JP2003190817A - Method for manufacturing catalyst composition for catalytic cracking of hydrocarbon oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a catalyst composition for catalytic cracking used in fluidized catalytic cracking of a hydrocarbon oil, particularly heavy hydrocarbon oil, having high cracking activity and showing excellent effects such as high yields of gasoline, a high yield of kerosene and light oil (LCO) and low yields of heavy residual oil (HCO), gas and coke. <P>SOLUTION: In the method for manufacturing the catalyst composition for catalytic cracking of hydrocarbon oil, a mixture is spray-dried which comprises (a) a crystalline aluminosilicate zeolite, (b) a pseudo-boehmite type alumina hydrate whose slurry has an aluminum-acid dissolution index of 5-30 and (c) an inorganic oxide matrix precursor. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a catalyst composition for catalytic cracking of hydrocarbon oil, and more particularly to a method for fluid catalytic cracking of hydrocarbon oil, especially heavy hydrocarbon oil, which has a cracking activity. Catalytic composition for catalytic cracking showing high effects such as high gasoline yield and kerosene light oil (light cycle oil; LCO) yield, and low heavy residue oil (heavy cycle oil; HCO), gas and coke yields. The present invention relates to a method of manufacturing a product.

[0002]

2. Description of the Related Art In the catalytic cracking of hydrocarbon oils, heavy metals such as nickel and vanadium and feedstock oil having a high residual carbon content must be introduced into a fluid catalytic cracking unit in accordance with the recent heavy-duty and lower quality of crude oil. There is something that must happen. Therefore, the demand for improved performance of catalytic cracking catalyst compositions is becoming stronger and stronger, it has excellent metal resistance, can efficiently decompose heavy residual oil components in the feed oil, and has selectivity for gasoline and kerosene gas oil fractions. There is a demand for research and development of a catalytic cracking catalyst composition having a high temperature.

The applicant of the present invention discloses a catalyst composition satisfying the above-mentioned requirements in Japanese Patent Application Laid-Open No. 9-164338.
(1) Crystalline aluminosilicate zeolite, and (2)
Acid was added to pseudo-boehmite-type alumina hydrate having a crystallite size in the range of 45 to 105Å to adjust the pH to 1.0 to 4.5 and (3) Acid was added to water glass. A method for producing a catalyst composition for catalytic cracking of hydrocarbon oil, which comprises mixing a silicic acid solution prepared in the range of pH 1.0 to 2.5, and spray-drying the resulting mixture. is suggesting.

[0004] Further, Japanese Patent Laid-Open No. Hei 11 (1999) filed by the present applicant
In -50063 _discloses, SiO 2 / _Al 2 _{O 3}
The weight ratio is in the range of 0.01 to 0.85, and the alumina component contains a catalyst component starting from a composite material composed of pseudo-boehmite type alumina hydrate having a crystallite diameter of 40 Å or less. And a catalyst composition for catalytic cracking of hydrocarbon oil.

However, the demand for performance improvement of catalytic cracking catalyst compositions is more severe, and further improvements have been desired.

[0006]

The object of the present invention is to use in the fluid catalytic cracking of hydrocarbon oils, especially heavy hydrocarbon oils,
High cracking activity, gasoline yield and kerosene gas oil (LCO)
Another object of the present invention is to provide a method for producing a catalytic composition for catalytic cracking which exhibits excellent effects such as high yield and low yields of heavy residual oil (HCO), gas and coke.

[0007]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the pseudo-boehmite-type alumina in which the aluminum-acid solubility index of the alumina hydrate slurry is in a specific range. The present inventors have found that the catalyst composition for catalytic cracking of hydrocarbon oil obtained by using a mixture containing a hydrate exhibits excellent performance for catalytic cracking reaction, and completed the present invention.

The first aspect of the present invention is (a) a crystalline aluminosilicate zeolite, (b) a pseudo-boehmite-type alumina hydrate in which the aluminum-acid solubility index of the alumina hydrate slurry is in the range of 5 to 30, and ( The present invention relates to a method for producing a catalyst composition for catalytic cracking of hydrocarbon oil, which comprises spray-drying a mixture containing c) an inorganic oxide matrix precursor. A second aspect of the present invention is characterized in that the pseudo-boehmite-type alumina hydrate is fibrous particles, and the fibrous particles of the alumina hydrate have an average length in the range of 50 to 500Å. 1. A method for producing the catalyst composition for catalytic cracking of hydrocarbon oil according to 1.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The above (a) in the present invention
As the crystalline aluminosilicate zeolite, a zeolite used in a catalyst composition for usual catalytic cracking of hydrocarbon oil can be used, and synthetic zeolite such as Y-type zeolite and ZSM-type zeolite and β zeolite, M
Examples thereof include zeolites having a relatively large pore size such as CM-41, and at least one kind of zeolite selected from the group consisting of hydrogen, ammonium and polyvalent metals as in the case of a conventional catalytic catalyst for catalytic cracking. It is used in the ion-exchanged form with the cations. Y-type zeolite, particularly ultra-stable Y-type zeolite, is preferable because it has excellent hydrothermal resistance.

