JP2759099B2 - Catalyst composition for fluid catalytic cracking of hydrocarbon oils and fluid catalytic cracking using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbon oil and a fluid catalytic cracking method of hydrocarbon oil using the same (hereinafter referred to as fluid catalytic cracking for simplicity). The cracking is simply abbreviated as catalytic cracking.) Specifically, a catalyst composition comprising a specific crystalline metal silicate and a catalyst for contacting the catalyst composition with a hydrocarbon to efficiently produce gasoline having a high octane number. To a possible catalytic cracking method.

(Problems to be Solved with Conventional Techniques) In petroleum refining, it is generally the most important issue to produce catalytic cracked gasoline having a high octane number with a high yield. A gas oil fraction obtained by pressure distillation or vacuum distillation, an atmospheric distillation residue, and a vacuum distillation residue are subjected to a catalyst comprising a stabilized zeolite such as X or Y zeolite or USY zeolite (ultrastable Y zeolite) and an inorganic matrix. And a method of catalytic cracking.

Many techniques have already been proposed for catalysts for the above purpose, and for example, stabilized Y zeolite is disclosed in U.S. Pat. Nos. 3,293,192 and 3,402,996. or,
U.S. Pat.Nos. 3,894,933, 3,894,934, 4,368,114
No. 4,416,765 discloses a case where ZSM-5 is used as a catalyst component. However, the stabilized Y zeolite has the disadvantage that the amount of acid is reduced due to the reduction of aluminum in the framework of the zeolite, and the decomposition activity of the catalyst is reduced. Therefore, a decrease in the activity is avoided by increasing the zeolite content in the catalyst.
When the type 5 zeolite is used, the octane value is improved, but the decomposition of the gasoline fraction into LPG is promoted, and the gasoline yield decreases. Conversely, there is a disadvantage that the octane number is sacrificed when trying to maintain the gasoline yield. That is, at present, stabilized Y zeolite and ZSM-
When the type 5 zeolite is used, it is not always sufficient to simultaneously improve the octane number and the gasoline yield, and a new catalyst for further improving the octane number and the gasoline yield is expected.

(Means and Actions for Solving the Problems) The inventors of the present invention have conducted intensive studies to further develop the prior art, and as a result, have found that a catalyst containing a crystalline metal silicate having a specific structure or this crystalline metal silicate It has been found that the catalytic cracking of hydrocarbon oils using a catalyst having an active species of Y zeolite and / or stabilized Y zeolite can increase the octane number while maintaining the gasoline yield. Reached.

Accordingly, an object of the present invention is to provide a catalyst composition capable of producing gasoline having a high octane number without causing excessive cracking of hydrocarbon oil, and an excellent catalytic cracking method of hydrocarbon oil using these catalysts. is there.

That is, the present invention provides the following composition formula (A) (a) in which the crystalline metal silicate is dehydrated and represented by the number of moles of the oxide: (Wherein R is one or more alkali metals or alkaline earth metals, M is scandium, lanthanum,
Titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, gallium, germanium, at least one metal selected from the group consisting of platinum, a ≧ 0.05, b ≧ 0, c ≧ 10, valence of m: R, valence of n: M), and (b) the composition after ion exchange of the crystalline metal silicate represented by the composition of the above (a) is: The content of the alkali metal or alkaline earth metal oxide is less than 1% by weight of the oxide, and (c) the crystalline metal silicate has an X-ray diffraction pattern substantially as shown in FIG. A catalyst composition for fluid catalytic cracking of hydrocarbon oils, which comprises a crystalline metal silicate as an essential component, or the above catalyst further comprising (B) Y zeolite and / or stabilized Y zeolite as a component. A fluidized catalytic cracking process for a hydrocarbon oil, comprising fluid catalytically cracking a hydrocarbon mixture boiling above the gasoline range using the second catalyst, and a fluidized catalytic cracking process for the hydrocarbon oil. Zeolites and / or A fluid catalytic cracking process of a hydrocarbon oil which comprises fluid catalytic cracking hydrocarbon mixtures boiling in the gasoline range or with a mixture of catalyst containing stabilized Y zeolite.

