JP2013031845A - Method for producing fluid catalytic cracking catalyst of hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluid catalytic cracking catalyst of hydrocarbons, which has large pore volume and high wear resistance.SOLUTION: The method for producing the fluid catalytic cracking catalyst of hydrocarbons comprises the steps of: spray-drying a slurried mixture of an inorganic oxide matrix precursor containing basic aluminum chloride with zeolite to obtain spherical particles; washing the spherical particles; and drying the washed spherical particles; or further firing the dried spherical particles. Phosphoric acid or a phosphate of 0.1-3 mass% in terms of POis incorporated in an inorganic oxide matrix of the fluid catalytic cracking catalyst but phosphorus is not incorporated in the zeolite thereof.

Description

  The present invention relates to a method for producing a hydrocarbon fluid catalytic cracking catalyst having a large pore volume and high wear resistance.

  Conventional hydrocarbon fluid catalytic cracking catalysts have improved wear resistance by, for example, using raw materials with small particle diameters or increasing the amount of binder to increase the particle density of the catalyst. However, the catalyst produced by the above-described method has a problem that since the pore volume is small, the raw material oil is difficult to diffuse into the catalyst particles, and the cracking activity of the catalyst with respect to the raw material oil is reduced. Therefore, a hydrocarbon fluid catalytic cracking catalyst using basic aluminum chloride (aluminum chlorohydrol) having a high binding force as a binder component and having high wear resistance and a large pore volume has been proposed (for example, patents). Reference 1).

JP-A-62-14947

However, even the hydrocarbon fluid catalytic cracking catalyst using basic aluminum chloride as a binder component is not satisfactory in terms of wear resistance.
Therefore, an object of the present invention is to provide a method for producing a hydrocarbon fluid catalytic cracking catalyst having a large pore volume and high wear resistance.

The above problems are solved by the following inventions 1) to 3).
1) A mixed slurry of an inorganic oxide matrix precursor containing basic aluminum chloride and zeolite is spray-dried, and the resulting spherical particles are washed, then dried or calcined after drying, and a fluidized catalytic cracking catalyst for hydrocarbons In the inorganic oxide matrix of the fluid catalytic cracking catalyst, 0.1 to 3% by mass of phosphoric acid or phosphate as P ₂ O ₅ is contained, and the zeolite contains phosphorus. A method for producing a fluidized catalytic cracking catalyst for hydrocarbons, wherein
2) The method for producing a hydrocarbon fluid catalytic cracking catalyst according to 1), wherein phosphoric acid or a phosphate is contained in at least one of the following steps.
(A) Phosphoric acid or phosphate is mixed in advance with one or more of raw materials comprising an inorganic oxide matrix precursor containing basic aluminum chloride and zeolite.
(B) In the mixed slurry stage, phosphoric acid or phosphate is mixed.
(C) Phosphoric acid or phosphate is mixed with the spherical particles.
(D) Phosphoric acid or phosphate is mixed with the cleaning particles.
(E) The washed particles are dried and further baked, and then mixed with phosphoric acid or phosphate.

3) The method for producing a hydrocarbon fluid catalytic cracking catalyst according to 1) or 2), wherein the zeolite is in an atmosphere having a pH of 2 or higher.

Since the hydrocarbon fluid catalytic cracking catalyst produced according to the present invention contains 0.1 to 3% by mass of phosphorus as P ₂ O ₅ , the basic chloride whose phosphate group (PO ₄ ) is the catalyst component is used. By reacting with aluminum, aluminum phosphate is formed on the surface of the basic aluminum chloride crystal, and the bonding force between the contact surfaces of the adjacent basic aluminum chloride crystals can be increased. As a result, the wear resistance can be increased while maintaining the catalyst performance. Therefore, it is possible to produce a catalyst having a large pore volume and excellent wear resistance.

