JPH0790170B2 - Catalytic composition for catalytic cracking of hydrocarbon oil and catalytic cracking method using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalytic composition for catalytic cracking of hydrocarbon oil and a catalytic cracking method of hydrocarbon oil using the same, and more specifically to a specific metal by a specific method. The present invention relates to a catalyst composition comprising the novel crystalline aluminosilicate introduced and a catalytic cracking method capable of producing gasoline having a high octane number by bringing the catalyst composition into contact with a hydrocarbon oil.

(Problems to be Solved by Prior Art) Generally, in petroleum refining, efficient production of catalytically cracked gasoline having a high octane number is the most important issue. Catalytically cracked gasoline can be obtained by catalytically cracking light oil fractions from crude oil under atmospheric distillation or vacuum distillation, atmospheric distillation residue and vacuum distillation residual oil using a catalyst consisting of crystalline aluminosilicate and matrix. .

Many techniques have already been proposed as catalysts for the production of high octane catalytic cracking gasoline. For example, in the case of using stabilized Y zeolite or ZSM-5 as a catalyst component, JP-A-56-5889, JP 47-8074, JP 61-
82845, JP 59-49289, JP 55-147590, JP 57
-51790. However, when the stabilized Y zeolite and ZSM-5 are used, the octane number is improved, but the olefin content is inevitably increased. Olefin is considered to adversely affect the stability of gasoline, and the fact is that the olefin content in motor gasoline is limited. Therefore, even if the octane number of the catalytically cracked gasoline is improved, if the olefin content is increased, the mixing ratio of the catalytically cracked gasoline, which is an inexpensive gasoline base material, to the motor gasoline must be reduced, which is a serious problem. Therefore, the advent of a new catalyst that improves the octane number while reducing the content of the olefin that is also an octane booster is awaited. In order to solve these problems, a catalytic composition for catalytic cracking using an ion-exchange type zeolite obtained by ion-exchanging zeolite with a metal compound has been disclosed, but it is not sufficient because the increase in octane number is small.

(Means and Actions for Solving the Problems) As a result of intensive studies to further develop the conventional technique, the present inventors have used a catalyst made of a crystalline aluminosilicate in which a specific metal is introduced by a specific method, It has been found that catalytic cracking of hydrocarbon oil gives catalytic cracking gasoline with low olefin and high octane number, and the present invention has been completed.

That is, an object of the present invention is to provide a catalyst composition capable of producing a gasoline having a low olefin and a high octane number by catalytically cracking a hydrocarbon oil, and an excellent catalytic cracking method for a hydrocarbon oil using these catalyst compositions. To do.

That is, the present invention comprises physically mixing fine particles of a metal oxide of at least one active metal selected from the group consisting of iron, nickel, copper and gallium with a mixture of a crystalline aluminosilicate and a matrix. A catalyst composition for catalytic cracking of hydrocarbon oils, characterized in that the active metal content is 0.1 to 10% by weight as a metal oxide on a catalyst basis, and also comprises a crystalline aluminosilicate, a matrix and an active metal component. The active metal component is obtained by impregnating and supporting at least one active metal compound selected from the group consisting of iron, nickel, copper and gallium, and then calcining it to form a metal oxide. A catalyst composition for catalytic cracking of hydrocarbon oils, characterized in that it is 0.1 to 10% by weight based on the catalyst. It exists in a catalytic cracking method for hydrocarbon oils that catalytically cracks hydrocarbon mixed oils that boil over a range of temperatures above.

It has been conventionally considered that the introduction of an active metal by physical mixing of metal oxides is not effective as compared with the method by ion exchange because the dispersion of the active metal is insufficient. When we proceeded, we obtained the finding that when the catalyst composition in which the active metal was introduced by physically mixing the fine particles of the specific metal oxide was used, the octane number increased and the one with a low olefin content was obtained. The present invention has been completed by finding similar effects even when a catalyst composition in which a specific amount of a metal oxide is supported by firing after impregnation with a solution of an active metal compound is completed.

Hereinafter, the present invention will be described in more detail.

