JP2006142273A - Process for producing catalyst composition for hydrocarbon fluid catalytic cracking - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a catalyst composition for hydrocarbon fluid catalytic cracking which, when used in fluid catalytic cracking of heavy hydrocarbons, has a high residual oil (bottom) cracking capability, is less likely to produce hydrogen, dry gas, and coke, has a high capability of producing gasoline having a low olefin content, and, at the same time, has excellent thermal stability. <P>SOLUTION: This process for producing a catalyst composition for hydrocarbon fluid catalytic cracking is characterized by comprising spray drying an aqueous mixture of (A) a phosphorus-treated alumina hydrate-coated zeolite prepared by treating an alumina hydrate-coated Y-type zeolite with an aqueous phosphate ion-containing solution and (B) an inorganic oxide matrix precursor containing basic aluminum chloride as a binder. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a catalyst composition for fluid catalytic cracking of hydrocarbons, and more particularly, it is used for fluid catalytic cracking of hydrocarbons, particularly heavy hydrocarbons such as residual oils, and exhibits high cracking activity. The present invention relates to a method for producing a catalyst composition for hydrocarbon fluid catalytic cracking that produces less dry gas (methane, ethane) and coke, is excellent in producing gasoline with low olefin content, and has excellent heat stability.

As the hydrocarbon feedstock oil has become heavier in recent years, the amount of coke adhering to the fluid catalytic cracking catalyst composition (FCC catalyst) during catalytic cracking in a fluid catalytic cracking (FCC) unit has increased. The regeneration temperature of the FCC catalyst is high. For this reason, FCC catalysts are required to be used for fluid catalytic cracking of heavy hydrocarbons, exhibit high cracking activity, produce less hydrogen, dry gas and coke, and have excellent heat stability.
On the other hand, the amount of olefins contained in commercially available gasoline is limited from the viewpoint of handling safety, and some refineries desire FCC gasoline with a low olefin content.
In response to such a demand, various hydrocarbon fluid catalytic cracking catalyst compositions and production methods thereof have been proposed.

For example, Patent Document 1 discloses that a phosphorus-containing Y-type in which Y-type faujasite is treated with an aqueous solution containing phosphate ions and the phosphorus content is 0.3 to 15% by weight as P ₂ O _5. A faujasite is prepared, the phosphorus-containing Y-type faujasite is mixed with an aqueous suspension of a porous matrix precursor, and the aqueous mixture is spray-dried, washed and dried. A method for producing a catalytic composition for catalytic cracking of hydrocarbon oil is described, and the catalyst composition is used for catalytic cracking of hydrocarbon oil to produce coke even though it exhibits high cracking activity. It is disclosed that there are few and it is excellent in thermal stability.

In Patent Document 2, NaY-zeolite is first subjected to ammonium exchange, the obtained ammonium-exchanged zeolite is subjected to aluminum exchange, the aluminum-exchanged zeolite is subjected to steam calcination, and a phosphorus component is added. A process for preparing a modified Y-type zeolite characterized in that it is incorporated into a steam-fired zeolite and an FCC catalyst containing the aluminum-exchanged phosphorus-containing Y-zeolite are described, wherein the FCC catalyst is aluminum-exchanged as compared to FCC catalyst containing any one of zeolites contain and or phosphorus and are described to exhibit less coking and C ₃ improved selectivity to olefins.
Although these catalysts have high cracking activity and little production of hydrogen and coke and have a temporary effect such as lowering the ratio of propylene (C ₃ =) / propane (C ₃ ), further improvements have been desired.

  On the other hand, Patent Document 3 discloses a catalyst composition for catalytic catalytic cracking of hydrocarbons using an ultrastable Y-type zeolite coated with alumina hydrate, which exhibits excellent effects when used for catalytic cracking of heavy hydrocarbons. A production method is described, and the ultrastable Y-type zeolite coated with the alumina hydrate is a Y-type having a non-framework alumina (NFA) content of 2.0 wt% or more and a crystallinity of 80% or more. It is disclosed that the zeolite is suspended in an acidic aqueous solution, and then the suspension and the alkaline aqueous solution are mixed at a ratio such that the pH of the system is in the range of 7.0 to 9.5.

  Patent Document 4 discloses a method for producing a catalyst containing a hydrocarbon catalytic cracking catalyst, and describes a method for producing an abrasion-resistant catalyst using aluminum chlorohydrol as a binder. .