Phosphorus (phosphorus refers to phosphate group (PO ₄ )) and aluminum compounds (eg, alumina) have high affinity, and basic aluminum chloride is cross-linked with phosphorus to increase the binding strength of basic aluminum chloride. Can do. This improves the wear resistance of the catalyst.
Further, if the phosphorus content of the catalyst is less than 0.1% by mass as P ₂ O ₅ , the amount of aluminum phosphate formed on the surface of the basic aluminum chloride crystal decreases, and the basic aluminum chloride bonds to each other. If the force cannot be increased and the amount exceeds 3% by mass, excess phosphorus may block the pores of the catalyst, which may reduce the pore volume.
In the present invention, “phosphoric acid” means orthophosphoric acid (orthophosphoric acid). Examples of the phosphate include ammonium phosphate, hydrogen phosphate-ammonium phosphate, diammonium hydrogen phosphate, primary aluminum phosphate, primary magnesium phosphate, and the like.

Basic aluminum chloride can be produced by dissolving metallic aluminum (for example, aluminum powder, aluminum foil) in an aluminum chloride aqueous solution, and is represented by the following formula (1).
[Al ₂ (OH) _n Cl _6-n ] _m (1)
(However, 0 <n <6, 1 ≦ m ≦ 10, preferably 4.8 ≦ n ≦ 5.3, 3 ≦ m ≦ 7, where m represents a natural number.)
Constituent components of the inorganic oxide matrix precursor include kaolin, activated alumina, metal trapping agent and the like in addition to basic aluminum chloride.
Examples of the metal trapping agent include alumina particles, phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesia, magnesia-alumina, and the like. .
The catalyst may contain rare earth (rare earth metal). Examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd). Usually, one or more rare earth element chlorides (rare earth) are used. Metal chloride).

The zeolite is preferably in an atmosphere having a pH of 2 or more during the production of a fluid catalytic cracking catalyst for hydrocarbons, and more preferably has a pH of 3-12. Since the pH of the zeolite particle surface cannot be measured directly, the pH is the pH of the system (solution) in which the zeolite particles are present. If the pH is less than 2, the zeolite particles may be dealuminated and the zeolite may be destroyed.
As the zeolite, Y-type zeolite, ultra-stabilized Y-type zeolite (USY), rare earth-exchanged Y-type zeolite (RE-Y), and rare-earth exchanged ultra-stabilized Y-type zeolite (RE-USY) are used.

The hydrocarbon fluid catalytic cracking catalyst produced according to the present invention has a wear resistance index (CCIC Attrition Index. CAI) of 6 or less and a total pore volume (pore diameter of 5.5 to 500 nm) measured by mercury porosimetry. ) Is preferably 0.10 to 0.40 ml / g.
Here, the abrasion resistance index is the value of the catalyst chemical technical report Vol. 13, no. 1, P65, a value measured by the method described in 1996. If the wear resistance index exceeds 6, the catalyst is pulverized during use, which may lead to loss of the catalyst, trouble in the fluid catalytic cracking device, mixing of the catalyst powder into the product (particularly HCO), etc., which is not preferable. .
The total pore volume measured by the mercury intrusion method is a pore having a pore diameter of 5.5 to 500 nm, which is a pore formed in the matrix. Note that the pores of zeolite cannot be measured by the mercury intrusion method. If the total pore volume is less than 0.10 ml / g, hydrocarbons cannot be decomposed efficiently, and if it exceeds 0.40 ml / g, the strength (wear resistance) may be reduced.
For example, the cleaning particles are dried at about 100 to 200 ° C., and the baking is performed at about 500 to 600 ° C.