The crystalline aluminosilicate (sometimes abbreviated as zeolite) to be mixed in the catalyst of the present invention may be natural or synthetic, and examples thereof include faujasite X-type zeolite and faujasite Y-type. Zeolites, chabazite-type zeolites, mordenite-type zeolites, so-called ZSM-based zeolites containing organic cations (Z
As SM type zeolite, ZSM-4, ZSM-5, ZSM-8, Z
SM-11, ZSM-12, ZSM-20, ZSM-21, ZSM-23, ZSM-3
4, ZSM-35, ZSM-38, ZSM-43). Atomic ratio of silicon element to aluminum element contained Si / Al is about 1
The above is preferable. The cation species of these zeolites are preferably NH ₄ ⁺ or H ⁺ type, and those in which these are ion-exchanged with alkaline earth metal ions such as Mg ⁺⁺ , Ca ⁺⁺ and Ba ⁺⁺ . If the content of alkali metal ions such as Na ⁺ in zeolite is large, the catalytic activity will be lowered, so it is usually preferable to set the content to about 0.5% by weight or less based on the amount of zeolite.

The amount of the crystalline aluminosilicate to be blended is about 5 to 80% by weight, preferably about 10 to 60% by weight, based on the final catalyst composition. If the amount is too large, the wear resistance is deteriorated, which is not preferable.

Examples of the matrix used in the catalyst of the present invention include silica, alumina, boria, chromia, magnesia, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, chromia-alumina, titania-alumina, titania-silica, titania-. It is an amorphous inorganic oxide such as zirconia or alumina-zirconia, or a mixture thereof, and may contain at least one clay mineral such as montmorillonite, kaolin, halloysite, bentonite, attapulgite, and bauxite. The matrix enhances the strength of the catalyst and also reduces excessive activity.

In the introduction of the active metal used in the present invention, in order to introduce fine particles of a metal oxide into a mixture composed of a crystalline aluminosilicate and a matrix, a mixture composed of a crystalline aluminosilicate and a matrix, for example, a crystalline aluminosilicate and a matrix. The component hydrogel is thoroughly mixed and stirred, and at least one metal oxide fine particle of an active metal selected from the group consisting of iron, nickel, copper and gallium is added to the mixture, and the metal content of the metal oxide is metal oxide based on the catalyst. 0.1 to 10% by weight, preferably about 0.5
Mix to ~ 5% by weight. Then, it is dried into fine particles with a spray dryer, washed with distilled water and dried. If the metal content is too low, the effect does not appear, and if it is too high, the effect does not extend so much. The fine particles of metal oxide are about 0.05 to
10 μm, preferably mixed in a size of about 0.1 to 5 μm. As these metal oxides, commercially available ones can be generally used as they are if the particle diameter is within the above range.

In the introduction of the active metal used in the present invention, in order to carry the active metal in the mixture consisting of the crystalline aluminosilicate and the matrix, the mixture consisting of the crystalline aluminosilicate and the matrix, for example, the hydrogel of the crystalline aluminosilicate and the matrix component. Is thoroughly mixed and stirred, and is dried and atomized by a spray dryer.The catalyst obtained is immersed in an impregnated carrier solution containing a soluble compound of an active metal, which is adjusted to a specified concentration in advance, supported, dried, and calcined. To get The soluble compound of the active metal becomes an oxide upon firing. In this case, chlorides, nitrates, sulfates, etc. of iron, nickel, copper and gallium are used as the compounds of the above-mentioned metals, and the catalyst is immersed in an aqueous solution containing one or more of these metal compounds. .

In order to support the metal component in this way, in addition to the above, a matrix is dispersed in an impregnated carrier solution adjusted to a prescribed concentration in advance to obtain a metal component-supporting matrix, and then a crystalline aluminosilicate is mixed to produce. In the same manner, it is also possible to obtain the metal component-supporting crystalline aluminosilicate in advance and then mix the matrix to produce the same. The amount of metal supported is about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, based on the catalyst, as a metal oxide. If the amount of the active metal is too small, the effect does not appear, and if the amount of the active metal is too large, the effect does not extend so much.

