JPH0576769A - Hydrogenolysis catalyst composition and production thereof - Google Patents

Abstract

PURPOSE:To provide a catalyst compsn. enabling the hydrogenelysis of hydrocarbon oil, especially heavy hydrocarbon oil at a high rate of conversion in a high yield of intermediate fraction. CONSTITUTION:A metal hydride is supported on a carrier consisting of modified faujasite type zeolite and a porous inorg. oxide to obtain a hydrogenelysis catalyst compsn. The modified faujasite type zeolite has 2 6 molar ratio of silica to alumina before heat history at >=150 deg.C and >=0.70 rate of ammonium ion exchange. Ammonium and/or rare earth metal cations may be substd. for at least part of the residual alkali metal in the zeolite.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrocracking catalyst composition for hydrocarbon oils, particularly heavy hydrocarbon oils, and a process for producing the same, and more specifically to a specific modified faujasite type zeolite and a porous material. The present invention relates to a hydrocracking catalyst composition in which a metal hydride component is supported on a carrier composed of an inorganic oxide, and a method for producing the same.

[0002]

2. Description of the Related Art In general, various catalyst compositions containing mainly faujasite type zeolite have been proposed as catalyst compositions for hydrocracking hydrocarbon oils. (For example, JP-A-62-298453) However, in the conventional hydrocracking catalyst composition containing a faujasite-type zeolite, the decomposition product is further decomposed due to its high decomposition activity, so that gas and naphtha There was a problem that the production rate was high and the yield of middle distillates was low.

[0003]

It is a novel object of the present invention to hydrocrack hydrocarbon oils, especially heavy hydrocarbon oils, with a high conversion, a high yield of middle distillates, and a low gas and naphtha production rate. The present invention provides a novel hydrocracking catalyst composition and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention provides a hydrocracking catalyst composition in which a metal hydride component is supported on a carrier composed of faujasite-type zeolite and a porous inorganic oxide, wherein the faujasite-type zeolite is 150 ° C. Modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more, or at least a part of its residual alkali metal, is an ammonium ion in a state where it is not subjected to the above heat history. And / or a hydrogen-cracking catalyst composition characterized by being substituted with a rare earth metal cation and a method for producing the same.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The modified faujasite-type zeolite in the hydrocracking catalyst composition of the present invention has an ammonium ion exchange ratio (NH
₄ Z) shows a high ion exchange rate of 0.70 or more, preferably 0.72 or more, a silica / alumina molar ratio of 6 or more, preferably in the range of 7 to 30, and a unit lattice constant of 24.65Å. Below, preferably 24.55 to 24.30
It is in the range of Å.

Such a modified faujasite-type zeolite is disclosed, for example, in Japanese Patent Application No. 3-99 filed previously by the present applicant.
390, that is, by contacting a faujasite-type zeolite that has not been subjected to heat history with a dealuminating agent in the presence of soluble silica in an aqueous phase at a pH of 4 or less.

The soluble silica is a silicic acid contained in an aqueous solution, which is in a state of producing yellow molybdosilicic acid by adding an ammonium molybdate solution by acidifying the aqueous solution with sulfuric acid. Sources of soluble silica include orthosilicic acid, metasilicic acid, etc. xSiO ₂ · y
Silicic acid represented as H ₂ O; silicates such as metasilicate, orthosilicate, disilicate, trisilicate, etc .; silica sol in which silicic acid is highly polymerized; silane compounds, etc. it can. The amount of soluble silica present in the aqueous solution is preferably 130 ppm or more. The amount of soluble silica present in the aqueous solution is 130
If it is less than ppm, the crystal structure of zeolite is destroyed by the acid treatment, which is not desirable.

Examples of the dealumination agent include mineral acids such as sulfuric acid, nitric acid and hydrochloric acid, organic acids such as acetic acid, and EDTA.
Although a chelating agent such as and a dealuminating agent that is usually used for dealumination of zeolite can be used, sulfuric acid, nitric acid, and hydrochloric acid are particularly preferable.

In the modified faujasite-type zeolite, aluminum in the unit cell forming the hexagonal prism of the faujasite-type zeolite framework structure is preferentially dealuminated, and silicon is inserted at the dealuminated position. The aluminum content in the unit cell forming a hexagonal prism is lower than that of conventional faujasite-type zeolite in relation to the total aluminum content in the skeletal structure. Presumed to be excellent.