The aluminum-acid solubility index in the present invention is
It is an index indicating the difficulty of solubility of an alumina hydrate slurry in a nitric acid aqueous solution, and is related to the applicant of the present invention.
It is measured by a method similar to that described in Japanese Patent No. 173854. That is, the aluminum-acid solubility index is a value determined by the following measuring method. (1) 10.0 g of alumina hydrate slurry was sampled in terms of oxide in a glass beaker having a volume of 1 liter, and ion-exchanged water was added to obtain a suspension having a total volume of about 700 ml. (2) Then, the pH of this suspension was adjusted to 7.0 ±
Adjust to a range of 0.2 by adding a 10 wt% caustic soda solution or a 10 wt% nitric acid solution. (3) Next, 171 g of a 10 wt% nitric acid solution is added, and the mixture is transferred to a 1-liter measuring flask, and the total volume is made 1-liter using ion-exchanged water. The total amount of this suspension was transferred to a 2-liter separable flask with a reflux condenser, and the mixture was stirred at 90 ° C.
Heat at ℃ for 1 hour. (4) After cooling, the mixture is filtered through 0.4 μm and 0.2 μm filter paper (DISMIC-25HP manufactured by Toyo Roshi Kaisha, Ltd.) to measure the aluminum concentration in the filtrate. (5) The aluminum-acid solubility index is calculated by the following formula.

## EQU1 ## (Aluminum-acid solubility index) = 100 × (Al concentration in filtrate) ÷ [Al concentration when it is assumed that all alumina contained in 10.0 g of alumina hydrate (as oxide) is dissolved. ]

The alumina hydrate slurry according to the present invention is a pseudo-boehmite type alumina hydrate characterized by having an aluminum-acid solubility index in the range of 5 to 30. The aluminum-acid solubility index of the alumina hydrate slurry is 5
When it is less than, when mixed with an inorganic oxide matrix precursor such as silica sol or silicic acid solution, the reactivity with the inorganic oxide is poor, and the solid acid of the catalyst composition for catalytic cracking of the resulting hydrocarbon oil is obtained. Since the amount thereof is small, the bottom resolution is deteriorated, and the Lewis acid contained in alumina is strongly expressed, so that the amount of hydrogen and coke produced is unfavorably increased. When the aluminum-acid solubility index is greater than 30, the amount of alumina dissolved in the acid that reacts with the inorganic oxide increases when mixed with an inorganic oxide matrix precursor such as silica sol or silicic acid solution. Since the amount of solid acid and acid strength suitable for catalytic cracking of hydrocarbon oil cannot be obtained because alumina elutes during catalyst preparation, the catalytic composition for catalytic cracking obtained has low cracking activity, which is not preferable.

Further, in the present invention, the pseudo-boehmite-type alumina hydrate is fibrous particles, and it is preferable that the fibrous particles of the alumina hydrate have an average length in the range of 50 to 500Å. To confirm that the alumina hydrate is fibrous particles, confirm that the alumina hydrate slurry is 120 to 140 ° C.
Dry for 10 to 15 hours with a transmission electron microscope (T
Observe the photograph taken by EM). For the length of the fibrous particles of the alumina hydrate, the major axis of the fibrous particles of the alumina hydrate taken in the TEM photograph is measured. The average length of the fibrous particles of the alumina hydrate is an average value obtained by measuring the length of at least 50 fibrous particles. When the average length of the fibrous particles of the alumina hydrate is larger than 500Å, the aluminum-acid solubility index of the alumina hydrate slurry becomes small, and the bottom resolution is poor and the formation of hydrogen and coke due to the reasons described above. There is a possibility that a large amount of the catalytic composition for catalytic cracking may be obtained, which is not preferable. Further, when the average length of the fibrous particles of the alumina hydrate is smaller than 50Å, the aluminum-acid solubility index of the alumina hydrate slurry becomes large, and for the reasons described above, the catalyst for catalytic cracking having low decomposition activity is obtained. The composition may be obtained, which is not preferable. More preferably, the average length of the fibrous particles of the hydrated alumina is 50 to 4
It is 00Å. The aspect ratio (length / diameter) of the fibrous particles of the hydrated alumina is preferably in the range of 5 to 20.