[Example 1]
<Production of basic aluminum chloride aqueous solution>
7245 g of aluminum chloride hexahydrate (manufactured by Kanto Chemical Co., Ltd., first grade reagent) was inserted into a titanium tank with a steam jacket (capacity: 70 L) containing 33.7 kg of pure water, and stirred sufficiently. An aqueous aluminum chloride solution was obtained. After this aluminum chloride aqueous solution was heated to 95 ° C. with stirring, 4050 g of aluminum foil (aluminum foil) having a purity of 99.9% was gradually added over 6 hours while maintaining the liquid temperature (about 11.25 g / min). In) to dissolve the aluminum foil. When the aluminum foil was dissolved, a large amount of hydrogen gas was generated, and water in the aqueous solution evaporated as water vapor. Therefore, 95 ° C. pure water was appropriately replenished so that the amount of the aqueous solution stored in the tank was constant. After the aluminum foil was completely dissolved, the aqueous solution was cooled to 30 ° C. to obtain 45.0 kg of basic aluminum chloride aqueous solution. This basic aluminum chloride aqueous solution had a pH of 3.9 and contained 20.5% basic aluminum chloride as Al ₂ O ₃ . The basic aluminum chloride aqueous solution was also used in the following examples and comparative examples.
<Production of fluid catalytic cracking catalyst>
975.6 g of this basic aluminum chloride aqueous solution (10% by mass based on catalyst), 1093.0 g of kaolin (47% by mass based on catalyst), 222.2 g of activated alumina (10% by mass based on catalyst), metal trap As an agent, 20.0 g of manganese dioxide (1% by mass on the basis of catalyst) was mixed to obtain an inorganic oxide matrix precursor. Furthermore, 1818.2 g of super-stabilized Y-type zeolite slurry (including 600.0 g of super-stabilized Y-type zeolite. 30% by mass based on catalyst) was added to the obtained inorganic oxide matrix precursor to obtain a mixed slurry. It was. After adding 16.2 g of 85% phosphoric acid (orthophosphoric acid, hereinafter the same) to this mixed slurry (0.5% by mass as P ₂ O _{5 based on the} catalyst) and stirring sufficiently, a 20% magnesium hydroxide aqueous solution was added. Was added to adjust the pH to 4.8 to obtain a phosphorus-containing slurry.
The phosphorus-containing slurry is spray-dried to prepare fine spherical particles (average particle size is about 60 μm), and then washed until the Na ₂ O content is 0.5% by mass or less, and further contains rare earth. After ion exchange so that the RE ₂ O ₃ is 1.5% by mass using an aqueous solution, it is dried at 135 ° C. and fluidized catalytic cracking catalyst A of hydrocarbon (hereinafter simply referred to as “catalyst A”. The same applies hereinafter. ) Was manufactured. The properties of the obtained catalyst A are shown in Table 1.

[Example 2]
The point of producing fluid catalytic cracking catalyst B with 1081.4 g of kaolin (46.5% by mass based on catalyst) and 32.5 g of 85% phosphoric acid (1.0% by mass as P ₂ O _{5 based on} catalyst) However, this is different from the first embodiment.

[Example 3]
Point of producing fluid catalytic cracking catalyst C with 1058.1 g of kaolin (45.5% by mass based on catalyst) and 64.9 g of 85% phosphoric acid (2.0% by mass as P ₂ O _{5 based on} catalyst) However, this is different from the first embodiment.

[Comparative Example 1]
The difference from Example 1 is that the fluid catalytic cracking catalyst D was produced with 1104.7 g of kaolin (47.5 mass% based on the catalyst) and without mixing 85% phosphoric acid.

[Comparative Example 2]
The point of producing fluid catalytic cracking catalyst E with 1011.6 g of kaolin (43.5% by mass based on catalyst) and 129.9 g of 85% phosphoric acid (4.0% by mass as P ₂ O _{5 based on} catalyst) However, this is different from the first embodiment.

[Example 4]
An aqueous solution obtained by previously adding 16.2 g of 85% phosphoric acid (0.5% by mass as P ₂ O _{5 on a} catalyst basis) to 975.6 g of a basic aqueous aluminum chloride solution (10% by mass on a catalyst basis) , 1093.0 g of kaolin (47% by mass based on catalyst), 222.2 g of activated alumina (10% by mass based on catalyst) and 20.0 g of manganese dioxide (1% by mass based on catalyst) as a metal trapping agent Thus, an inorganic oxide matrix precursor was obtained. Furthermore, 1818.2 g of super-stabilized Y-type zeolite slurry (including 600.0 g of super-stabilized Y-type zeolite. 30% by mass based on catalyst) was added to the obtained inorganic oxide matrix precursor to obtain a mixed slurry. It was. A 20% magnesium hydroxide aqueous solution was added to the mixed slurry to adjust the pH to 4.8 to obtain a phosphorus-containing slurry.
The phosphorus-containing slurry is spray-dried to prepare fine spherical particles (average particle size is about 60 μm), and then washed until the Na ₂ O content is 0.5% by mass or less, and further contains rare earth. After ion exchange so that the RE ₂ O ₃ is 1.5% by mass using an aqueous solution, it is dried at 135 ° C. and fluidized catalytic cracking catalyst F of hydrocarbon (hereinafter also simply referred to as “catalyst F”. ) Was manufactured.

