JPS61227843A - Catalyst composition for catalytic cracking of hydrocarbon and its preparation - Google Patents

Abstract

PURPOSE:To obtain a catalyst composition having the resistance to metallic properties by adding the alumina particles contg. a metallic component (alkaline earth metal and rare earth metal) and phosphorus component to a catalyst for the catalytic cracking contg. crystalline aluminosilicate. CONSTITUTION:Al2O3 is impregnated in an aq. soln. contg. one or more kinds of alkaline earth metal and rare earth metal and phosphate ion and calcined about at 250-850 deg.C and the metallic component and phosphorus component are fixed on Al2O3. The particle size of Al2O3 is regulated to 2-60mu and the quantities of metal and phosphorus are respectively regulated to the range of 0.1-5wt% and 0.6-12.2wt%. A catalyst composition for the catalytic cracking is obtained by dispersing uniformly the obtained Al2O3 particles and crystalline aluminosilicate in a precursor slurry of a porous inorganic oxide matrix such as silica hydrosol and spray-drying it like an ordinary method. Since the metallic pollutants are collectively deposited on Al2O3, the high cracking activity and the high gasoline selectivity are maintained in this catalyst.

Description

Detailed Description of the Invention "Industrial Applications" The present invention relates to a catalyst composition for catalytic cracking of hydrocarbons, and more specifically, it relates to a catalyst composition for catalytic cracking of hydrocarbons, and more specifically, it relates to a catalyst composition for catalytic cracking of hydrocarbons. To be used for the catalytic cracking of heavy hydrocarbon oils, exhibiting excellent metal resistance, maintaining high cracking activity and high gasoline selectivity for a long period of time, and suppressing the production of hydrogen and coke to low levels. The present invention relates to a catalyst composition capable of producing the same and a method for producing the same.

[Prior art] Catalytic cracking of hydrocarbons is originally intended for the production of gasoline, so the catalyst used for this must naturally have high cracking activity and high gasoline selectivity. Therefore, metal resistance is required for catalysts for catalytic cracking. The worsening oil situation in recent years has forced the use of low-grade heavy hydrocarbon oil, typically residual oil containing heavy metals such as vanadium, nickel, iron, and copper, as a raw material for catalytic cracking. This makes the metal resistance of catalytic cracking catalysts increasingly important.

Generally, during the catalytic cracking of heavy hydrocarbon oils, metal contaminants contained in the feedstock oil are deposited on the catalyst, which causes the cracking activity and gasoline selectivity of the catalyst to be more or less reduced. Therefore, the catalysts for catalytic cracking that are currently commonly used commercially, typically catalysts for catalytic cracking in which zeolite is dispersed in a porous inorganic oxide 71-lix, are somewhat satisfactory even if a certain amount of metal is deposited. Usually, it has enough metal resistance to maintain the desired catalytic performance. However, when this type of catalyst is used to catalytically crack low-grade heavy hydrocarbon oil as described above, the catalyst is also contaminated with multiple metal contaminants. is deposited, which promotes the dehydrogenation reaction, increasing the production of hydrogen and coke, and even destroying the crystal structure of the zeolite, making it impossible to fulfill the original purpose of catalytic cracking.

Under these circumstances, as a countermeasure when subjecting low-grade heavy hydrocarbon oil with a large amount of metal contaminants to catalytic cracking,
Measures have been taken such as increasing the amount of catalyst used to reduce the amount of deposited metal per catalyst particle, or adding an antimony compound to the feedstock oil to suppress the decrease in catalyst activity caused by deposited metals. I came here. However, these countermeasures for operation I- are not advantageous because the driving cost 1- increases. On the other hand, as a measure to improve the performance of the catalyst, it is known that the amount of zeolite dispersed in the catalyst is increased compared to that of a normal catalytic cracking catalyst.
No. 430,199 describes a catalytic cracking catalyst in which a phosphorus compound is added to the catalytic cracking catalyst containing Ezeolite 1 to improve the metal resistance of the catalyst. Furthermore, U.S. Pat. No. 4,228,036 discloses a catalyst for catalytic cracking in which zeolite is dispersed in a matrix of alumina-aluminum phosphate-silica.

In addition, U.S. Patent No. 4,222,896 describes Mg0
-A 120. - A catalyst in which zeolite is dispersed in a matrix consisting of A I PO4 was published in JP-A-59-150.
No. 539 proposes a catalyst in which zeolite is dispersed in an alumina-magnesia matrix.