The ammonium ion exchange rate (NH ₄ Z) of a conventional faujasite type zeolite (zeolite Y) which has not been subjected to a heat history of 150 ° C. or higher is usually about 0.68. In general, a zeolite having a low silica / alumina molar ratio tends to have a high ammonium ion exchange rate (NH ₄ Z), but a zeolite having a silica / alumina molar ratio of 5 or more has an ammonium ion exchange rate of 0.70 by the above method. No more. Therefore, in order to increase the ammonium ion exchange rate, NH ₄ —Na-faujasite-type zeolite once subjected to ammonium ion exchange is repeatedly ion-exchanged to increase the ion exchange rate, or the zeolite is calcined at a temperature of 400 to 700 ° C. After that, a method of further exchanging ammonium ions is being carried out.

In the present invention, the state of not being subjected to a heat history of 150 ° C. or higher means that the starting material and the modified faujasite type zeolite have no history of being calcined at a temperature of 150 ° C. or higher, or a modified faujasite type. When the zeolite is calcined at a temperature of 150 ° C. or higher, it defines the silica / alumina molar ratio and the ammonium ion exchange rate of the modified faujasite-type zeolite before calcining.

Further, the ammonium ion exchange rate in the present invention is described in "Zeolite Mole" by DONALD W. BREK.
cular Sieves ”A WILEY-INTERSCIENCE PUBLICATION (19
74) Chapter Seven ； Ion Exchenge Reactions in Zeo
It is the value displayed by the method described in lites and measured as follows. That is, 1 sample of faujasite-type zeolite that has not been subjected to a heat history of 150 ° C or higher
Suspend in 0 times the amount of pure water (ion-exchanged water). To this suspension, 10 times as many salt (NaCl) as the number of moles (m) of alumina, which was previously obtained from the composition analysis of the sample zeolite, was added, and the mixture was heated to 80 ° C. with stirring. Then, a 3.0 wt% NaOH solution was added at a temperature of 80 ° C. to adjust the pH of the suspension to 8.
After adjusting to 5 and stirring for 1 hour, the temperature is further heated to 90 ° C. and stirring is performed for 30 minutes. The suspension is then filtered,
Thoroughly wash with warm water at 80 ° C. to obtain Na (+) exchanged zeolite. By this operation, a sodium ion-exchanged zeolite is obtained. Na obtained by the above operation
Ammonium ion exchange is performed as follows using (+) exchanged zeolite. That is, Na (+)-exchanged zeolite was suspended in 10 times the amount of pure water (ion-exchanged water), and ammonium sulfate was added to this suspension in an amount of 5 times the number of moles (m) of alumina obtained from the composition analysis of the sample zeolite in advance. And warm to 80 ° C. with stirring. The suspension was then maintained at a temperature of 80 ° C. for 1 hour with stirring and then filtered,
It is thoroughly washed with warm water of 0 ° C. and dried at 120 ° C. for 24 hours to obtain an ammonium ion exchanged zeolite. Similarly, ammonium ion exchange of Na (+) exchanged zeolite is performed using 10 times the amount of ammonium sulfate. The ammonium ion exchange rate (NH ₄ Z) in the present invention was calculated from the analytical values of Na (+) exchanged zeolite and NH ₄ (+) exchanged zeolite and the amount of ammonium sulfate used for ammonium ion exchange for these two NHs. The result of the ₄ (+) exchange is shown in an ion exchange equilibrium diagram, and the ammonium ion exchange rate (NH ₄ Z) when the equilibrium fraction of NH ₄ + in the solution is 0.9.
Indicated by.

As the modified faujasite-type zeolite of the present invention, the above-mentioned faujasite-type zeolite which has not been subjected to a heat history of 150 ° C. or higher is brought into contact with a dealuminating agent at a pH of 4 or less in the presence of soluble silica in an aqueous phase. In addition to those manufactured by the above method, those ion-exchanged with ammonium ions and / or rare earth metal ions,
And those obtained by firing these in air or in a steam atmosphere can also be used.