The pseudo-boehmite alumina hydrate having the above-mentioned properties can be produced, for example, as follows. Alumina (Al ₂ O
₃ ) 0.5-15% by weight, preferably 1-1
An aluminum sulfate aqueous solution having a concentration of 0% by weight is prepared. Separately, sodium aluminate is dissolved to form alumina (Al ₂
The O ₃ ) concentration is 0.5 to 15% by weight, preferably 1 to
An aqueous solution of sodium aluminate having a concentration of 12% by weight is prepared.
Then, the aluminum sulfate aqueous solution and the sodium aluminate aqueous solution are both added at 20 to 90 ° C, preferably 40 to 80 ° C.
While stirring at the temperature
Prepared in the range of 9.0, preferably 6.0 to 8.0,
Use alumina hydrate slurry. After filtering and washing this alumina hydrate slurry, pure water (alumina (Al ₂ O)
₃ ) Alumina hydrate slurry prepared to have a concentration of 2 to 20% by weight, preferably 5 to 17% by weight is treated with an ammonia solution to adjust the pH of the slurry to 9.0 to 12.0, preferably 9.5 to 11 Prepared in the range of 0.5 and a temperature of 50 to 1
The pseudo-boehmite-type alumina hydrate (b) can be obtained by preparing by stirring and aging at 20 ° C., preferably 70 to 110 ° C. for 1 to 24 hours, preferably 3 to 20 hours.

The inorganic oxide matrix precursor (c) in the present invention includes silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, etc.
Inorganic oxide matrix precursors used in conventional catalyst compositions for catalytic cracking of hydrocarbon oils that also act as binders can be used. The inorganic oxide matrix precursor may also contain a clay substance such as kaolin, halosite and montmorillonite, and a metal scavenger such as alumina and manganese compound.

The catalyst composition for catalytic cracking of hydrocarbon oil obtained by the method of the present invention comprises (a) a crystalline aluminosilicate zeolite in an amount of 1 to 50% by weight, preferably 5 to 40% by weight. %, (B) 0.5 to 30% by weight, preferably 1 to 20% by weight, of alumina derived from a pseudo-boehmite type alumina hydrate with respect to the catalyst composition.
It is desirable that (c) the inorganic oxide matrix is contained in the range of 20 to 98.5% by weight, preferably 40 to 94% by weight, based on the catalyst composition.

In the method of the present invention, a mixture containing the above-mentioned (a) crystalline aluminosilicate zeolite, (b) pseudo-boehmite alumina hydrate and (c) inorganic oxide matrix precursor is spray-dried by a usual method. And average particle size 40
Spherical particles in the range of ˜100 μm are obtained, and if necessary, the spherical particles are washed, dried and introduced with rare earth to obtain a catalytic composition for catalytic cracking.

In the method of the present invention, a mixture containing the above-mentioned (a) crystalline aluminosilicate, (b) pseudo-boehmite alumina hydrate, and (c) inorganic oxide precursor is spray-dried by a usual method. To obtain spherical particles having an average particle shape of 40 to 100 μm. In the present invention, the crystalline aluminosilicate zeolite contained in the spherical particles is ion-exchanged with a rare earth element, if necessary. Preferably. The rare earth element is not particularly limited, but examples thereof include Ce, La, Nd, Pr and Sm. Usually, these components are used in the form of an inorganic compound capable of ion-exchange of the crystalline aluminosilicate, such as chloride or nitrate. The catalytic composition for catalytic cracking obtained by ion-exchanging the crystalline aluminosilicate zeolite contained in the spherical particles obtained by spray drying with a rare earth element, has a decomposition activity due to an increase in the solid acid amount of the crystalline aluminosilicate zeolite. It is possible to exert effects such as improvement of hydrogen acid and coke yield due to the weakened solid acid strength, and improvement of hydrothermal resistance of the catalyst composition.

The catalyst composition for catalytic cracking obtained by the method of the present invention is a pseudo-boehmite-type alumina hydrate and a silica sol in which the aluminum-acid solubility index of the alumina hydrate slurry is within a specific range during production. , A solid acid amount and acid strength suitable for catalytic cracking reaction of hydrocarbon oil can be obtained by mixing with an inorganic oxide matrix precursor such as silicic acid solution, so that cracking activity is high, gasoline yield and It has effects such as high LCO yield, excellent bottom resolution, and low gas and coke yields.