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

The crystalline metal silicate used in the present invention is scandium, lanthanum, titanium, zirconium, vanadium,
It is a crystalline metal silicate containing at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel, gallium, germanium, and platinum (which may also contain aluminum) as a metal constituting the crystal.

The production of these crystalline metal silicates is specifically performed by the following method. That is, usually at least one silica source, at least one metal source corresponding to M in the above composition formula, at least one alkali metal or alkaline earth metal compound, and at least one organic cation compound and, if necessary, Prepared from an aqueous mixture containing at least one alumina source in a certain proportion. As the silica source, one or two of silicon compounds such as alkali metal silicates such as sodium silicate and potassium silicate, silica hydrogel, silica gel, silica alumina hydrogel, silica alumina sol, and silicic acid are used.
Mixtures of more than one species can be used.

As the alumina source, aluminum sulfate, nitrate,
Chloride and the like, sodium aluminate, colloidal alumina, alumina and the like, preferably, aluminum sulfate and sodium aluminate are used. As a metal source of scandium, lanthanum, titanium, and the above-mentioned metal M, sulfates, nitrates, hydroxides, oxides and chlorides of these metals are used. As the alkali metal or alkaline earth metal compound, hydroxides such as sodium, potassium and calcium are typically used. In addition, sodium silicate, silica alumina hydrogel, sodium aluminate, etc. can act as a plurality of metal sources by themselves.
Organic ionic compounds include organic amines and organic ammonium salts. Examples of the organic amine include monoalkylamines such as n-propylamine, n-butylamine, n-hexylamine, neopetylamine, tert-butylamine, and sec-butylamine; dialkylamines such as dibutylamine; tributylamine; tripropylamine; A trialkylamine or piperidine,
Cyclic amines such as alkylpiperidine and hexamethylenetetramine; Typical examples of the organic ammonium salt include alkyl ammonium compounds such as triethyl-n-propylammonium bromide, tetrapropylammonium bromide, and triethyl-n-butylammonium bromide. The above aqueous mixture can be obtained by keeping it under hydrothermal synthesis conditions until the formation of the silicate, and then separating the silicate crystals from the mother liquor.

As for the hydrothermal synthesis conditions, the reaction temperature is room temperature to 250 ° C, preferably about 80 to 200 ° C. The reaction pressure is not particularly limited, and it is preferable to carry out the reaction under so-called self-pressure, that is, under the equilibrium pressure of the reactants at that temperature without pressure adjustment. The appropriate reaction time depends on the reaction temperature and the composition of the raw materials, but usually requires several hours to about 100 hours. If the reaction temperature is too low, a long reaction time is required.

The crystalline metal silicate used in the present invention is preferably water glass as a silica source, a sulfate of these metals as an M metal source, an alkali metal, or a hydroxide of sodium as an alkaline earth metal compound, Aluminum sources include aluminum sulfate or sodium aluminate,
As the organic cation compound, a tetraalkylammonium bromide in a molar ratio of Si (M + Al) = about 10 or more, and OH ⁻ / SiO ₂ =
About _{0.1~1.0, H 2 O / SiO 2} = about 30~100, AN ⁺ / SiO ₂ = about 0.05
~0.2, NaCl / H ₂ O = about 0.01 to 0.1 (wherein, AN ⁺ is the total tetraalkylammonium cation, OH ^- represents a hydroxide ion in the mixture.) Is synthesized from a raw material obtained by compounding a percentage of You. The chemical composition of the product obtained under the above conditions has the following formula: (R is one or two or more alkali metals or alkaline earth metals, a ≧ 0.05, b ≧ 0 c ≧ 10, m: valence of R, n: valence of M, M: Sc, La, Ti, Z
r, V, Cr, Mn, Fe, Co, Ni, Ga, Ge or PT. ) Is a crystalline metal silicate represented by In the production of the catalyst of the present invention, the organic cation introduced during the production is further calcined before being used as a catalyst, followed by ion exchange to produce the catalyst. Ion exchange can be performed by a conventionally known method, and can be used as H type or various metal cation types. Examples of such metals include rare earth metals and many other metals such as Fe, Ni, and Co.