Japanese Unexamined Patent Publication No. 63-197549 JP-T 8-508970 JP 2001-212462 A JP-A-62-14947

  The object of the present invention is the fluid catalytic cracking of hydrocarbons, particularly heavy hydrocarbons such as crude oils containing metal contaminants such as nickel and vanadium, vacuum residue oils, atmospheric residue oils, hydrotreated oils and vacuum gas oils. Hydrocarbon fluid catalytic cracking catalyst composition with high residual oil (bottom) resolution, low hydrogen, dry gas and coke production, low olefin content and excellent heat resistance stability It is in providing the manufacturing method of a thing.

As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have obtained a phosphorus-treated alumina hydrate coating obtained by treating an ultrastable Y-type zeolite coated with alumina hydrate with a phosphate ion-containing aqueous solution. An FCC catalyst produced using zeolite and basic aluminum chloride as a binder has been found to achieve the above-mentioned object, and the present invention has been completed.
That is, the first of the present invention is (A) a phosphorous-treated alumina hydrate-coated zeolite obtained by treating Y-type zeolite coated with alumina hydrate with a phosphate ion-containing aqueous solution, and (B) a bond. The present invention relates to a process for producing a hydrocarbon fluid catalytic cracking catalyst composition characterized by spray-drying an aqueous mixture with an inorganic oxide matrix precursor containing basic aluminum chloride as an agent.
The second of the present invention, the phosphorus content of the phosphorus-treated alumina hydrate coating zeolite is in the range of 0.1-20 weight% as P ₂ O ₅ with respect to the oxide sum of zeolite and alumina and phosphorus The present invention relates to a method for producing a hydrocarbon fluid catalytic cracking catalyst composition according to claim 1.

  The hydrocarbon fluid catalytic cracking catalyst composition obtained by the production method of the present invention has excellent hydrothermal stability even when the regeneration temperature of the regeneration tower in the FCC unit is high, and has a high residual oil (bottom) resolution, Since it produces less hydrogen, dry gas and coke, and is excellent in producing gasoline with low olefin content, it is suitably used in refineries where FCC gasoline with low olefin content is desired.

In the method for producing a hydrocarbon fluid catalytic cracking catalyst composition of the present invention, (A) a phosphorus-treated alumina hydrate obtained by treating a Y-type zeolite coated with alumina hydrate with a phosphate ion-containing aqueous solution. Use coated zeolite.
Y-type zeolite coated with the alumina hydrate is prepared according to the method described in Patent Document 3 of the applicant's application. That is, a Y-type zeolite having a non-framework alumina (NFA) content of 2.0 wt% or more and a crystallinity of 80% or more is suspended in an acidic aqueous solution, and then the suspension and the alkaline aqueous solution are combined. Alumina hydrate-coated zeolite is prepared by mixing at a ratio of pH ranging from 7.0 to 9.5. The content of extra-framework alumina (NFA) in the Y-type zeolite is preferably in the range of 2.0 to 17.0 wt%. Further, the alumina content of the alumina hydrate covering the Y-type zeolite is preferably in the range of 1 to 20 wt% as Al ₂ O ₃ (total basis of zeolite-coated alumina).

The phosphorus-treated alumina hydrate-coated zeolite in the present invention is prepared by treating the above-mentioned alumina hydrate-coated zeolite with an aqueous solution containing phosphate ions.
A phosphate ion-containing aqueous solution can be prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates in water at an arbitrary concentration. The phosphoric acid-treated alumina hydrate-coated zeolite is prepared by bringing the phosphate ion-containing aqueous solution into contact with the alumina hydrate-coated zeolite. The contact between the phosphate ion-containing aqueous solution and the alumina hydrate-coated zeolite can be performed at a temperature ranging from room temperature to about 100 ° C. within a pH range of 3 to 8. The phosphorus content of the phosphorus-treated alumina hydrate-coated zeolite obtained by this treatment is preferably in the range of 0.1 to 20 wt% as P ₂ O _{5 with} respect to the total oxide of zeolite, alumina and phosphorus. When the phosphorus content is less than 0.1 wt%, a sufficient suppression effect of coke formation may not be obtained. In addition, when the phosphorus content is more than 20 wt%, the gasoline yield may decrease. The phosphorus content is more preferably in the range of 0.5 to 15 wt%.