14 = [Problems to be solved by the invention] Among the conventional catalysts for catalytic cracking developed to improve the metal resistance of catalysts, catalysts with increased zeolite content are I- itself is expensive and therefore cannot be made into a commercially attractive catalyst. Also,
Catalysts containing phosphorus components and/or magnesium components do not necessarily have satisfactory metal resistance.

It is true that the phosphorus and/or magnesium components contribute to improving the metal resistance of catalytic cracking catalysts, but in conventional catalysts of this type, the phosphorus and/or magnesium components are not uniform throughout the catalyst. It is presumed that if too much metal is deposited, the metal resistance of the catalyst will deteriorate, making it impossible to obtain satisfactory results.

According to the knowledge obtained by the present inventors, when an alumina-containing catalytic cracking catalyst is used for catalytic cracking of hydrocarbon oil to deposit vanadium, and the spent catalyst is analyzed with an X-ray microanalyzer, the deposited vanadium is The distribution corresponds well to that of alumina. This fact suggests that by allowing alumina to exist in the form of blocks in the catalyst for catalytic cracking, it is possible to concentrate the waste contaminants on the blocks of alumina.

[Means for Solving the Problems] The present invention consists of alumina having a particle size of 2 to 60μ with a fixed amount of phosphorus and one or more metal components selected from alkaline earth metals and rare earth metals. Provided is a catalyst composition for catalytic cracking of hydrocarbons in which particles and crystalline aluminosilicate-1 are uniformly dispersed in a porous inorganic oxide 71-lix.

In this catalyst composition, the metal component and phosphorus component-containing alumina particles are in the range of 5 to 75 percent, the crystalline aluminosilicate is in the range of 5 to 50 percent, and the porous inorganic oxide is in the range of 71 percent. -Rix can be adjusted within the range of 20 to 50% by weight.

The catalyst composition of the present invention can be produced by spray-drying a slurry of a mixture of alumina particles containing a metal component and a phosphorus component, crystalline aluminosilicates 1 to 1, and a 71-rix precursor. The alumina particles to which the components and phosphorus components are fixed must have a particle size in the range of 2 to 60 microns. If fine alumina particles with a particle size below this range are used, the alumina particles will be uniformly dispersed in the catalyst composition, and the side bottom tube [1
This is because it is not possible to make it unevenly distributed in a tsuku-like manner, and
This is because it is not preferable for the particle size to exceed the above range in relation to the average particle size of the catalyst composition finally obtained.

Therefore, the metal component and phosphorus component-containing alumina particles of the present invention include alumina or alumina hydrate with a particle size of 2 to 60p prepared in advance, an aqueous solution containing phosphate ions (PO43), an alkaline earth metal and/or Contact with a rare earth metal-containing aqueous solution, dry and calcinate, or bring coarse-grained alumina or alumina hydrate into contact with a phosphate ion-containing aqueous solution and an alkaline earth metal and/or rare earth metal-containing aqueous solution and dry. After firing, the particle size is 2 to 6011.
It is manufactured by grinding into When impregnating alumina with metal components and phosphorus components, both components can be simultaneously impregnated using a mixed solution of an aqueous solution containing phosphate ions and an aqueous solution containing alkaline earth metals and/or rare earth metals. , it is also possible to impregnate both components separately. In the latter case, although the order does not matter, it is preferable to dry and sinter the alumina after the first impregnation step is completed. In any case, the phosphate ion-containing aqueous solution includes phosphoric acid, ammonium hydrogen phosphate,
Aqueous solutions of ammonium phosphate, phosphate esters, etc. or mixtures thereof can be used. Furthermore, as the aqueous solution containing alkaline earth metals and/or rare earth metals, aqueous solutions of nitrates, carbonates, chlorides, etc. of these metals can be used.

