurry containing silica hydrosol, Y-type crystalline aluminosilicate zeolite, and kaolin clay prepared by the same method as in Example 1, and spray-dried to obtain fine spherical particles. It was Next, the particles were washed, and RECl ₃ was added so that RE was 0.5 wt% (based on oxide) at the time of washing, and then dried to obtain a fluid catalytic cracking catalyst E. When the P ₂ O ₅ content of the catalyst E was analyzed, it was 0.5 wt% based on the catalyst.

Comparative Example 2 The Y-type crystalline aluminosilicate zeolite used in Example 1 was suspended in an aqueous solution of ammonium sulfate with phosphoric acid added, stirred at 90 ° C. for 0.5 hours, washed by filtration, and containing phosphorus. NH ₄ Y faujasite was prepared. When the phosphorus content was analyzed, it was 1.9 wt%. The obtained phosphorus-containing NH ₄ Y faujasite was prepared by the same method as in Example 1, silica hydrosol, alumina particles,
This was mixed with a mixed slurry containing kaolin clay and spray-dried to obtain fine spherical particles. Next, the particles are washed, and RE is 0.5 wt% (based on oxide) during washing.
So that RECl ₃ was added, and then dried to obtain a fluid catalytic cracking catalyst F. When the content of P ₂ O _{5 in} the catalyst F was analyzed, it was 0.5% by weight.

Comparative Example 3 Phosphorus-containing alumina particles and phosphorus-containing Y-type crystalline aluminosilicate zeolite were prepared in the same manner as in the methods of Comparative Example 1 and Comparative Example 2. However, here, the P ₂ O ₅ content in the phosphorus-containing alumina particles is 6 wt%, and the P ₂ O ₅ content in the phosphorus-containing Y-type crystalline aluminosilicate zeolite is 6% by weight.
_{The 2} O ₅ content was adjusted to 1.0 wt%. These were mixed with silica hydrosol and kaolin clay prepared by the same method as in Example 1, spray-dried, and then RECl was adjusted to 0.5 wt% (oxide based) during washing. ₃ was added and then dried to obtain a fluid catalytic cracking catalyst G. The content of P ₂ O _{5 in} the catalyst G is 0.5 wt.
%Met.

<Performance test> The catalyst particles A to G obtained in the examples and comparative examples were subjected to the catalyst circulation regeneration method Midg.
Performance was evaluated using the et-2 pilot plant. The operating conditions are as follows. Feedstock: Desulfurized atmospheric residual oil (40%) and desulfurized vacuum gas oil (6
Oil mixed with 0%) Weight hourly space velocity: 25 hr ^-1 catalyst / oil 7 weight ratio Reaction temperature 520 ℃ Regeneration tower temperature 670 ℃ Stripping temperature 500 ℃ Coke on regenerated catalyst 0.05 wt% Catalyst for performance evaluation Pseudo-equilibrium treatment was performed. Nickel and vanadium are added to each catalyst by 200
0, 4000 ppm was deposited. That is, after each catalyst was previously calcined at 600 ° C. for 1 hour, a predetermined amount of nickel naphthenate and vanadium naphthenate solution was absorbed in each catalyst,
Then, it was dried at 110 ° C. and baked at 600 ° C. for 1.5 hours. In order to pseudo-equilibrium these catalysts, each catalyst was heated to 810 ° C.
The sample was subjected to fluidized steam treatment for 6 hours and subjected to measurement. The measurement results are shown in Tables 1 and 2.

As shown in Table 1, the catalysts B, C of the present invention,
D is LCO / HC showing a bottom resolution as compared with the phosphorus-free catalyst A or the catalysts E, F and G shown in the comparative examples.
The O ratios show almost the same value, while H ₂ / k and Coke / k, which show the amount of hydrogen and coke produced, both show low values. It can be seen that the catalyst keeps the amount low.