In the production method of the present invention, (B) an inorganic oxide matrix precursor containing basic aluminum chloride as a binder is used.
Basic aluminum chloride (basic aluminum chloride) is a polyaluminum chloride represented by the general formula [Al ₂ (OH) _n Cl _6-n ] _m (where 0 <n <6, m ≦ 10), and is commercially available. . In particular, highly basic aluminum chloride having a value of n of 4 to 5 is preferably used because of its strong bonding strength.
As the inorganic oxide matrix precursor in the present invention, an inorganic oxide matrix precursor commonly used in ordinary FCC catalysts can be used except that it contains basic aluminum chloride as a binder. The inorganic oxide matrix precursor is composed of 5 to 30 wt% alumina derived from basic aluminum chloride as a binder (binder) and 20 to 70 wt% clay such as kaolin, based on the oxide weight of the final catalyst composition. It is preferable that a metal scavenger such as alumina particles or manganese oxide particles is contained in the range of 0.5 to 20 wt%.

In the production method of the present invention, an aqueous mixture of the above-mentioned phosphor-treated alumina hydrate-coated zeolite and the above-mentioned inorganic oxide matrix precursor containing basic aluminum chloride as a binder is spray-dried by a usual method. To obtain microspherical particles. The mixing ratio of the phosphorus-treated alumina hydrate-coated zeolite is _{5 to 5} of the final catalyst composition as the sum of zeolite (SiO ₂ —Al ₂ O ₃ standard), alumina (Al ₂ O ₃ ) and phosphorus (P ₂ O ₅ ). It is preferable to be in the range of 50 wt%. The obtained microspherical particles are washed and dried by a usual method, and a rare earth component is introduced as necessary.
When using the catalyst composition, the usual catalytic cracking reaction conditions can be adopted, and the regeneration temperature of the regeneration tower in the FCC apparatus can be increased.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by a following example, unless the summary is exceeded.

Example 1
Based on Example 1 of JP-A-2001-212462, an alumina hydrate-coated ultrastable Y-type zeolite slurry was prepared.
That is, 1650 g of ultrastable Y-type zeolite (USY) having a lattice constant of 24.57 L (based on SiO ₂ —Al ₂ O ₃ ) was suspended in 3350 g of deionized water while stirring and heated to 60 ° C. To this zeolite suspension slurry, 25 wt% sulfuric acid was added to adjust the pH to 2.8. Separately, 2850 g of a sodium aluminate solution having an Al ₂ O ₃ concentration of 5 wt% heated to 60 ° C. was prepared. The zeolite suspension slurry adjusted to pH 2.8 was added to the sodium aluminate solution over 5 minutes. The pH of the mixed slurry after the addition was 7.8. After stirring the mixed slurry for 1 hour, it is separated into solid and liquid using a vacuum suction filter and washed with deionized water at 60 ° C to remove residual salt such as Na ions and SO ₄ ions. Thus, USY coated with alumina hydrate was prepared. The alumina hydrate-coated USY was slurried in 4000 g of deionized water to obtain an alumina hydrate-coated USY slurry.
While stirring the 25 wt% slurry of the alumina hydrate-coated USY, an orthophosphoric acid having a concentration of 85 wt% was added so that the phosphorus content (as P ₂ O ₅ ) in the phosphorus-treated alumina hydrate-coated USY zeolite was 5 wt%. In addition, the mixture was stirred at 60 ° C. for 20 minutes. In this way, a phosphorylated alumina hydrate-coated USY slurry was prepared.
On the other hand, 33.7 kg of pure water was weighed in a 70 L tank with a steam jacket, and heated to 95 ° C. while stirring 7245 g of aluminum chloride hexahydrate-first grade reagent (manufactured by Kanto Chemical Co., Inc.). In this aluminum chloride solution, 4050 g of household metal aluminum foil was dissolved over 6 hours, and then cooled to 30 ° C. to prepare a basic aluminum chloride slurry having an Al ₂ O ₃ concentration of 20.5 wt% and pH 3.9.
The basic aluminum chloride slurry was weighed so that the Al ₂ O ₃ concentration was 10 wt% based on the weight of the final composition, and kaolin and activated alumina were respectively added to 65.5 wt% based on the weight of the final catalyst composition. In addition, an inorganic oxide matrix precursor was prepared so as to be 3 wt%. Furthermore, the content of the phosphorus-treated alumina hydrate-coated USY slurry in the inorganic oxide matrix precursor as an oxide of the phosphorus-treated alumina hydrate-coated USY is 20 wt% based on the weight of the final catalyst composition. And mixed. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. A catalyst composition A containing 2 wt% of a rare earth component as (RE ₂ O ₃ ) was prepared.