In the present invention, the composition after ion-exchange of the crystalline metal silicate represented by the above composition formula has an alkali metal or alkaline earth metal oxide content of less than 1 wt%. In the production of crystalline metal silicate, as shown in the above composition, an alkali metal or alkaline earth metal oxide which is present in an amount of more than 1 wt% is obtained.
Thereafter, ion exchange is carried out by a conventionally known method such as ammonium nitrate to produce an alkali metal or alkaline earth metal oxide having a content of less than 1 wt%, preferably 0.01 wt% or more and less than 0.5 wt%. If a large amount of alkali metal or alkaline earth metal is present in the crystalline metal silicate, the decomposition activity of the catalyst is reduced, and nickel, vanadium, etc., which are heavy metals contained in the base oil, especially heavy oil base oil, etc. In the case where is adhered, there is a problem that the activity is easily deteriorated.

The crystalline metal silicate as the active species of the catalyst in the present invention has substantially the X-ray diffraction pattern shown in FIG.
The X-ray diffraction diagram typically has the values shown in Table 1 below. That is, the lattice spacings (d) at which the highest intensities were actually measured are 11.1 ± 0.2 °, 10.1 ± 0.2 °, and 3.85 ± 0.1 °.

Here, I ₀ means the intensity of the strongest line. Irradiation is copper K
-Alpha rays.

The catalyst composition of the present invention comprises the above crystalline metal silicate
A catalytic composition for the catalytic cracking of hydrocarbon oils comprising 0.1 to 40% by weight, preferably about 1 to 10% by weight, and about 5 to 60% by weight, preferably about 10 to 40% by weight of Y zeolite or stabilized Y zeolite. . Here, the remainder of the catalyst composition is an inorganic matrix. The total content of the crystalline metal silicate and the Y zeolite or the stabilized Y zeolite in the catalyst composition is about 50 wt.
%, There is a possibility that a problem may occur in abrasion.

Known Y zeolites or stabilized Y zeolites used in the present invention can be used. Y zeolite has basically the same crystal structure as natural faujasite, and is represented as an oxide by the composition formula: Wherein R is Na, K or another alkali metal or alkaline earth metal ion, and m is its valence.

Stabilized Y zeolites are described, for example, in US Pat. No. 3,293,192.
No. 3,402,996. It shows remarkable resistance to deterioration of crystallinity by performing high temperature and steam treatment several times.

The content is about 4 wt% or less, preferably about 1 wt% or less, and the unit cell size is about 24.5 °. Also, it means a Y zeolite characterized in that the atomic ratio of Si / Al is about 3 to 7 or more. These Y zeolites or stabilized Y
Zeolites, when rich in alkali or alkaline earth metal oxides, undergo ion exchange to remove these undesirable alkali or alkaline earth metal oxides. When the proportion of the Y zeolite in the catalyst composition of the present invention is small, the decomposition activity decreases.

Examples of the inorganic matrix include silica, alumina, boronia, chromia, magnesia, zirconia, titania,
Silica-alumina, silica-magnesia, silica-zirconia, chromia-alumina, titania-alumina, titania-silica, titania-zirconia, alumina-zirconia, etc., or a mixture thereof; montmorillonite, kaolin, halloysite, bentonite, attapulgite, It can also contain at least one clay mineral such as bauxite.

The method for producing the catalyst composition of the present invention can be carried out by a usual method, and typically, a suitable inorganic matrix such as silica-
The above-mentioned crystalline metal silicate, or this metal silicate and Y zeolite and / or stabilized Y are added to alumina hydrogel, silica sol or aqueous slurry of alumina sol.
The zeolite is added, mixed well, stirred and then spray-dried to obtain catalyst fine particles.

Another of the catalytic cracking methods of the present invention uses a mixture of the prior art catalyst containing Y zeolite and the above-mentioned catalyst containing a crystalline metal silicate. Also in this case, the crystalline metal silicate in the mixed catalyst composition is about
0.1 to 40% by weight, preferably about 1 to 10% by weight, about 5 to 60% by weight of Y zeolite and / or stabilized Y zeolite;
Preferably, it can be used by being added so as to have a ratio of about 10 to 40% by weight.

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

In the present invention, the hydrocarbon mixture boiling above the gasoline range means a gas oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil, an atmospheric distillation residual oil and a vacuum distillation residual oil, and of course, coker gas oil and solvent removal. It also includes bitumen, solvent deasphalted asphalt, tar sand oil, shale oil oil, and coal liquefied oil.