As the porous inorganic oxide in the present invention, A
_{l 2 O 3, SiO 2,} SiO 2 -Al 2 O 3, Al 2 O 3 -Ti
_{O 2, Al 2 O 3 -B} 2 O 3, Al 2 O 3 -P 2 O 5, Al 2 O 3
A porous inorganic oxide used in a general hydrotreating catalyst composition such as —SiO ₂ —TiO ₂ or Al ₂ O ₃ —ZrO ₂ —B ₂ O ₃ is used.

As the metal hydride component in the present invention, a known metal component conventionally used for this type of hydrogenolysis can be used, and for example, it can be selected from Group VIII and / or VIA of the periodic table. A metal component may be used. As a preferable metal component, a combination of Mo, W and Co, Ni is exemplified.

In the hydrocracking catalyst composition of the present invention, the content of the modified faujasite-type zeolite in the carrier is 2
It is desirable that the content of the metal hydride component in the hydrocracking catalyst composition is 0 to 80 wt%, preferably 30 to 70 wt%, and the content of the Group VIII metal component as an oxide is 0.2. ~ 15wt%, Group VIA metal component 5 ~ 3
It is preferably in the range of 0 wt%.

The hydrocracking catalyst composition according to the present invention is obtained by, for example, mixing the modified faujasite-type zeolite with a precursor of a porous inorganic oxide and molding the mixture into a desired shape by a usual method, followed by drying. , A method of producing a carrier by firing, impregnating a metal hydride component by a usual method, and then drying and firing, or a method in which the modified faujasite zeolite and the precursor of the porous inorganic oxide are hydrogenated metal components. And mix
It is manufactured by a method such as molding into a desired shape, drying and firing. Further, although the precursor of the porous inorganic oxide is used in the above-mentioned production method, the porous inorganic oxide itself can be used as long as it can be mixed with other catalyst composition components and molded into a desired shape. For the calcination of the carrier and the hydrocracking catalyst composition, conventional calcination conditions for this type of catalyst are applied, and the range of 400 to 650 ° C is preferable. Further, the hydrocracking catalyst composition according to the present invention can be applied with processing conditions in which a conventional catalyst of this kind is used for hydrocracking of hydrocarbon oil, generally at a temperature of 300 to 500 ° C. and hydrogen pressure. 40-300 kg / cm ² , liquid space velocity 0.1-10 h
Processing conditions in the range of r ^-1 are adopted. The present invention will be specifically described below with reference to examples.

[0018]

【Example】

Example 1 NaY zeolite (molar composition _{Na 2 O · Al 2 O 3} · 5S
Ion exchange was repeated without firing 1392 g of iO ₂ ) by a conventional method to prepare an ammonium-exchanged zeolite having a Na residual ratio of 25%. This ammonium-exchanged zeolite was suspended in 13.92 liters of warm water at 80 ° C as it was. A silicic acid solution 1 having a pH of 2.0 obtained by neutralizing No. 3 water glass separately diluted with silica concentration of 1% with sulfuric acid
7.1 kg was prepared. First 930 g from this silicic acid solution
Was added to the suspension with stirring. Then the temperature is raised to 95
The temperature was raised to ℃, and 41.16 kg of sulfuric acid having a concentration of 2.5% and 10.77 kg of the remaining silicic acid solution were respectively 823.8 g / hr and 3
P was added continuously at a rate of 23.4 g / hr for 50 hours.
It was set to H1.8. After the addition of the sulfuric acid and silicic acid solution, the zeolite is separated, washed and dried to obtain modified zeolite SA.
I-1 was obtained. The properties of this modified zeolite are shown in Table 1. This modified zeolite (SAI-1) and a part of the starting NaY zeolite were examined for ammonium ion exchange properties. As the ammonium ion exchange method, according to the above-mentioned method, Na (+) exchanged zeolite was used, and then the amount of ammonium sulfate was changed to obtain the ion exchange rate at 80 ° C. As a result, NH _{4 in} the solution
Table 1 also shows the ammonium ion exchange rate (NH ₄ Z) when the equilibrium fraction of (+) was 0.9. Meanwhile, the aqueous solution of aluminum sulfate and the aqueous solution of sodium aluminate were adjusted to pH 7.5.
The precipitate obtained by the neutralization reaction with was dehydrated and washed to prepare a coagulated boehmite-like alumina hydrate. 900 g of this condensed boehmite-like alumina hydrate was collected in terms of oxide, and 600 g of the above-mentioned SAI-1 zeolite (Dry Basi).
s) is mixed in a kneader and mixed by heating to adjust the water content, and then extruded into a cylinder of 1.6 mmφ, and after drying 55
The carrier was obtained by baking at 0 ° C. for 3 hours. This carrier was impregnated with an aqueous solution of ammonium paramolybdate and dried, further impregnated with an aqueous solution of nickel nitrate, dried, and calcined at 550 ° C. for 3 hours to hydrogenate MoO ₃ at 15 wt% and NiO at 4 wt%. A catalyst A containing a metal component was prepared. The properties of catalyst A are shown in Table-2.