One embodiment of the present invention is a catalyst for catalytic cracking comprising a catalyst comprising a mixture of a crystalline aluminosilicate and a matrix, and a physical mixture of an oxide of an active metal, and a catalyst impregnated with an active metal. It is a catalyst composition, and as the crystalline aluminosilicate of these catalyst compositions, known ones such as Y zeolite or stabilized Y zeolite can be used as described above.

Y zeolite has basically the same crystal structure as natural faujasite, and is expressed as an oxide and has the composition formula: (Wherein R is Na, K or another alkali metal ion or alkaline earth metal ion, and m is its valence).

Stabilized Y-zeolite is obtained by subjecting Y-zeolite to high temperature steam treatment for several times, and shows remarkable resistance to deterioration of crystallinity. R2 / mO content is about 4% by weight.
Below, preferably about 1% by weight or less and the unit cell size is about 2
It means about 4.5Å and the Si / Al atomic ratio is about 3 to 7 or more, and means Y zeolite. Also in this case, the content of the active metal in the mixed catalyst composition is 0.1 to 10% by weight as an oxide, preferably 0.5 to 5% by weight.

Furthermore, one aspect of the present invention is a catalytic cracking method for hydrocarbon oils, which catalytically cracks hydrocarbon oils boiling above the gasoline range using the catalyst composition.

The catalytic cracking can be performed by a known catalytic cracking method.

The hydrocarbon mixed oil boiling above the gasoline range in the present invention means a gas oil fraction or atmospheric distillation residual oil and vacuum distillation residual oil obtained by atmospheric distillation or vacuum distillation of crude oil,
Of course, it also includes coker light oil, solvent deasphalted oil, solvent deasphalted asphalt, tar sand oil, shale oil, and coal liquefied oil.

Catalytic cracking on a commercial scale usually consists of a vertically installed cracking reactor and a regenerator, which continuously circulates the catalyst in the two vessels. The hot regenerated catalyst exiting the regenerator is mixed with the oil to be cracked and directed upward in the cracking reactor. As a result, a carbonaceous material, generally called "coke", is deposited on the catalyst, so that the deactivated catalyst is separated from the decomposition products and transferred to a regenerator after stripping. Decomposition products include dry gas, LPG, gasoline fractions and light cycle oils (L
CO), heavy cycle oil (HCO) and one or more heavy fractions such as slurry oils. Of course, it is also possible to further promote the cracking reaction by recycling these heavy fractions to the reactor. The spent catalyst coke transferred to the regenerator is regenerated by being burned with air and recirculated to the reactor.

As operating conditions, the pressure is normal pressure to about 5 kg / cm ² , preferably normal pressure to about 3 kg / cm ² , and the temperature is about 400 ° C to 600 ° C, preferably about 450 ° C to 550 ° C. The catalyst / raw material weight ratio is about 2-20, preferably about 5-15.

(Effects of the Invention) By using a catalyst using a crystalline aluminosilicate, for example, Y zeolite and / or stabilized Y zeolite, in which a specific active metal is introduced by a specific method, in the catalytic cracking reaction, the active metal is introduced. The aromatic content in the gasoline is increased as compared with the case where it is not introduced or the case where it is introduced into the zeolite by ion exchange, and a gasoline with a high octane number can be produced without increasing the olefin content. That is, the present invention is very useful in that a high octane gasoline can be obtained by increasing the aromatic content without increasing the olefin content by introducing a specific active metal into the catalytic cracking catalyst by a specific method. It provides a wide range of knowledge.

(Example) Below, the content of this invention is demonstrated concretely by an Example and a comparative example. The water contents of silica sol, kaolin and zeolite used in Examples and Comparative Examples are about 70%, about 13.9% and about 22.6%, respectively, and the weights are shown in the water-containing state. Also,
The particle diameter of the metal oxide was determined by an electron microscope (10.000 times) photograph.