Catalytic cracking on a commercial scale usually consists of a vertically installed cracking reactor and a regenerator, with continuous circulation of the catalyst through the two vessels. The hot regenerated catalyst coming out of the regenerator is mixed with the cracked oil and directed upward in the cracking reactor. As a result, carbonaceous material generally called "coke" precipitates on the catalyst, so that the deactivated catalyst is separated from decomposition products, and is transferred to a regenerator after stripping. Decomposition products include dry gas, LPG, gasoline fractions and, for example, light cycle oils (L
CO), heavy cycle oil (HCO) and one or more heavy fractions such as slurry oils. Of course, the decomposition reaction can be further advanced by recirculating these heavy fractions to the reactor. The spent catalyst coke transferred to the regenerator is regenerated by burning it with air and circulated again to the reactor.

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

(Effect of the Invention) The use of a catalyst having a crystalline metal silicate having a specific structure and a Y zeolite and / or a stabilized Y zeolite as an active species in a catalytic cracking reaction reduces the gasoline yield. And it is possible to produce gasoline having a higher octane number.

(Examples) Hereinafter, the content of the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1 Ferric sulfate (purity 72.4%) 6.27 g, tetra-n-bromide
Solution (A) consisting of 17.16 g of propylammonium, 18.60 g of sulfuric acid (95%), 35.85 g of sodium chloride and 180 ml of water, solution (B) consisting of 207 g of water glass (JIS No. 3) and 135 ml of water, tetra-n bromide -Propyl ammonium 6.48 g, sodium chloride 121.77 g, sodium hydroxide 7.
A solution (C) consisting of 17 g, 5.40 g of sulfuric acid (95%) and 624 ml of water was prepared, respectively.

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After firing for 5 hours, 55.4 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed the X-ray diffraction pattern shown in FIG. Also, solid-state NMR
As a result, iron was incorporated in the crystal lattice. This crystalline iron silicate has the following composition in a molar ratio.

1.1Na ₂ O.100SiO ₂ .1.0Fe ₂ O ₃ The crystalline iron silicate obtained by the above method was ion-exchanged twice with a 5-fold amount of 1N ammonium nitrate, and washed three times with 200 ml of distilled water. Then dried at 120 ° C for 12 hours, 5
Calcined at 40 ° C for 5 hours and the content of sodium oxide is 0.03wt
% H-type.

Next, the obtained H-type crystalline iron silicate and H-type Y zeolite were each contained in the final catalyst at a content of 10% by weight.
Was added to a silica-alumina gel (alumina content: 30% by weight) slurry prepared by a usual method. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Example 2 Lanthanum sulfate nonahydrate (purity 99.0%) 7.35 g, tetra-n-propylammonium bromide 17.16 g, sulfuric acid (95%)
Solution (A) consisting of 18.60 g, 35.85 g of sodium chloride and 180 ml of water, 207 g of water glass (JIS No. 3) and 135 ml of water
(B), 6.48 g of tetra-n-propylammonium bromide, 121.77 g of sodium chloride, 7.17 g of sodium hydroxide, 5.40 g of sulfuric acid (95%) and 624 ml of water, respectively, were prepared.

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After firing for 5 hours, 54.0 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed an extremely similar X-ray diffraction pattern substantially the same as that of FIG. Also, as confirmed by solid-state NMR, lanthanum was incorporated in the crystal lattice. The crystalline lanthanum silicate has the following composition in a molar ratio.

1.3Na ₂ O ・ 100SiO ₂・ 1.0La ₂ O ₃ The crystalline lanthanum silicate obtained by the above method was
Ion exchange twice with twice the volume of 1N ammonium nitrate
Washed three times with 0 ml of distilled water. It is then dried at 120 ° C for 12 hours, calcined at 540 ° C for 5 hours, and subjected to sodium oxide content.
The H type was 0.21 wt%.