Comparative Example 1 NaY zeolite (molar composition Na ₂ O.Al ₂ O ₃ .5S)
1392 g of iO ₂ ) was repeatedly ion-exchanged by a usual method to prepare an ammonium-exchanged zeolite having a Na residual ratio of 25%. This zeolite was washed, dried and then calcined at 550 ° C. for 3 hours. Next, the calcined zeolite was further ion-exchanged using ammonium sulfate to prepare NH ₄ —Y zeolite (Na ₂ O content 1.37 wt%) having an ammonium exchange rate of 91%. This NH ₄ —Y zeolite with an exchange rate of 91% was heated at 600 ° C. for 3 hours in a steam atmosphere.
It was calcined for an hour to obtain ultra stable zeolite (US-Y) Z-1. The properties of this ultra stable zeolite are shown in Table 1. Then, the same operation as in Example 1 was carried out to obtain a catalyst B using the ultrastable zeolite. The properties of catalyst B are shown in Table-2.

Example 2 In the production of the modified zeolite in Example 1, 527.22 kg of nitric acid having a concentration of 2.5% was added to 1057.2 g / hr.
Modified zeolite SAI-2 was obtained in exactly the same manner as in Example 1, except that the addition was continuously performed at the rate of 50 hours.
The properties of this modified zeolite are shown in Table 1. On the other hand, the aqueous solution of No. 3 water glass and the aqueous solution of aluminum sulfate were reacted and the pH was adjusted to 7.0 with the aqueous solution of sulfuric acid to precipitate silica-alumina hydrate (SiO ₂ / Al ₂ O ₃ = 85/15). Was generated, dehydrated and washed to obtain a silica-alumina hydrate slurry. This silica-alumina hydrate slurry is weighed in an amount of 600 g in terms of oxide and put in a kneader, and then 600 g of the above-mentioned SAI-2 zeolite is weighed in a dry weight of 600 g and mixed with the kneader. After adjustment, 1.
It was extruded into a cylindrical shape of 6 mmφ. Example 1
In the same manner as above, the carrier was obtained by baking at 550 ° C. for 3 hours. This carrier was impregnated with an aqueous solution of ammonium paratungstate and dried, further impregnated with an aqueous solution of nickel nitrate, dried, and calcined at 550 ° C. for 3 hours to give WO ₃ of 15w.
A catalyst C containing t% and a metal hydride component of 4 wt% as NiO was prepared. The properties of catalyst C are shown in Table-3.

Comparative Example 2 600 g of the ultra-stable zeolite Z-1 obtained in Comparative Example 1 was sampled by dry weight, and 600 g of the silica-alumina hydrate slurry obtained in Example 2 in terms of oxide. After mixing with a kneader, heating and mixing, and adjusting the water content, the mixture was extruded into a cylinder of 1.6 mmφ. Then, the obtained molded body is 550
A carrier was prepared by firing at 3 ° C for 3 hours. Using this carrier, in the same manner as in Example 2, 15 wt% of WO _{3 was} added.
And a catalyst D containing 4 wt% NiO were prepared. Catalyst D
The properties of are shown in Table-3.