Example 1 46.3 g of water and 46.7 g of silica sol were stirred and mixed, and after adjusting to a predetermined pH, 30.1 g of kaolin, 2.1 g of copper oxide fine particles (0.5 to 2 μ particles, most of which are 0.5 to 0.8 μ) H type Y
Further, 36.2 g of zeolite and 74 g of water were added and mixed with stirring.
The obtained mixture was dried with a spray drier, atomized, and washed 5 times with 2000 ml of distilled water. Then 105 ℃, 24
After drying for an hour, a catalyst was obtained. In this case, the active metal was 3.0% by weight as an oxide, based on the catalyst.

Example 2 50 ml of an aqueous solution of copper nitrate having a concentration of 5% by weight as an impregnating carrier liquid
40g of kaolin dispersed in it,
After stirring for a minute, it was evaporated to dryness with a rotary evaporator and then calcined in an electric furnace at 550 ° C. for 3 hours to obtain copper-supported kaolin.

Next, 46.3 g of water and 46.7 g of silica sol were mixed with stirring to obtain a predetermined amount.
After adjusting the pH, 32.5 g of the above copper-supported kaolin, 36.2 g of H-type Y zeolite and 74 g of water were further added and mixed with stirring. The obtained mixture was dried and atomized with a spray dryer, and 2000
It was washed 5 times with ml of distilled water. Then, it was dried at 105 ° C. for 24 hours to obtain a catalyst. In this case, the active metal was 1.0% by weight as an oxide, based on the catalyst.

Example 3 Fine particles of copper oxide (0.5 to 5 μm, most of which are
0.5-0.8 μm) was used, and a catalyst was prepared in the same manner as in Example 1 except that iron oxide fine particles were used. In this case, the active metal was 3.0% by weight as an oxide, based on the catalyst.

Example 4 As an impregnating and supporting liquid, 50 ml of a nickel nitrate aqueous solution having a concentration of 5% by weight was prepared in advance, 40 g of kaolin was dispersed therein, and the mixture was stirred at room temperature for 30 minutes, evaporated to dryness by a rotary evaporator, and then heated in an electric furnace. At 550 ° C. for 3 hours, nickel-supported kaolin was obtained.

Next, 46.3 g of water and 46.7 g of silica sol were mixed with stirring to obtain a predetermined amount.
After adjusting to pH, the above-mentioned nickel-supported kaolin 32.5 g, H type Y
Further, 36.2 g of zeolite and 74 g of water were added and mixed with stirring.
The resulting mixture is dried and atomized with a spray dryer,
It was washed 5 times with 2000 ml of distilled water. Then, it was dried at 105 ° C. for 24 hours to obtain a catalyst. In this case, the active metal was 1.0% by weight as an oxide, based on the catalyst.

Example 5 A catalyst was prepared in the same manner as in Example 1 except that 31.7 g of kaolin and 0.7 g of gallium oxide fine particles (0.5-5 μm particles, most of which were 0.5-0.8 μm) were added. In this case, the active metal was 1.0% by weight as an oxide, based on the catalyst.

Example 6 As an impregnating and supporting liquid, an aqueous solution of copper nitrate having a concentration of 2.4% by weight in advance of 50 m
l was prepared and 40 g of H-type Y zeolite was dispersed therein,
After stirring at room temperature for 30 minutes, the mixture was evaporated to dryness with a rotary evaporator and then calcined in an electric furnace at 550 ° C. for 3 hours to obtain a copper-supported H type Y zeolite.

Next, 46.3 g of water and 46.7 g of silica sol were mixed with stirring to obtain a predetermined amount.
After adjusting the pH, 32.5 g of kaolin, 36.2 g of the above H-type Y zeolite supporting copper and 74 g of water were further added and mixed with stirring. The obtained mixture was dried and atomized with a spray dryer, and 2000
It was washed 5 times with ml of distilled water. Then, it was dried at 105 ° C. for 24 hours to obtain a catalyst. In this case, the active metal was 0.5% by weight as an oxide, based on the catalyst.