Next, the obtained H-type crystalline lanthanum silicate and H-type Y zeolite were each contained in the final catalyst at a content of 10%.
It was added to a silica-alumina gel (alumina content 30% by weight) slurry prepared by a usual method so as to be a% by weight. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Example 3 7.10 g of zirconium sulfate tetrahydrate (purity 99.0%), 17.16 g of tetra-n-propylammonium bromide, sulfuric acid (95%)
%) Solution (A) consisting of 18.60 g, 35.85 g of sodium chloride and 180 ml of water, 207 g of water glass (JIS No. 3 product) and 13 parts of water
A solution (B) consisting of 5 ml, a solution (C) consisting of 6.48 g of tetra-n-propylammonium bromide, 121.77 g of sodium chloride, 7.17 g of sodium hydroxide, 5.40 g of sulfuric acid (95%) and 624 ml of water were respectively prepared. .

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After firing for 5 hours, 55.8 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed an extremely similar X-ray diffraction pattern substantially the same as that of FIG. Further, as confirmed by solid-state NMR, zirconium was incorporated in the crystal lattice. This crystalline zirconium silicate has the following composition in a molar ratio.

0.6Na ₂ O.100SiO ₂ .1.0ZrO ₂ The crystalline zirconium silicate obtained by the above method was ion-exchanged twice with a 5-fold amount of 1N ammonium nitrate, and washed three times with 200 ml of distilled water. Next, it was dried at 120 ° C. for 12 hours and calcined at 540 ° C. for 5 hours to obtain an H-form having a sodium oxide content of 0.08 wt%.

Next, a silica-alumina gel (having an alumina content of 30% by weight) was prepared so that the obtained H-type crystalline zirconium silicate and H-type Y zeolite each had a content in the final catalyst of 10% by weight. %) Was added to the slurry. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Example 4 8.30 g of potassium sulfate n-hydrate (purity 51.5%), 17.16 g of tetra-n-propylammonium bromide, sulfuric acid (95%)
Solution (A) consisting of 18.60 g, 35.85 g of sodium chloride and 180 ml of water, 207 g of water glass (JIS No. 3) and 135 ml of water
(B), 6.48 g of tetra-n-propylammonium bromide, 121.77 g of sodium chloride, 7.17 g of sodium hydroxide, 5.40 g of sulfuric acid (95%) and 624 ml of water, respectively, were prepared.

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After firing for 5 hours, 57.2 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed an extremely similar X-ray diffraction pattern substantially the same as that of FIG. In addition, gallium was incorporated into the crystal lattice as confirmed by solid-state NMR. This crystalline gallium silicate has the following composition in a molar ratio.

1.1Na ₂ O ・ 100SiO ₂・ 1.0Ga ₂ O ₃ The crystalline gallium silicate obtained by the above method was
Ion exchange twice with twice the volume of 1N ammonium nitrate
Washed three times with 0 ml of distilled water. It is then dried at 120 ° C for 12 hours, calcined at 540 ° C for 5 hours, and subjected to sodium oxide content.
It was H type of 0.01 wt%.

Next, the obtained H-type crystalline gallium silicate and the H-type Y zeolite each had a content of 10% in the final catalyst.
It was added to a silica-alumina gel (alumina content 30% by weight) slurry prepared in a usual manner to give a weight%. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Example 5 Chromium sulfate (purity 88.6%) 4.42 g, tetra-n-bromide
Solution (A) consisting of 17.16 g of propylammonium, 18.60 g of sulfuric acid (95%), 35.85 g of sodium chloride and 180 ml of water, solution (B) consisting of 207 g of water glass (JIS No. 3) and 135 ml of water, tetra-n bromide -Propyl ammonium 6.48 g, sodium chloride 121.77 g, sodium hydroxide 7.
A solution (C) composed of 17 g, 5.40 g of sulfuric acid (95%) and 624 ml of water was prepared.

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After calcination for 5 hours, 56.6 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed an extremely similar X-ray diffraction pattern substantially the same as that of FIG. Chromium was incorporated into the crystal lattice as confirmed by solid-state NMR. This crystalline chromium silicate has the following composition in a molar ratio.

1.1Na ₂ O ・ 100SiO ₂・ 1.0Cr ₂ O ₃ The crystalline chromium silicate obtained by the above method was ion-exchanged twice with 5 times amount of 1N ammonium nitrate, and 200m
Washed three times with 1 liter of distilled water. It is then dried at 120 ° C for 12 hours, calcined at 540 ° C for 5 hours, and subjected to sodium oxide content.
The H type was 0.05 wt%.