Example 2
Phosphorus-treated alumina hydrate-coated USY zeolite has a phosphorus content (as P ₂ O ₅ ) of 8 wt% with stirring in a 25 wt% slurry of alumina hydrate-coated USY similar to that used in Example 1. Thus, orthophosphoric acid having a concentration of 85 wt% was added and stirred at 60 ° C. for 20 minutes. In this way, a phosphorylated alumina hydrate-coated USY slurry was prepared.
The same basic aluminum chloride slurry as used in Example 1 was weighed so that the Al ₂ O ₃ concentration was 10 wt% based on the weight of the final composition, and kaolin and activated alumina were measured based on the weight of the final catalyst composition. In addition to the basic aluminum chloride slurry, inorganic oxide matrix precursors were prepared so as to be 65.5 wt% and 3 wt%, respectively. Furthermore, the content of the phosphorous-treated alumina hydrate-coated USY slurry as an oxide of the phosphorous-treated alumina hydrate-coated USY in the inorganic oxide matrix precursor is 20 wt% based on the weight of the final catalyst composition. And mixed. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. Catalyst composition B containing 2 wt% rare earth component as (RE ₂ O ₃ ) was prepared.

Example 3
The 25 wt% slurry of alumina hydrate-coated USY similar to that used in Example 1 has a phosphorus content (as P ₂ O ₅ ) of 15 wt% in the phosphated alumina hydrate-coated USY zeolite with stirring. In this way, a mixed solution of orthophosphoric acid and monoammonium phosphate (phosphoric acid: monoammonium phosphate = 7: 3) was added and stirred at 60 ° C. for 20 minutes. In this way, a phosphorylated alumina hydrate-coated USY slurry was prepared.
The same basic aluminum chloride slurry as used in Example 1 was weighed so that the Al ₂ O ₃ concentration was 10 wt% based on the weight of the final composition, and kaolin and activated alumina were measured based on the weight of the final catalyst composition. In addition to the basic aluminum chloride slurry, inorganic oxide matrix precursors were prepared so as to be 65.5 wt% and 3 wt%, respectively. Furthermore, the content of the phosphorus-treated alumina hydrate-coated USY slurry in the inorganic oxide matrix precursor as an oxide of the phosphorus-treated alumina hydrate-coated USY is 20 wt% based on the weight of the final catalyst composition. And mixed. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. Catalyst composition C containing 2 wt% rare earth component as (RE ₂ O ₃ ) was prepared.

Comparative Example 1
The same basic aluminum chloride slurry as used in Example 1 was weighed so that the Al ₂ O ₃ concentration was 10 wt% based on the weight of the final composition, and kaolin and activated alumina were measured based on the weight of the final catalyst composition. In addition to the basic aluminum chloride slurry, inorganic oxide matrix precursors were prepared so as to be 65.5 wt% and 3 wt%, respectively. Further, a 25 wt% slurry of alumina hydrate-coated USY similar to that used in Example 1 was added to the above-mentioned inorganic oxide matrix precursor as an oxide of alumina hydrate-coated USY. It added and mixed so that it might become 20 wt% on a weight basis. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. A catalyst composition D containing 2 wt% of a rare earth component as (RE ₂ O ₃ ) was prepared.

Comparative Example 2
The 25 wt% slurry of alumina hydrate-coated USY similar to that used in Example 1 has a phosphorus content (as P ₂ O ₅ ) in the phosphated alumina hydrate-coated USY zeolite of 5 wt% while stirring. Thus, orthophosphoric acid having a concentration of 85 wt% was added and stirred at 60 ° C. for 20 minutes. In this way, a phosphorylated alumina hydrate-coated USY slurry was obtained.
A silica hydrosol having a SiO ₂ concentration of 12.5 wt% was prepared by continuously adding 25 wt% sulfuric acid to a water glass having a SiO ₂ concentration of 17 wt%. The silica hydrosol is weighed so that the SiO ₂ concentration is 20 wt% based on the weight of the final catalyst composition, and kaolin and activated alumina are respectively 55.5 wt% and 3 wt% based on the weight of the final catalyst composition. In addition to the silica hydrosol, an inorganic oxide matrix precursor was prepared. Furthermore, the content of the phosphorus-treated alumina hydrate-coated USY slurry as an oxide of the phosphor-treated alumina hydrate-coated USY in the inorganic oxide matrix precursor is 20 wt% based on the weight of the final catalyst composition. And mixed. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. Catalyst composition E containing 2 wt% rare earth component as (RE ₂ O ₃ ) was prepared.