The catalytic composition for catalytic cracking prepared by the method of the present invention can be used for fluid catalytic cracking of commonly used hydrocarbon oils, and as hydrocarbon oils, particularly metal contamination such as nickel and vanadium. Using a heavy hydrocarbon oil containing a normal pressure residual oil containing a substance, a desulfurized normal pressure residual oil, a reduced pressure residual oil, a desulfurized reduced pressure residual oil, etc., a reaction temperature of 470 to 550.
C, regeneration temperature 650-800 C, reaction pressure 1-3 kg /
cm ² , catalyst / oil weight ratio 3 to 15, contact time 0.1 to 1
It is preferable to use the reaction condition of 0 seconds.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of catalyst A: batch production of alumina hydrate) 11.4 kg of a sodium aluminate solution having a concentration of 22% by weight of Al ₂ O ₃ and 38.6 kg of pure water were mixed. , Al
_A sodium aluminate solution having a ₂ O ₃ concentration of 5% by weight was prepared and kept at 60 ° C. On the other hand, 17.8 kg of an aluminum sulfate solution having an Al ₂ O ₃ concentration of 7.04% by weight and 32.2 kg of pure water were mixed to prepare an aluminum sulfate solution having an Al ₂ O ₃ concentration of 2.5% by weight. , 60 ° C
Held in. The concentration of Al ₂ O ₃ of 5 wt% sodium aluminate solution was transferred to a stirred tank volume 100 liters as, in addition stirring concentration of _Al 2 _{O 3} as a 2.5 wt% aluminum sulfate solution in 5 minutes Adjust the pH to 7.
The mixture was adjusted to 2 and stirred at 60 ° C. for 1 hour. Next, 56 kg of the obtained alumina hydrate slurry was collected by dehydration with a filter and washed with 70 liters of 0.3% by weight ammonia water. 1250 g of this washed alumina hydrate cake was sampled on a dry basis, and pure water was added to make an alumina hydrate slurry having an Al ₂ O ₃ concentration of 12.5 wt%. While stirring this alumina hydrate slurry, 15 wt% ammonia water was added to adjust the pH to 1
After adjusting to 0.5, transfer to a closed aging tank, and
The mixture was stirred and aged at 0 ° C. for 10 hours. One part of this alumina hydrate slurry aged with stirring was sampled, and the aluminum-acid solubility index was measured to be 25. Also,
When the sampled alumina hydrate slurry was dried at 130 ° C. for 12 hours and subjected to X-ray diffraction, it was confirmed to be pseudo-boehmite alumina hydrate. Further, a photograph of the pseudo-boehmite-type alumina hydrate dried under the above conditions was photographed with a transmission electron microscope (TEM), and from observation of the photographed photograph, the pseudo-boehmite-type alumina hydrate was found to be fibrous particles. The average length of the fibrous particles of the hydrated alumina was 96Å. Next, the temperature of the stirred and aged alumina hydrate slurry was lowered to room temperature, 250 g of Al ₂ O ₃ was measured, and a 25% by weight sulfuric acid solution was added with stirring to adjust the pH to 3.1. Separately, 25% by weight
While stirring violently, 4.0 kg of sulfuric acid solution of
JIS No. 3 water glass solution having an O ₂ concentration of 15% by weight 8.
2 kg was added to prepare a silicic acid solution having a pH of 1.6. 1000 g of this silicic acid solution is weighed on the basis of SiO ₂ and mixed with an alumina hydrate slurry whose pH has been adjusted with a sulfuric acid solution, and then kaolin clay is dried on a dry basis of 2000 g, 30% by weight of an ultra-stable Y-type zeolite slurry. 15 by standard
00g was mixed and stirred well. Next, this slurry was passed through a colloid mill once and then supplied to a spray dryer for spray drying to obtain 4800 g of spherical particles on a dry basis. These spherical particles were added to 24 liters of pure water at 60 ° C. to make a slurry, and 1 kg of ammonium sulfate was added to the slurry to give 2
Stir for 0 minutes. The slurry was subjected to solid-liquid separation with a Buchner funnel, washed with 24 liters of pure water at 60 ° C., and this operation was repeated 3 times. Also, this washed cake is 60
20% by weight of rare earth chloride (In ₂ O ₃ ) as rare earth element oxide (RE ₂ O ₃ )
product name: Rare Earth Chloride, manufactured by dian Rare Earths Ltd.
384g containing various kinds of rare earth chlorides)
In addition, the mixture was stirred for 20 minutes. The slurry was subjected to solid-liquid separation with a Buchner funnel and washed with 24 liters of pure water at 60 ° C. The obtained cake was dried at 130 ° C. for 16 hours to obtain catalyst A.
Got Table 1 shows the properties of the catalyst A.