Next, a silica-alumina gel (having an alumina content of 30% by weight) was prepared by a conventional method so that the obtained H-type crystalline chromium silicate and the H-type Y zeolite each contained 10% by weight in the final catalyst. %) Was added to the slurry.
Then, after homogenizing and mixing well with a homogenizer,
The particles were dried and atomized with a spray dryer.

Example 6 3.90 g of aluminum sulfate (purity 87.2%), lanthanum sulfate nonahydrate (purity 99.0%), 7.35 g, tetra-n-bromide
Solution (A) consisting of 17.16 g of propylammonium, 18.60 g of sulfuric acid (95%), 35.85 g of sodium chloride and 180 ml of water, solution (B) consisting of 207 g of water glass (JIS No. 3) and 135 ml of water, tetra-n bromide -Propyl ammonium 6.48 g, sodium chloride 121.77 g, sodium hydroxide 7.
A solution (C) composed of 17 g, 5.40 g of sulfuric acid (95%) and 624 ml of water was prepared.

Next, the solution (A) and the solution (B) were gradually dropped into the solution (C) at the same time while stirring at room temperature. After the completion of the dropping, the mixture was further stirred to obtain a mixture. This mixture is
Into an autoclave and stirred at 300 rpm.
The temperature was raised from room temperature to 160 ° C. for 90 minutes, and from 160 ° C. to 210 ° C. for 250 minutes, and reacted under self-pressure. Thereafter, the reaction mixture was cooled and washed eight times with 200 ml of distilled water. Then, the solid content was separated by filtration, dried at 120 ° C for 12 hours, and then dried at 540 ° C for 5 hours.
After firing for 5 hours, 56.3 g of crystalline silicate was obtained. When this crystalline silicate was confirmed by X-ray diffraction, it showed an extremely similar X-ray diffraction pattern substantially the same as that of FIG. This crystalline lanthanum aluminosilicate has the following composition in a molar ratio.

0.8Na ₂ O.50SiO _2. [0.5La ₂ O ₃ .0.5Al ₂ O ₃ ] The crystalline lanthanum aluminosilicate obtained by the above method is ion-exchanged twice with 5 times the amount of 1N ammonium nitrate, and 200 ml of Washed three times with distilled water. Then at 120 ° C 12
After drying for 5 hours, the mixture was calcined at 540 ° C. for 5 hours to obtain an H-form having a sodium oxide content of 0.01 wt%.

Next, the obtained H-type crystalline lanthanum aluminosilicate and the H-type Y zeolite were each prepared by a usual method so that the content in the final catalyst was 10% by weight. Wt%) was added to the slurry. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Example 7 10% sulfuric acid was added to colloidal silica (SI-350 manufactured by Catalyst Chemicals Co., Ltd.) to adjust the pH of the solution to 3.2, and the crystalline H-type iron silicate obtained by the method described in Example 1 above was added thereto. Kaolin was added to give a final catalyst content of 20% and 50% by weight, respectively. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Next, H-form Y zeolite was added to a silica-alumina gel (alumina content 30% by weight) slurry prepared by a conventional method so that the content in the final catalyst was 20% by weight.
Then, after homogenizing and mixing well with a homogenizer,
The particles were dried and atomized with a spray dryer.

The above catalyst containing crystalline iron silicate is added to this catalyst.
The mixture was stirred and mixed to be 10% by weight.

Example 8 10% sulfuric acid was added to colloidal silica (SI-350 manufactured by Catalyst Chemicals Co., Ltd.) to adjust the pH of the solution to 3.2, and the crystalline H-type iron silicate obtained by the method described in Example 1 above was added thereto. Kaolin was added to give a final catalyst content of 20% and 50% by weight, respectively. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Next, H-form Y zeolite was added to a silica-alumina gel (alumina content 30% by weight) slurry prepared by a conventional method so that the content in the final catalyst was 20% by weight.
Then, after homogenizing and mixing well with a homogenizer,
The particles were dried and atomized with a spray dryer.

The above catalyst containing crystalline iron silicate is added to this catalyst.
The mixture was stirred and mixed to be 50% by weight.