The amount of phosphorus introduced into the alumina particles by contact with the aqueous solution containing phosphate ions is 0.6-12.2% by weight of the alumina as elemental phosphorus (P/AI atomic ratio = 0.01-12.2% by weight of the alumina).
0.20) is allowed. This is because if the content is below this range, the effect of containing phosphorus will not be realized, and if it is above this range, the pore volume of the alumina will decrease too much, which is not preferable. On the other hand, the amount of alkaline earth metal and/or rare earth metal introduced into alumina can be in the range of 0.1 to 5% by weight of alumina as elemental metal, and if it deviates from this range, it will not be possible to achieve the desired amount. can't get any effect. Firing after introduction of metal components and phosphorus components is generally performed at a temperature of 25%.
The firing is carried out at a temperature range of 0 to 850°C, and the metal components and phosphorus components are fixed to the alumina by this firing.

Synthetic Y-type zeolite, mordenite, ZSM-type zeolite, natural zeolite, etc. can be used as the crystalline aluminosilicate of the present invention, and these can contain hydrogen, ammonium, and polyvalent zeolites, as in the case of ordinary catalysts for catalytic cracking. It is used in an ion-exchanged form with a cation selected from metals. Porous inorganic oxides include silica, silica-alumina, silica-magnesia, etc.
Matrix components commonly used in conventional catalytic cracking catalysts can also be used in the present invention.

The catalyst composition of the present invention can be produced in a manner similar to that of conventional crystalline aluminosilicate-containing catalysts for catalytic cracking, except for the use of the specific alumina particles described above.

That is, the catalyst composition of the present invention can be applied to a precursor slurry of a porous inorganic oxide matrix, such as silica hydrosil, silica-alumina hydrosil, etc.
It can be prepared by adding and uniformly dispersing the alumina particles described above and crystalline aluminosilicate, and spray-drying the resulting mixture slurry in a conventional manner. The amounts of the matrix precursor slurry, metal component- and phosphorus component-containing alumina particles, and crystalline aluminosilicate to be used are such that the final catalyst composition contains the above alumina particles in a range of 5 to 75% by weight. The content of crystalline aluminosilicate-1. is adjusted to be in the range of 5 to 50% by weight, and the content of the matrix is adjusted to be in the range of 20 to 50% by weight, respectively. Then, the spray-dried particles are washed as necessary, and after washing, they are dried again.

[Function] In the catalytic cracking reaction of hydrocarbon oil, metal contaminants such as vanadium and nickel contained in the feedstock oil are deposited on the catalyst, reducing the cracking activity and gasoline selectivity of the catalyst, and further reducing the deposited metals. Due to the dehydrogenation reaction, the production capacity of coke and hydrogen increases significantly. Especially vanadium is usually 63
In a catalyst regeneration atmosphere maintained at a temperature of 0° C. or higher, it moves near the crystalline aluminosilicate and destroys its crystal structure.

The catalyst composition for catalytic cracking of the present invention has alumina particles fixed with one or more metal components selected from alkaline earth metals and rare earth metals and a phosphorus component with a particle size of 2 to 60.
Because it is dispersed in the composition in the form of blocks of μ, it is considered a catalyst.
Second, the metal contaminants deposited on the particles are captured and aggregated, and are not dispersed in the composition. Therefore, even in a catalyst regeneration atmosphere maintained at 630° C. or higher, the movement of deposited metal, especially vanadium, to the vicinity of the crystalline aluminosilicate is suppressed, and as a result, the destruction of its crystal structure is also suppressed. Further, it is presumed that the phosphorus introduced into alumina promotes the aggregation of metals such as vanadium and nickel captured on the alumina, and promotes the inactivation of these metals. Furthermore, according to the experimental results of the present inventors, alkaline earth metals and rare earth metals have a very strong affinity with metal oxides such as vanadium and nickel.

Therefore, it is presumed that the action of alumina to trap metal contaminants deposited on the catalyst is further promoted by metal components such as alkaline earth and rare earth.

Thus, the catalyst composition of the present invention can maintain high cracking activity and high gasoline selectivity even when a large amount of metal contaminants are deposited, and can suppress the production of coke and hydrogen to a small amount.

Example 1 Aluminum hydroxide obtained by Bayer method was dissolved in air at 60%
2′# at 0℃! Inter-calcined 9 then this calcined alumina 5
A phosphoric acid aqueous solution prepared by diluting 82 g of orthophosphoric acid with a concentration of 85% with water to make 115n+1 was added to the calcined alumina and blended for 10 minutes. After drying these phosphoric acid-added alumina particles at 110°C for 17 hours,
Phosphorus-containing alumina particles were prepared by firing at 600° C. for 1 hour. The average particle size of these phosphorus-containing alumina particles is 30μ, and the phosphorus content is 4.2% by weight (P/AI atomic ratio is 0.
．． 07). RECI corresponding to 2.1% by weight of rare earth metal (RE) in the phosphorus-containing alumina particles.