Example 2 (Preparation of catalyst B: continuous production method of alumina hydrate) 45.4 kg of a sodium aluminate solution having a concentration of 22% by weight of Al ₂ O ₃ and 159.6 kg of pure water were mixed. , A
A sodium aluminate solution having a concentration of ₁₂ O ₃ of 5% by weight was prepared and kept at 60 ° C. On the other hand, 71.0 kg of aluminum sulfate solution having an Al ₂ O ₃ concentration of 7.04% by weight
And 129.0 kg of pure water are mixed to prepare an aluminum sulfate solution having an Al ₂ O ₃ concentration of 2.5% by weight.
Hold at 0 ° C. Al at a flow rate of 1.7 kg per minute with a pump
_A sodium aluminate solution having a concentration of ₂ O ₃ of 5% by weight was supplied to a tank A with a stirrer having a volume of 30 liters, and 5 minutes after the supply, 5 minutes per minute of Al ₂ O ₃ was pumped with stirring. An aluminum sulfate solution having a concentration of 2.5 wt% was supplied to a tank A equipped with a stirrer and having a volume of 30 liters, and the pH was lowered to 7.2. Then the pH is adjusted to 7.2
5% by weight as Al ₂ O ₃ concentration while maintaining ± 0.2
Of sodium aluminate solution and Al ₂ O ₃ concentration of 2.5
The aluminum sulphate solution of wt% was kept flowing at a flow rate of 1.7 kg per minute for 90 minutes with stirring, and the alumina hydrate slurry overflowing from the tank A was provided at the bottom of the volume 4
Received in tank B of 00 liters and kept at 60 ° C for 1
Stir for hours. Thereafter, in the same manner as in Example 1, 56 kg of the obtained alumina hydrate slurry was dehydrated and collected by a filter and washed with 70 liters of 0.3% by weight ammonia water. 1250 g of this washed cake of alumina hydrate was sampled on a dry basis, and pure water was added to the sample to add Al ₂ O ₃
An alumina hydrate slurry having a concentration of 12.5% by weight was used. While stirring this alumina hydrate slurry, 15
After adjusting the pH to 10.5 by adding a wt% aqueous ammonia, the mixture was transferred to a closed aging tank and aged with stirring at 95 ° C. for 10 hours. One part of this stirred and aged alumina hydrate slurry was sampled, and the aluminum-acid solubility index was measured to be 18. Further, the sampled alumina hydrate slurry was dried at 130 ° C. for 12 hours and subjected to X-ray diffraction to confirm that it was a pseudo-boehmite type alumina hydrate. Further, the transmission electron microscope (T
EM), a photograph was taken, and from observation of the photograph, the pseudo-boehmite-type alumina hydrate was a fibrous particle, and the average length of the fibrous particle of the alumina hydrate was 166.
It was Å. The following catalyst was prepared in the same manner as in Example 1 to obtain a catalyst B. Table 1 shows the properties of the catalyst B.

Example 3 (Preparation of catalyst C) Al_TwoO_Three22% by weight of sodium aluminate dissolved
11.4 kg of liquid and 38.6 kg of pure water were mixed to obtain Al.
_TwoO_ThreePrepare a sodium aluminate solution with a concentration of 5% by weight.
Manufactured and kept at 40 ° C. On the other hand, Al_TwoO_ThreeAs concentration
With 17.8 kg of a 7.04% by weight aluminum sulfate solution
Mix with 32.2 kg of pure water to obtain Al_TwoO_ThreeAs concentration
Prepare a 2.5 wt% aluminum sulphate solution at 40 ° C
Held in. Al_TwoO_ThreeAluminum with a concentration of 5% by weight
200 liters capacity soda solution tank with agitator
To Al and stirring_TwoO_Three2.5 weight as concentration
% Aluminum sulfate solution for 5 minutes to bring the pH to 7.
Prepared to 2. Add this alumina hydrate slurry to tank C
To 60 ° C while stirring and heating to 60 ° C.
While circulating this slurry in the circulation line
Connect the circulation pump outside tank C from the bottom of the
Install a piping line from the circulation pump to the upper part of tank C
10) to the line for adding the slurry flowing through the pipe).
m^ThreeIt was circulated through at a flow rate of / hr. Out of circulation line
Al in a static mixer installed in the mouth _TwoO_ThreeAs concentration
225 kg / hr of 5 wt% sodium aluminate solution
And Al_TwoO_ThreeAluminum sulfate with a concentration of 2.5% by weight
Separately separate the nitric acid solution at a flow rate of 240 kg / hr.
Mixed in with a static mixer.
Mixed alumina hydrate at the outlet of the circulation line
Keep the slurry at pH 7.0-7.5
It was circulated for 2 hours. The following is the same as in Example 1,
Filter 56 kg of the obtained alumina hydrate slurry
Dehydrated and collected at 70 liters of 0.3% by weight ammonia water
-Washed. This washed alumina hydrate cake
Sampling 1250g on dry basis, adding pure water
l_TwoO_ThreeAlumina hydrate powder with a concentration of 12.5% by weight
It was a rally. Do not stir this alumina hydrate slurry
The pH is adjusted to 10.5 by adding 15% by weight of ammonia water.
Then, transfer it to a closed type aging tank and
The mixture was stirred and aged for 0 hours. This stirring and aged alumina water
1 part of the Japanese slurry was sampled and aluminum-acid
When the solubility index was measured, it was 7. Also, the sample
Aged alumina hydrate slurry at 130 ° C for 12 hours
When dried and subjected to X-ray diffraction, pseudo-boehmite type aluminum
It was confirmed to be monohydrate. Also, dry under the above conditions
Transmission pseudo electron microscope of hydrated pseudo-boehmite alumina hydrate
Take a picture with (TEM) and observe this picture
Therefore, pseudo-boehmite-type alumina hydrate is a fibrous particle.
And the average length of the fibrous particles of the alumina hydrate is 270
It was Å. The following catalyst was prepared in the same manner as in Example 1.
Conducted to obtain a catalyst C. Table 1 shows the properties of the catalyst C.