Comparative Example 1 Example 1 except that H-type crystalline aluminosilicate (ZSM-5) was used in place of H-type crystalline iron silicate.
A catalyst was prepared in the same manner as described above.

Comparative Example 2 H-type zeolite was added to a silica-alumina gel (alumina content 30% by weight) slurry prepared by a conventional method so that the content in the final catalyst was 20% by weight. Then, the mixture was thoroughly mixed with a homogenizer, stirred and homogenized, and then dried and atomized with a spray drier.

Micro-activity test 1 ASTM standard fixed-bed micro-activity test (Micro-activ
The catalytic cracking characteristics of each of the catalyst compositions of Examples 1 to 6 and Comparative Example 1 were tested using the same feedstock and the same measurement conditions using an apparatus for measuring the catalytic cracking. Prior to the test, each test catalyst was treated at 800 ° C. for 6 hours in a 100% steam atmosphere. Desulfurized vacuum gas oil was used as a feed oil, and the test conditions were as follows.
The test results are shown in Table 2.

Reaction temperature: 500 ° C Catalyst / feedstock: 3.0 (weight ratio) WHSV: 16h ^-1 Test time: 75 seconds Note that these microactivity tests were performed using a fixed-bed test device, and preferred conditions are described in the text. Does not necessarily correspond to the industrial fluid catalytic cracking apparatus described in (1).

As is clear from Table 2, the catalyst compositions of Examples 1 to 6 have a higher gasoline yield and are superior in gasoline selectivity as compared with those of Comparative Example 1. The octane number shows a high value almost equal to that of Comparative Example 1.

Micro-Activity Test 2 The catalytic cracking characteristics of each of the catalyst compositions of Examples 7 to 8 and Comparative Example 2 were tested using the same apparatus, raw material oil and measurement conditions as in Activity Test 1 above. Prior to the test, each test catalyst was heated at 800 ° C for 6 hours.
The treatment was performed in a steam atmosphere for 100% of the time. Table 3 shows the test results.

As is clear from Table 3, the catalyst compositions of Examples 7 and 8 show a higher octane number than that of Comparative Example 2. The gasoline yield is equivalent to that of Comparative Example 2.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of the crystalline iron silicate obtained in Example 1 of the present invention with a copper K-α ray. In the figure, 1, 2 and 3 are peaks of the lattice spacing (d) showing the strongest diffraction, located at 11.2 ± 0.2 °, 10.1 ± 0.2 ° and 3.85 ± 0.1 °, respectively.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Mitsugu Tsujii 1246-78 Kanazaki, Showa-cho, Kita-Katsushika-gun, Saitama 63-156889 (JP, A) JP-A-60-144389 (JP, A) JP-A-60-19040 (JP, A) JP-B-62-29370 (JP, B2)

Claims (4)

(57) [Claims] (1) The following composition formula (A) wherein (a) the crystalline metal silicate is dehydrated and represented by the number of moles of an oxide: (Wherein R is one or more alkali metals or alkaline earth metals, M is scandium, lanthanum,
Titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, gallium, germanium, at least one metal selected from the group consisting of platinum, a ≧ 0.05, b ≧ 0, c ≧ 10, valence of m: R, valence of n: M), and (b) the composition after ion exchange of the crystalline metal silicate represented by the composition of the above (a) is: The content of the alkali metal or alkaline earth metal oxide is less than 1% by weight of the oxide, and (c) the crystalline metal silicate has an X-ray diffraction pattern substantially as shown in FIG. A catalyst composition for fluid catalytic cracking of hydrocarbon oils, comprising a crystalline metal silicate as an essential component. 2. The catalyst composition according to claim 1, further comprising (B) Y zeolite and / or stabilized Y zeolite as a constituent. 3. A fluid catalytic cracking method for a hydrocarbon oil, comprising subjecting a hydrocarbon mixture boiling above the gasoline range to fluid catalytic cracking using the catalyst according to claim 2. 4. Hydrocarbons comprising the fluid catalytic cracking of a hydrocarbon mixture boiling above the gasoline range using a mixture of the catalyst according to claim 1 and a catalyst comprising a Y zeolite and / or a stabilized Y zeolite. Fluid catalytic cracking of oil.