[Example 5]
975.6 g basic aluminum chloride aqueous solution (10% by mass based on catalyst), 1093.0 g kaolin (47% by mass based on catalyst), 222.2 g activated alumina (10% by mass based on catalyst), metal trapping agent As a mixture, 20.0 g of manganese dioxide (1% by mass on the basis of catalyst) was mixed to obtain an inorganic oxide matrix precursor. Furthermore, 1818.2 g of super-stabilized Y-type zeolite slurry (including 600.0 g of super-stabilized Y-type zeolite. 30% by mass based on catalyst) was added to the obtained inorganic oxide matrix precursor to obtain a mixed slurry. It was. A 20% magnesium hydroxide aqueous solution was added to the mixed slurry to adjust the pH to 4.8 to obtain a slurry.
The slurry is spray-dried to prepare fine spherical particles (average particle size is about 60 μm), and then washed until the Na ₂ O content is 0.5 mass% or less. And then ion-exchanged to 1.5% by mass as RE ₂ O ₃ , and then added to this aqueous solution 16.2 g of 85% orthophosphoric acid (0.5% by mass as P ₂ O _{5 on a} catalyst basis). Then, after sufficiently bringing the microparticles into contact with the aqueous solution, the microparticles were collected and dried to produce a hydrocarbon fluid catalytic cracking catalyst G (hereinafter also simply referred to as “catalyst G”, hereinafter the same).

[Example 6]
975.6 g basic aluminum chloride aqueous solution (10% by mass based on catalyst), 1093.0 g kaolin (47% by mass based on catalyst), 222.2 g activated alumina (10% by mass based on catalyst), metal trapping agent As a mixture, 20.0 g of manganese dioxide (1% by mass on the basis of catalyst) was mixed to obtain an inorganic oxide matrix precursor. Furthermore, 1818.2 g of super-stabilized Y-type zeolite slurry (including 600.0 g of super-stabilized Y-type zeolite. 30% by mass based on catalyst) was added to the obtained inorganic oxide matrix precursor to obtain a mixed slurry. It was. A 20% magnesium hydroxide aqueous solution was added to the mixed slurry to adjust the pH to 4.8 to obtain a slurry.
This slurry is spray-dried to prepare fine spherical particles (average particle size is about 60 μm), then washed until the Na ₂ O content is 0.5% by mass or less, and dried at 135 ° C., Further, the product calcined at 600 ° C. was impregnated with 16.2 g of 85% phosphoric acid (0.5% by mass as P ₂ O _{5 based on the} catalyst), and fluidized catalytic cracking catalyst H (hereinafter also simply referred to as “catalyst H”). The same applies hereinafter.

[Example 7]
The difference from Example 6 is that fluid catalytic cracking catalyst I was produced by impregnating diammonium hydrogen phosphate with 18.6 g (0.5% by mass based on catalyst) instead of phosphoric acid.

Catalysts A to I were each subjected to catalytic cracking reaction under the same feedstock and the same reaction conditions using an FCC catalyst evaluation device (manufactured by Kaiser, ACE-MAT model R +). Table 1 shows the results. The catalysts A to I were impregnated with 2,000 wtppm of vanadium naphthenate as V ₂ O ₅ and 2,000 wtppm of nickel naphthenate as NiO in advance, based on the weight of the catalyst, at 780 ° C. for 13 hours in a 100% steam atmosphere. Pre-processed.
Here, the catalytic cracking reaction conditions were as follows.
Reaction temperature: 520 ° C
Raw material oil: Desulfurized atmospheric distillation residue oil Cat. / Oil ratio (mass ratio of catalyst and oil): 4 wt% / wt% (catalyst 9 g, oil 2.25 g) and 5 wt% / wt% (catalyst 9 g, oil 1.80 g)