Example 3 (Evaluation Test I) A catalyst evaluation test was conducted using the catalysts A and B prepared in Example 1 and Comparative Example 1. In the test method, a predetermined amount of each catalyst was filled in a microreactor having an inner diameter of 24 mm and the catalyst was subjected to a sulfurization treatment, and then an atmospheric residual oil having the following properties was hydrocracked under the following reaction conditions. Properties of atmospheric residual oil: Specific gravity 0.985 (15/4 ° C) Sulfur content 3.92 (wt%) Ni 19 (ppm) V 60 (ppm) Reaction conditions: Temperature 400 (° C) LHSV 0.2 (hr ^-1 ) Pressure 150 (kg / cm ² G) H ₂ / Oil 700 (N liter / liter) Table 2 shows the evaluation results.

Example 4 (Evaluation Test II) A catalyst evaluation test was conducted using the catalysts C and D prepared in Example 2 and Comparative Example 2. In the test method, a predetermined amount of each catalyst was filled in a microreactor having an inner diameter of 24 mm and the catalyst was subjected to sulfurization treatment, and then vacuum gas oil having the following properties was hydrocracked under the following reaction conditions. Properties of vacuum gas oil; Specific gravity 0.920 (15/4 ° C) Sulfur content 2.26 (wt%) N ₂ 1140 (ppm) 360 ° C (+) fraction 81.8 (wt%) Reaction conditions; Temperature 400 ( C) LHSV 1.5 (hr ^-1 ) pressure 47 (kg / cm ² G) H ₂ / Oil 500 (N liter / liter) Table 3 shows the evaluation results.

[0024]

[Table 1] * ¹ Crystallinity is 100 for NaY zeolite starting material
Relative value when expressed as%. * ^{2 In the} ion exchange equilibrium diagram, the ammonium ion exchange rate of zeolite when the equilibrium fraction of NH ₄ (+) in the solution is 0.9.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Effect] The hydrocracking catalyst composition of the present invention is used for hydrocracking of hydrocarbon oil, has excellent thermal stability, shows a high cracking rate, and has a high yield of middle distillates. It has excellent characteristics such as low production rate.

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

Claims (6)

[Claims] 1. A hydrocracking catalyst composition comprising a support comprising a faujasite-type zeolite and a porous inorganic oxide and a metal hydride component supported thereon, wherein the faujasite-type zeolite has a thermal history of 150 ° C. or higher. A hydrocracking catalyst composition, which is a modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in a state of not undergoing treatment. 2. A modified faujasite-type zeolite produced by contacting a faujasite-type zeolite that has not been subjected to a thermal history of 150 ° C. or higher with a dealuminating agent in the presence of soluble silica in an aqueous phase at a pH of 4 or less, 2. The hydrocracking catalyst composition according to claim 1, wherein the modified faujasite-type zeolite is further calcined and used as a carrier faujasite-type zeolite. 3. A modified faujasite-type zeolite produced by contacting a faujasite-type zeolite that has not been subjected to a heat history of 150 ° C. or higher with a dealuminating agent in the presence of soluble silica in an aqueous phase at a pH of 4 or less. At least a part of the remaining alkali metal is replaced with ammonium ions and / or rare earth metal cations, or a product obtained by further subjecting this to a calcination treatment,
The hydrocracking catalyst composition according to claim 1, which is used as a faujasite-type zeolite as a carrier. 4. A modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in a state where it has not been subjected to a heat history of 150 ° C. or more, and a porous inorganic material. It is characterized in that an oxide precursor is mixed, the mixture is formed into a desired shape, dried and baked to produce a carrier, and the carrier is impregnated with a metal hydride component, and then dried and baked again. The method for producing the hydrocracking catalyst composition according to claim 1. 5. A modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in the state of not being subjected to a heat history of 150 ° C. or more, and a porous inorganic oxide. The method for producing a hydrocracking catalyst composition according to claim 1, wherein a mixture of a precursor of the product and a metal hydride component is formed, the mixture is shaped into a desired shape, and then dried and calcined. 6. A modified faujasite-type zeolite having a silica / alumina molar ratio of 6 or more and an ammonium ion exchange rate of 0.70 or more in a state where it is not subjected to a heat history of 150 ° C. or more, and a porous inorganic material. The precursor of the hydrocracking catalyst composition according to claim 1, wherein a metal hydride component is supported on a carrier composed of an oxide precursor.