Comparative Example 1 11.4 kg of a sodium aluminate solution having a concentration of 22% by weight of Al ₂ O ₃ and 38.6 kg of pure water were mixed to obtain Al.
_A sodium aluminate solution having a ₂ O ₃ concentration of 5% by weight was prepared and kept at 35 ° C. On the other hand, 17.8 kg of an aluminum sulfate solution having an Al ₂ O ₃ concentration of 7.04% by weight and 32.2 kg of pure water were mixed to prepare an aluminum sulfate solution having an Al ₂ O ₃ concentration of 2.5% by weight. , 35 ° C
Held in. The concentration of Al ₂ O ₃ of 5 wt% sodium aluminate solution was transferred to a stirred tank volume 100 liters as, in addition stirring concentration of _Al 2 _{O 3} as a 2.5 wt% aluminum sulfate solution in 5 minutes Adjust the pH to 7.
The mixture was adjusted to 2 and stirred at 35 ° C. for 1 hour. In the same manner as in Example 1 below, 56 kg of the obtained alumina hydrate slurry was dehydrated and collected by a filter to give 0.3% by weight.
It was washed with 70 liters of ammonia water. 1250 g of this washed cake of alumina hydrate was sampled on a dry basis, and pure water was added to obtain an Al ₂ O ₃ concentration of 12.5 g.
It was a wt% alumina hydrate slurry. This alumina hydrate slurry was adjusted to pH 10.5 by adding 15% by weight of ammonia water while stirring, and then transferred to a hermetically-sealed aging tank, and aged with stirring at 95 ° C. for 10 hours. A part of this agitated and aged alumina hydrate slurry was sampled and the aluminum-acid solubility index was measured to be 3
It was 5. Further, the sampled alumina hydrate slurry was dried at 130 ° C. for 12 hours and subjected to X-ray diffraction to confirm that it was a pseudo-boehmite type alumina hydrate. Further, a photograph of the pseudo-boehmite-type alumina hydrate dried under the above conditions was photographed with a transmission electron microscope (TEM), and from observation of the photographed photograph, the pseudo-boehmite-type alumina hydrate was found to be fibrous particles. The average length of the fibrous particles of the hydrated alumina was 36Å. The following catalyst was prepared in the same manner as in Example 1 to obtain a catalyst D. Table 1 shows the properties of the catalyst D.