[0014]

[Table 1]

[0015]

[Table 2] * ² BP, 204-343 ° C fraction * ³ BP, 343 ° C ⁺ fraction

Specific embodiments of the present invention will be described below. 1. A catalyst composition for fluid catalytic cracking of hydrocarbons, which is constituted by containing an alumina, a crystalline aluminosilicate zeolite and an inorganic oxide matrix other than alumina, and in which all of the above components contain a phosphorus atom. 2. Alumina 1 to 30% by weight, preferably 3 to 20% by weight, crystalline aluminosilicate zeolite 5 to 50% by weight, preferably 5 to 40% by weight, inorganic oxide matrix other than alumina 20 to 94% by weight, preferably 35 ~
A catalyst composition for fluid catalytic cracking of hydrocarbons, which is constituted by containing 92% by weight and in which each of the above components contains a phosphorus atom. 3. 0.1 to 3% by weight of phosphorus atom as phosphorus as P ₂ O ₅ ,
The catalyst composition for fluid catalytic cracking according to 1 or 2 above, which is preferably contained in the range of 0.1 to 1.5% by weight. 4. The above 1, 2 in which the phosphorus atom is contained in the form of P ₂ O _5.
Alternatively, the catalyst composition for fluid catalytic cracking according to 3 above. 5. 5. The catalytic composition for fluid catalytic cracking according to 1, 2, 3 or 4, wherein the crystalline aluminosilicate zeolite is ion-exchanged with at least one cation selected from the group consisting of hydrogen, ammonium and polyvalent metals. Stuff.

6. The catalyst composition for fluid catalytic cracking according to the above 5, wherein the crystalline aluminosilicate zeolite is a Y-type zeolite, preferably a super-stable Y-type zeolite. 7. 7. The catalyst composition for fluid catalytic cracking according to the above 1, 2, 3, 4, 5 or 6, wherein the alumina is alumina and / or alumina hydrate. 8. 8. The catalyst composition for fluid catalytic cracking according to 7, wherein the alumina is ρ- and / or χ-alumina having a particle size of 3 to 70 μm, which is obtained by air-flow firing of aluminum hydroxide. 9. Crystalline aluminosilicate zeolite, alumina and fine spherical particles composed of the above components obtained by spray-drying a mixed slurry of a precursor of an inorganic oxide matrix other than alumina are prepared. Fluid contact of hydrocarbons according to the above 1, 2, 3, 4, 5, 6, 7 or 8, characterized in that the phosphorus component is introduced into any of the above components by contacting with a phosphate ion-containing aqueous solution. A method for producing a decomposition catalyst composition. 10. For fluid catalytic decomposition according to the above 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the contact between the fine spherical particles and the phosphate ion-containing aqueous solution is carried out within the range of pH 2 to 6, preferably pH 3 to 4. A method for producing a catalyst composition. 11. 11. The method for producing a catalyst composition for fluid catalytic cracking according to 10 above, wherein the contact between the fine spherical particles and the phosphate ion-containing aqueous solution is performed at room temperature to about 100 ° C.

[0018]

[Effect] In the method of the present invention, the phosphorus atom is introduced into any of the crystalline aluminosilicate zeolite, alumina and the inorganic oxide matrix, so that the obtained catalyst composition contains a metal contaminant such as vanadium or nickel. It exhibits an excellent effect on catalytic cracking of heavy hydrocarbons. In particular, it has a characteristic that the decomposition rate of the bottom is high.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Morio Fukuda 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Catalyst Catalyst Wakamatsu Plant Co., Ltd.

Claims (3)

[Claims] 1. A fluid catalytic cracking of a hydrocarbon comprising an alumina, a crystalline aluminosilicate zeolite and an inorganic oxide matrix other than alumina, wherein all of the components contain a phosphorus atom. Catalyst composition. 2. 1 to 30% by weight of alumina, 5 to 50% by weight of crystalline aluminosilicate zeolite, and 20 to 94% by weight of an inorganic oxide matrix other than alumina, and any one of the above components. A catalyst composition for fluid catalytic cracking of hydrocarbons, which contains phosphorus atoms. 3. A fine spherical particle is prepared by spray-drying a mixed slurry prepared by mixing alumina, crystalline aluminosilicate zeolite and precursors of an inorganic oxide matrix other than alumina in a predetermined ratio. The method for producing a catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1 or 2, wherein the particles are contacted with an aqueous solution containing phosphate ions.