Comparative Example 3
The phosphorus content (as P ₂ O ₅ ) in the phosphorus-treated ultrastable Y-type zeolite was 5 wt% while stirring in a 33 wt% slurry of the superstable Y-type zeolite having a lattice constant of 24.57 L that had undergone hydrogen ion exchange. Then, orthophosphoric acid having a concentration of 85 wt% was added and stirred at 60 ° C. for 20 minutes. In this way, a phosphorus-treated ultrastable Y-type zeolite was obtained.
The same basic aluminum chloride slurry as used in Example 1 was weighed so that the Al ₂ O ₃ concentration was 10 wt% based on the weight of the final composition, and kaolin and activated alumina were measured based on the weight of the final catalyst composition. In addition to the basic aluminum chloride slurry, inorganic oxide matrix precursors were prepared so as to be 65.5 wt% and 3 wt%, respectively. Further, the 33 wt% slurry of the phosphorus-treated ultrastable Y-type zeolite is added to the inorganic oxide matrix precursor as an oxide of the phosphorus-treated superstable Y-type zeolite based on the weight of the final catalyst composition. It added and mixed so that it might become 20 wt%. Finally, manganese dioxide as a metal trapping agent was added to 1.5 wt% based on the weight of the final catalyst composition to obtain a mixed slurry.
The mixed slurry is spray-dried to prepare fine spherical particles, washed until the Na ₂ O content is 0.5 wt% or less, immersed in a rare earth chloride aqueous solution at 60 ° C., and then dried to form an oxide. A catalyst composition F containing 2 wt% rare earth component as (RE ₂ O ₃ ) was prepared.

Example 4 (Catalyst use example)
For each of the catalysts A, B, C and D, E, F prepared in the examples and comparative examples, catalytic cracking reaction tests were performed using the reaction test equipment ASTM MAT under the same feedstock and the same reaction conditions. Prior to conducting the reaction test, each catalyst was impregnated with 4000 wtppm of vanadium naphthenate as V ₂ O ₅ and 2000 wtppm of nickel naphthenate as NiO and 100% at 780 ° C. for 13 hours, based on the weight of the final composition. Pre-treatment was performed in a steam atmosphere.
The catalytic cracking reaction conditions were as follows.
Reaction temperature: 510 ° C
Raw material oil: Mixed oil of desulfurized atmospheric distillation residue oil (DSAR) 40 wt% and desulfurized vacuum gas oil (DSVGO) 60 wt%.
WHSV: 40 hr ⁻¹
Catalyst / oil ratio: 4 wt% / wt%
The reaction results are shown in Table 1.
In addition, the item of activity evaluation of Table 1 represents the following meaning.
Conversion rate (wt%) = (A−B) / A × 100
A: Weight of raw material oil
B: Weight of a fraction having a boiling point of 216 ° C. or higher in the product oil Gasoline (wt%) = C / A × 100
C: Weight of gasoline in boiling oil (boiling range: C5 to 216 ° C.) LCO (wt%) = D / A × 100
D: weight of LCO ^{* 1} ) (boiling range: 216 to 343 ° C.) in the product oil
* 1) Light cycle oil HCO (wt%) = E / A x 100
E: Weight of HCO ^{* 2} ) (boiling range: 343 ° C. −) in the product oil
* 2) Heavy cycle oil Coke (wt%) = F / A x 100
F: Weight of coke deposited on catalyst mixture K = decomposition rate / (100-decomposition rate)
K: Rate constant LPG Olefinity = Percentage of olefin in LPG (C3 + C4)
LPG Olefinity was displayed as an index indicating the olefin content in gasoline.
As can be seen from Table 1, the hydrocarbon fluid catalytic cracking catalyst composition obtained by the production method of the present invention has a high conversion rate, a high gasoline yield, and a small amount of hydrogen and coke production.

Claims (2)

  (A) A phosphorous-treated alumina hydrate-coated zeolite obtained by treating a Y-type zeolite coated with alumina hydrate with a phosphate ion-containing aqueous solution, and (B) containing basic aluminum chloride as a binder. A method for producing a hydrocarbon fluid catalytic cracking catalyst composition comprising spray drying an aqueous mixture with an inorganic oxide matrix precursor. Claim 1, wherein the phosphorus content of the phosphorus-treated alumina hydrate coating zeolite is in the range of 0.1-20 weight% as P ₂ O ₅ with respect to the oxide sum of zeolite and alumina and phosphorus A method for producing a catalyst composition for fluid catalytic cracking of hydrocarbons.