After adding and stirring an aqueous solution of , it was dried at 110°C for 17 hours and further calcined at 600°C for 2 hours to prepare RE-fixed phosphorus-containing alumina particles.

500 g of the above RE-fixed phosphorus-containing alumina particles were added to 4000 g of silica hydrosil containing 5% by weight of 5in2 prepared by adding sulfuric acid to water glass, and 300 g of Y-type crystalline aluminosilicate (zeolite) subjected to hydrogen ion exchange. was added to make a mixed slurry. This mixed slurry was then spray-dried, washed, and further dried to obtain the catalyst composition for catalytic cracking of the present invention.

This catalyst composition contains 50% RE-fixed phosphorus-containing alumina particles.
Weight %, l-T-Y type zeolite 30 weight 1%, 71
It contained 20% by weight of silica derived from -Rix. This catalyst silk product is referred to as catalyst A.

Example 2 A catalyst composition was prepared in the same manner as in Example 1 except that an aqueous Mg(NO3)2 solution was used instead of the aqueous RECI3 solution. This catalyst composition contained 4.8% P2O5 and MgO
1.2% by weight and 44% by weight Al2O2.

This will be referred to as catalyst B.

Example 3 Aluminum hydroxide with an average particle size of 50μ obtained by the Bayer method was treated with phosphoric acid in the same manner as in Example 1, and the phosphorus content was 8.5% by weight of alumina (P/Al atomic ratio 0). .14
) were obtained. Ca equivalent to 2.1% as Ca in this phosphorus-containing alumina particle
A catalyst composition was obtained in the same manner as in Example 1, except that the CI 2 aqueous solution was added and the REC111 aqueous solution was not used. This is designated as catalyst C.

Comparative Example IPEC] A catalyst composition was obtained in the same manner as in Example 1 except that the aqueous solution was not used. This catalyst contained 50% by weight of phosphorus-containing alumina particles and 30% by weight of zeolite. Use this as a catalyst.

Comparative Example 2 An aluminum sulfate solution was neutralized with aqueous ammonia, and the generated aluminum hydroxide precipitate was washed to remove by-product salts. At20. To this alumina hydrogel slurry corresponding to 440 g of
g with stirring, then 12.4 g as MgO
An aqueous solution of magnesium nitrate corresponding to the above was added.

5i prepared by adding sulfuric acid to water glass was added to this slurry.
A mixed slurry was prepared by adding 4000 g of silica hydrosil with a concentration of 5 wt% and 300 g of H-Y type zeolite. Next, this slurry was spray dried in the same manner as in Example 1, washed, and further dried to obtain a catalyst composition for catalytic cracking.

This catalyst composition contained 4.8% by weight of P2O and 1% by weight of MgO.
．． 2% by weight, and 44% by weight of A120a. This is designated as catalyst E.

Example 4 (Example of catalyst use) For each of the above catalysts A-E, Performance evaluation was performed using ASTM MAT.

First, in order to examine metal resistance, nickel and vanadium were deposited on the famous catalyst as follows. That is, after each catalyst was preliminarily calcined at 600°C for 1 hour, a predetermined amount of a benzene solution of nickel naphthenate and vanadium naphthenate was absorbed into each catalyst, and then dried at 110°C and then heated at 600°C.
It was baked at 0°C for 1.5 hours. After that, each catalyst was steam-treated at 770°C for 6 hours to achieve pseudo-equilibration, and then steam-treated again at 770°C for 6 hours.
It was baked at 00°C for 1 hour. Moreover, each catalyst on which nickel and vanadium were not deposited was also subjected to a steam treatment at 770° C. for 6 hours for pseudo-equilibrium, and then calcined at 600° C. for 1 hour.

Using each catalyst pretreated in this way, ASTM
A MAT evaluation test was conducted. The results are shown in Table-1. still,
The reaction conditions are as follows.

Raw material oil: Desulfurized vacuum gas oil Reaction temperature = 482℃ Space velocity: 16hr"" Catalyst/oil hole: 3 (weight) (Margin below) As shown in Table 1, catalysts A and B of the present invention.