Comparative Example 2 Al_TwoO_Three22% by weight of sodium aluminate dissolved
11.4 kg of liquid and 38.6 kg of pure water were mixed to obtain Al.
_TwoO_ThreePrepare a sodium aluminate solution with a concentration of 5% by weight.
Manufactured and kept at 60 ° C. On the other hand, Al_TwoO_ThreeAs concentration
With 17.8 kg of a 7.04% by weight aluminum sulfate solution
Mix with 32.2 kg of pure water to obtain Al_TwoO_ThreeAs concentration
Prepare a 2.5 wt% aluminum sulphate solution at 40 ° C
Held in. Al_TwoO_ThreeAluminum with a concentration of 5% by weight
200 liters capacity soda solution tank with agitator
To Al and stirring_TwoO_Three2.5 weight as concentration
% Aluminum sulfate solution for 5 minutes to bring the pH to 7.
Prepared to 2. Add this alumina hydrate slurry to tank C
To 60 ° C while stirring and heating to 60 ° C.
While circulating this slurry in the circulation line
Connect the circulation pump outside tank C from the bottom of the
Install a piping line from the circulation pump at the top of tank C
10m to the line for adding the slurry flowing through the pipe)^Three
It was circulated through at a flow rate of / hr. At the exit of the circulation line
Al in the static mixer provided_TwoO_Three5 as concentration
Wt% sodium aluminate solution at 113 kg / hr and
And Al _TwoO_Three2.5% by weight of aluminum sulfate
The different solutions at different flow rates of 120 kg / hr.
, Mix evenly with a static mixer, and circulate.
Mixed alumina hydrate slurry at the exit of the ring line
-While maintaining the pH to 7.0-7.5,
Circulated for hours. The following was obtained in the same manner as in Example 1.
56 kg of alumina hydrate slurry
Collect and wash with 70 liters of 0.3% by weight ammonia water
Clean This washed alumina hydrate cake was dried with
Sampling 1250g, add pure water and add Al_TwoO
_ThreeAlumina hydrate slurry with a concentration of 12.5% by weight
And While stirring this alumina hydrate slurry 1
Adjust the pH to 10.5 by adding 5% by weight aqueous ammonia.
After that, transfer to a sealed aging tank and keep at 95 ° C for 10 hours.
The mixture was aged with stirring. This aged alumina hydrate powder
Sample 1 part of rally, aluminum-acid dissolving finger
It was 4 when the number was measured. Also sampled
Dried alumina hydrate slurry at 130 ° C for 12 hours
Then, X-ray diffraction was performed, and pseudo-boehmite-type alumina water
It was confirmed to be Japanese. Also, dried under the above conditions
Pseudo-boehmite-type alumina hydrate with transmission electron microscope (T
Take a picture with EM) and observe this picture.
, Pseudo-boehmite-type alumina hydrate is a fibrous particle.
And the average length of the fibrous particles of the alumina hydrate is 618
It was Å. The following catalyst was prepared in the same manner as in Example 1.
Conducted to obtain a catalyst E. Table 1 shows the properties of the catalyst E.

Comparative Example 3 Al_TwoO_Three22% by weight of sodium aluminate dissolved
11.4 kg of liquid and 38.6 kg of pure water were mixed to obtain Al.
_TwoO_ThreePrepare a sodium aluminate solution with a concentration of 5% by weight.
Manufactured and kept at 40 ° C. On the other hand, Al_TwoO_ThreeAs concentration
With 17.8 kg of a 7.04% by weight aluminum sulfate solution
Mix with 32.2 kg of pure water to obtain Al_TwoO_ThreeAs concentration
Prepare a 2.5 wt% aluminum sulphate solution at 40 ° C
Held in. Al_TwoO_ThreeAluminum with a concentration of 5% by weight
200 liters capacity soda solution tank with agitator
To Al and stirring_TwoO_Three2.5 weight as concentration
% Aluminum sulfate solution for 5 minutes to bring the pH to 7.
Prepared to 2. Add this alumina hydrate slurry to tank C
To 60 ° C while stirring and heating to 60 ° C.
While circulating this slurry in the circulation line
Connect the circulation pump outside tank C from the bottom of the
Install a piping line from the circulation pump at the top of tank C
10m to the line for adding the slurry flowing through the pipe)^Three
It was circulated through at a flow rate of / hr. At the exit of the circulation line
Al in the static mixer provided_TwoO_Three5 as concentration
A weight% sodium aluminate solution of 150 kg / hr and
And Al _TwoO_Three2.5% by weight of aluminum sulfate
Solution solution at a flow rate of 145 kg / hr on separate lines.
, Mix evenly with a static mixer, and circulate.
Mixed alumina hydrate slurry at the exit of the ring line
-Holding the pH at 7.8-8.0,
Circulated for hours. The following was obtained in the same manner as in Example 1.
56 kg of alumina hydrate slurry
Collect and wash with 70 liters of 0.3% by weight ammonia water
Clean This washed alumina hydrate cake was dried with
Sampling 1250g, add pure water and add Al_TwoO
_ThreeAlumina hydrate slurry with a concentration of 12.5% by weight
And While stirring this alumina hydrate slurry 1
Adjust the pH to 10.5 by adding 5% by weight aqueous ammonia.
After that, transfer to a sealed aging tank and keep at 95 ° C for 10 hours.
The mixture was aged with stirring. This aged alumina hydrate powder
Sample 1 part of rally, aluminum-acid dissolving finger
It was 2 when the number was measured. Also sampled
Dried alumina hydrate slurry at 130 ° C for 12 hours
Then, X-ray diffraction was performed, and pseudo-boehmite-type alumina water
It was confirmed to be Japanese. Also, dried under the above conditions
Pseudo-boehmite-type alumina hydrate with transmission electron microscope (T
Take a picture with EM) and observe this picture.
, Pseudo-boehmite-type alumina hydrate is a fibrous particle.
And the average length of the fibrous particles of the alumina hydrate is 814
It was Å. The following catalyst was prepared in the same manner as in Example 1.
Then, a catalyst F was obtained. Table 1 shows the properties of the catalyst F.