(1) Method for measuring specific surface area The specific surface area was measured by the BET method using a fully automatic gas adsorption amount measuring device (Multisorb 16 manufactured by Yuasa Ionics).
(2) Method for measuring bulk density The weight of the catalyst was measured using a 25 ml cylinder, and the bulk density was calculated from the weight per unit volume.
(3) Measuring method of abrasion resistance index (CAI) Catalytic conversion technical report Vol. 13, no. 1, measured by the apparatus and method described in P65 (1996) “Method for Measuring Abrasion Strength of Catalyst”.
(4) Conversion (mass%) = (A−B) / A × 100
A: Weight of raw material oil B: Weight of fraction having boiling point of 216 ° C. or higher in product oil (5) Gasoline yield (mass%) = C / A × 100
C: Weight of gasoline (boiling range: C5 to 216 ° C.) in the produced oil (6) LCO yield (% by mass) = D / A × 100
D: Weight of LCO (boiling range: 216 to 343 ° C.) in the product oil (7) HCO yield (% by mass) = E / A × 100
E: Weight of HCO (boiling range: from 343 ° C.) in the product oil (8) Coke yield (% by mass) = F / A × 100
F: Weight of coke deposited on the catalyst mixture

<About fluid catalytic cracking catalysts A to E>
Fluid catalytic cracking catalysts A to C containing 0.5 to 2% by mass of phosphorus as P ₂ O ₅ have a large specific surface area of 219 m ² / g or more and a high wear resistance index of 6 or less. It was. Thereby, abrasion resistance can be made high, maintaining catalyst performance. Therefore, a catalyst having a large pore volume and excellent wear resistance can be prepared. However, the fluid catalytic cracking catalyst D containing no phosphorus has poor wear resistance, and the fluid catalytic cracking catalyst E containing 4% by mass of phosphorus as P ₂ O ₅ has a pore volume of 0.198 ml / g. It became low.

<About fluid catalytic cracking catalysts A and F to I>
The fluid catalytic cracking catalyst A and fluid catalytic cracking catalysts F to I containing 0.5% by mass of phosphorus as P ₂ O ₅ in the production process have a large pore volume of 0.228 ml / g or more, The wear resistance index was as high as 6 or less. Thereby, abrasion resistance can be made high, maintaining catalyst performance. Therefore, a catalyst having a large pore volume and excellent wear resistance can be prepared. Further, in the fluid catalytic cracking catalyst H, when phosphoric acid is added after drying the washing particles, the zeolite is in an atmosphere having a pH of 2 or less, and the crystals of the zeolite tend to be broken. Thus, by adding diammonium hydrogen phosphate to make the zeolite in an atmosphere having a pH of 2 or more (pH 3 to 12) and preventing destruction of the zeolite crystals, the wear resistance can be improved.

  The present invention is not limited to the above-described embodiment, and can be changed without changing the gist of the present invention. For example, some or all of the above-described embodiments and modifications are possible. A combination of these is also included in the scope of the right of the present invention.

Claims (3)

Spray-drying a mixed slurry of inorganic oxide matrix precursor containing basic aluminum chloride and zeolite, washing the resulting spherical particles, drying or calcining after drying to produce hydrocarbon fluid catalytic cracking catalyst In the inorganic oxide matrix of the fluid catalytic cracking catalyst, 0.1 to 3% by mass of phosphoric acid or phosphate as P ₂ O ₅ is contained, and phosphorus is not contained in the zeolite. A process for producing a fluidized catalytic cracking catalyst for hydrocarbons. The method for producing a hydrocarbon fluid catalytic cracking catalyst according to claim 1, wherein phosphoric acid or phosphate is contained in at least one of the following steps.
(A) Phosphoric acid or phosphate is mixed in advance with one or more of raw materials comprising an inorganic oxide matrix precursor containing basic aluminum chloride and zeolite.
(B) In the mixed slurry stage, phosphoric acid or phosphate is mixed.
(C) Phosphoric acid or phosphate is mixed with the spherical particles.
(D) Phosphoric acid or phosphate is mixed with the cleaning particles.
(E) The washed particles are dried and further baked, and then mixed with phosphoric acid or phosphate.   The method for producing a hydrocarbon fluid catalytic cracking catalyst according to claim 1 or 2, wherein the zeolite is in an atmosphere having a pH of 2 or more.