C is MgO, P2O, p, 120. Compared to Catalyst E consisting of 71-Rix and zeolite in which 71-Rix and 5i02 were uniformly mixed, the conversion after nickel and vanadium deposition and gasoline yield were higher, and the amount of coke and hydrogen produced was lower. Further, catalysts A, B, and C have higher conversion rates and gasoline yields than catalysts containing no alkaline earth and/or rare earth elements.

[Effects] The catalyst composition for catalytic cracking of hydrocarbons of the present invention exhibits high cracking activity and high gasoline selectivity even when a large amount of metal contaminants are deposited on the catalyst, and reduces the amount of coke and hydrogen produced. can be kept to a low level.

Procedural amendment written in 1985 1 几 41 川 1, Indication of the case 1988 Patent Application No. 2712oo 2, Name of the invention / Catalyst composition for hydrocarbon catalytic cracking and its manufacturing method 3, Person making the amendment Case and Relationship between patent applicant 2-6-2 Otemachi, Chiyoda-ku, Tokyo Representative Masaru Ishiguro 4, agent 5 Contents of amendment Each column 6 of ``Detailed explanation'', contents of correction (, 1) after ``r blunting'' on page 6, line 15,
join.

(2) Page 16, line 4 (7) rPEcl, J to Ii
'REC1,,,l].

Written in April 3, 1986 (Kawa Patent Application No. 271200 of 1982, Title of Invention: Catalyst Composition for Catalytic Cracking of Hydrocarbons and Method for Manufacturing the Same) 2-chome Otemachi, Chiyoda-ku, Tokyo 1m G Tsume 213 Catalyst Chemicals'' Nigyo Co., Ltd. 11 Representative, To ■ Tadashi Ishiguro 4, Agent, Tokyo F, January II l1 M-cho 47 El 5 (〒
102) 5. 1-1 A.1 of the Procedural Amendment Directive April 22, 1985 [1 6, Subject of Amendment Section ``Subject of Amendment'' of the procedural amendment submitted dated January 3011, 1985] and Column 7゜ Details of the amendment As shown in the attachment 8 List of attached documents 1985 1.1” 130 roy 1 Submission of procedural amendment 1F 1 copy Procedure: h Oral letter January 30, 1985 Patent Agency Director Manabu Shiga1, Incident Indication Patent Application No. 271200 of 1982, Title of Invention Catalyst Composition for Catalytic Cracking of Hydrocarbons and Method for Producing the Same Catalystization Command, 2-6-2 Otemachi, Chiyoda-ku, Tokyo Kogyo Co., Ltd. Representative Masaru Ishiguro 4, Agent 4-5 Kojimachi, 1 Daita-ku, Tokyo (102) 5, Subject of amendment

Claims (1)

[Claims] 1. Particle size in which one or more metal components selected from alkaline earth metals and rare earth metals and a phosphorus component are fixed.
A catalyst composition for catalytic cracking of hydrocarbons in which alumina particles of ~60μ and crystalline aluminosilicate are uniformly dispersed in a porous inorganic oxide matrix. 2. The catalyst composition according to claim 1, wherein the amount of the metal component fixed to the alumina particles is 0.1 to 5% by weight of the alumina particles as elemental metal. 3. The catalyst composition according to claim 1, wherein the amount of phosphorus component fixed to the alumina particles is 0.6 to 12.2% by weight of the alumina particles as elemental phosphorus. 4. 5 to 75% by weight of alumina particles on which the metal component and phosphorus component are fixed, and 5% by weight of crystalline aluminohysilicate.
~50 wt%, porous inorganic oxide matrix ~20~
The catalyst composition according to claim 1, containing in the range of 50% by weight. 5. Alumina particles with a particle size of 2 to 60 μm in which one or more all metal components selected from alkaline earth metals and rare earth metals and a phosphorus component are fixed to a porous inorganic oxide precursor slurry, and crystals. 1. A method for producing a catalyst composition for catalytic cracking of hydrocarbons, which comprises mixing aluminosilicate and spray-drying the resulting mixed slurry. 6. The method according to claim 5, wherein the amount of metal component fixed to the alumina particles is 0.1 to 5% by weight of the alumina particles as elemental metal. 7. The method according to claim 5, wherein the amount of phosphorus component fixed on the alumina particles is 0.6 to 12.2% by weight of the alumina particles as elemental phosphorus.