[0027]

[Table 1]

(Activity Test) Catalysts A to F were calcined in air at 600 ° C. for 2 hours and then cooled with a desiccator so as not to absorb moisture. Nickel naphthenate and vanadium naphthenate dissolved in benzene in 100 g of each catalyst,
The catalyst was impregnated with Ni at 2000 wtppm and V at 4000 wtppm. After the impregnation, calcination was performed at 600 ° C. for 1 hour to remove organic substances in the catalyst, and subsequently pseudo equilibrium was performed at 780 ° C. for 13 hours under conditions of 100% steam partial pressure. Pseudo-equilibrium catalysts AF are Micr
The catalytic activity was measured by oActivity Tester (MAT).

(MAT measurement conditions) Reaction temperature: 510 ° C., WHSV: 40 hr ⁻¹ , feed oil: hydrodesulfurization atmospheric distillation residue (DSAR) 40% by volume
Mixed oil of 60% by volume of hydrodesulfurized atmospheric distillation gas oil (DSVGO), the yield at a cracking rate of 65% by weight, the yield results when the catalyst / oil weight ratios of 3, 4 and 5 were reacted. The respective yields are obtained when the decomposition rate is fixed at 65% by weight.

[0030]

[Table 2]

As shown in Table 2, for catalytic cracking of a hydrocarbon oil obtained from a mixture containing a pseudo-boehmite-type alumina hydrate having an aluminum-acid solubility index in the range of 5 to 30 in an alumina hydrate slurry. When the reaction was carried out using the catalyst composition, the effects of high cracking activity, high gasoline and LCO yields, and low HCO, gas and coke yields were obtained.

The embodiments of the present invention will be listed below. (1) (a) crystalline aluminosilicate zeolite,
A mixture comprising (b) a pseudo-boehmite-type alumina hydrate having an aluminum-acid solubility index in the range of 5 to 30 of the alumina hydrate slurry and (c) an inorganic oxide matrix precursor is spray-dried. And a method for producing a catalyst composition for catalytic cracking of hydrocarbon oil. (2) The pseudo-boehmite alumina hydrate is fibrous particles, and the fibrous particles of the alumina hydrate have an average length of 5
The method for producing a catalyst composition for catalytic cracking of hydrocarbon oil according to claim 1, wherein the catalyst composition is in the range of 0 to 500Å. (3) (a) crystalline aluminosilicate zeolite,
A mixture obtained by spray drying a mixture containing (b) a pseudo-boehmite-type alumina hydrate in which the aluminum-acid solubility index of the alumina hydrate slurry is in the range of 5 to 30 and (c) an inorganic oxide matrix precursor is obtained. A method for producing a catalyst composition for catalytic cracking of hydrocarbon oil, characterized in that (a) the crystalline aluminosilicate zeolite contained in the spherical particles is ion-exchanged with a rare earth element.

[0033]

The catalytic composition for catalytic cracking obtained by the method of the present invention is a pseudo-boehmite type alumina hydrate in which the aluminum-acid solubility index of the alumina hydrate slurry is within a specific range at the time of preparation. By mixing it with an inorganic oxide matrix precursor such as silica sol or silicic acid solution, a solid acid amount and acid strength suitable for the catalytic cracking reaction of hydrocarbon oil can be obtained, so that the cracking activity is high and the gasoline yield is high. And the yield of LCO are high, the bottom resolution is excellent, and the yields of gas and coke are low.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4G069 AA02 AA03 BA01A BA01B                       BA01C BA07A BA07B BA10B                       BB04B BC38B CC07 EA01Y                       FA01 FB06 FB08 FB63 FC02                       ZA04A ZA05A ZA05B ZF02A                       ZF02B                 4H029 BA11 BB05 BB06 BD01 BD08                       CA00 DA00

Claims (2)

[Claims] 1. Alumina silicate slurry comprising (a) crystalline aluminosilicate zeolite and (b) alumina hydrate slurry.
A catalyst composition for catalytic cracking of hydrocarbon oil, characterized in that a mixture containing a pseudo-boehmite-type alumina hydrate having an acid solubility index in the range of 5 to 30 and (c) an inorganic oxide matrix precursor is spray-dried. Method of manufacturing things. 2. The pseudo-boehmite-type alumina hydrate is fibrous particles, and the fibrous particles of the alumina hydrate have an average length in the range of 50 to 500Å. 1. A method for producing a catalyst composition for catalytic cracking of hydrocarbon oils.