Example 7 46.3 g of water and 46.7 g of silica sol were mixed with stirring and adjusted to a predetermined pH, and then 32.5 g of kaolin, 36.2 g of H type Y zeolite and water of 74
g was further added and mixed with stirring. The obtained mixture was dried and atomized with a spray dryer, and washed with 2000 ml of distilled water 5 times. Then, it was dried at 105 ° C. for 24 hours to obtain catalyst fine particles.

Next, as an impregnated carrier liquid, an aqueous solution of copper nitrate having a concentration of 6.6% by weight is used.
ml, in which 77 g of the above catalyst fine particles are dispersed,
After stirring at room temperature for 30 minutes, it was evaporated to dryness by a rotary evaporator and then calcined in an electric furnace at 550 ° C. for 3 hours to obtain a catalyst. In this case, the active metal is an oxide of 4 on a catalyst basis.
% By weight.

Comparative Example 1 46.3 g of water and 46.7 g of silica sol were stirred and mixed, and after adjusting to a predetermined pH, kaolin 32.5 g, H-type Y zeolite 36.2 g and water
74 g was further added and mixed with stirring. The obtained mixture was dried and atomized with a spray dryer, and washed with 2000 ml of distilled water 5 times. Then, it was dried at 105 ° C. for 24 hours to obtain a catalyst.

Comparative Example 2 80% of H type Y zeolite was mixed with 5 times amount of 1N aqueous copper nitrate solution.
Ion exchange at ℃ for 8 hours, then filter and wash, then 10
After drying at 0 ° C. for 12 hours and baking at 550 ° C. for 3 hours, a copper ion exchange type zeolite was obtained.

Next, a catalyst was prepared in the same manner as in Comparative Example 1 except that the above copper ion exchange type zeolite was used instead of the H type Y zeolite. In this case, the active metal was 1.4% by weight, based on the catalyst, as oxide.

Comparative Example 3 A catalyst was prepared in the same manner as in Comparative Example 2 except that an iron nitrate aqueous solution was used instead of the copper nitrate aqueous solution. In this case, the active metal was 1.5% by weight as an oxide, based on the catalyst.

Microactivity Test The catalytic cracking characteristics of each catalyst composition of Examples 1 to 7 and Comparative Examples 1 to 3 were tested under the same feedstock oil and the same measurement conditions using a fixed bed microactivity tester similar to the ASTM standard. Prior to the test, each test catalyst was simulated equilibrated with steam. The test conditions were as follows.

Reaction temperature: 500 ° C Catalyst / feed oil: 3.0 (weight ratio) WHSV: 16h ^-1 Test time: 75 seconds These micro-activity tests were carried out with a fixed bed test apparatus, and the preferred conditions are in the text. It does not necessarily correspond to the industrial fluid catalytic cracking apparatus described in 1. Desulfurized vacuum gas oil was used as the feedstock. The test results are shown in Table 1. As is clear from the results of Table 1, Examples 1, 2 and
6 and 7 are Comparative Examples 1 and 2, Examples 4 and 5 are Comparative Example 1 and Example 3 is Comparative Examples 1 and 3 in which the aromatic content is increased and the octane number is improved.

Claims (4)

[Claims] 1. A mixture of a crystalline aluminosilicate and a matrix is further physically mixed with fine particles of a metal oxide of at least one active metal selected from the group consisting of iron, nickel, copper and gallium. The active metal content of the metal oxide is 0.1-10% by weight based on the catalyst.
A catalyst composition for the catalytic cracking of hydrocarbon oils. 2. A crystalline aluminosilicate, a matrix and an active metal component, the active metal component being impregnated and supported with at least one active metal compound selected from the group consisting of iron, nickel, copper and gallium. , Which was calcined to form a metal oxide, and the supported amount was 0 based on the catalyst.
A catalyst composition for catalytic cracking of hydrocarbon oil, characterized in that it is 1 to 10% by weight. 3. A method for catalytically cracking a hydrocarbon oil, which comprises catalytically cracking a mixed oil of hydrocarbons boiling above the gasoline range using the catalyst composition according to claim 1. 4. A method for catalytically cracking a hydrocarbon oil, which comprises catalytically cracking a hydrocarbon mixed oil boiling above the gasoline range using the catalyst composition according to claim 2.