JPH1085603A - Catalyst composition for catalytic cracking of hydrocarbon oil and method for catalytically cracking hydrocarbon oil with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the production of coke as well as to enhance a heavy residual oil cracking ability of a catalyst compsn. suitable for use in the fluidized catalytic cracking of heavy residual oil (PFCC) by using a solid material composed of an alkali metallic-rare earth metallic multiple sulfate and silica as a catalyst in the catalyst compsn. SOLUTION: This catalyst compsn. suitable for use in the catalytic cracking of hydrocarbon oil such as vacuum distilled light oil, especially heavy residual oil contains a solid material composed of an alkali metallic-rare earth metallic multiple sulfate and silica as a catalyst. The multiple sulfate is composed of alkali metallic and rare earth metallic sulfates. The weight ratio of the silica to the multiple sulfate is 0.05-2.50. The solid material has 0.5-15m<2> /g specific surface area and contains 5-40μmol/g acids including 55-85% strong acid. The density of all the acids is preferably 5-15μmol/m<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst composition for catalytic cracking of hydrocarbon oils containing a novel solid substance as a catalyst component, and particularly to a catalyst composition suitable for use in fluid catalytic cracking (RFCC) of heavy residual oil. The present invention relates to a catalyst composition and a method for catalytically cracking a hydrocarbon oil in the presence of the catalyst composition.

[0002]

2. Description of the Related Art Feedstock oils used for catalytic cracking of hydrocarbon oils, particularly nickel, vanadium, etc., used for catalytic cracking (RFCC) of heavy residue oils such as atmospheric distillation residue oil and vacuum distillation residue oil And a large amount of a high molecular compound mainly composed of polycyclic aromatics called resin, asphaltene, and conradson carbon. In the catalytic cracking of such heavy residual oil, heavy metals are deposited on the catalyst, and the heavy metals have dehydrogenation activity, thereby increasing the production of undesirable hydrogen and coke, while producing useful gasoline. The amount is reduced. Further, in particular, vanadium destroys zeolite, which is a decomposition active component of a conventional catalyst, and thus has a problem in that the decomposition activity is reduced. In addition, it is difficult to effectively decompose asphaltene, Conradson carbon or a high-boiling fraction hydrocarbon oil close thereto to low-boiling hydrocarbon oils such as gasoline, and most of the coke becomes coke, and this coke serves as a catalyst active point. Poisoning causes catalyst deactivation. In the fluidized catalytic cracking unit, the catalyst after the reaction is removed and the remaining oil is removed by stripping and then regenerated in a regeneration tower.However, in the regeneration of the catalyst after catalytic cracking of heavy residual oil with a large amount of coke deposited In this case, the regeneration temperature is increased by the exothermic reaction due to the combustion of coke as compared with the conventional case of catalytic cracking of vacuum gas oil, and the zeolite is easily broken, which also causes deactivation.

[0003] From the above, as a catalyst for catalytic cracking of heavy residual oil, (1) to effectively decompose heavy residual oil into light hydrocarbon oils, that is, to have a residual oil decomposability;
(2) an increase in the amount of hydrogen generated by heavy metals and suppression of zeolite destruction, that is, having metal resistance;
(3) It is required that the activity is small due to regeneration at high temperature and that it is thermally stable, that is, it has hydrothermal stability. Generally, the catalyst for catalytic cracking of hydrocarbon oils is composed of a porous inorganic oxide matrix and an active component consisting of zeolite. However, when the feedstock is a heavy oil residue, the high boiling point hydrocarbon contained therein has a large molecular size and cannot easily penetrate into the pores of the zeolite having a pore diameter of about 3 to 9A. It is believed that it is not decomposed in the pores and is therefore mainly decomposed by the outer surface of the zeolite particles and / or the matrix having relatively large pores.

[0004] For this reason, various matrices having a solid acid, such as silica-alumina, alumina, silica-magnesia, silica-, for efficiently decomposing heavy residual oils.
A porous inorganic oxide such as zirconia is used. However, all of these have a decomposition activity with solid acid sites as active points (in solid acid substances), but the decomposition activity for heavy oil is too high because there are many acid points with strong solid acid strength (strong acid sites). However, there is a problem that a large amount of coke is generated. Further, these matrices generally have a problem that the deposited heavy metal is highly dispersed due to a large specific surface area and is not sufficiently passivated, so that the amount of hydrogen and coke generated by the dehydrogenation activity of the heavy metal is high.

Next, in order to remove the adverse effects of heavy metals,
It is desired that the matrix captures and inactivates heavy metals. Alkaline earth metals, rare earth metal oxides and the like are known as components having such ability. However, they are effective in inactivating heavy metals, but have no resolution alone.Especially alkaline earth metals reduce the hydrothermal resistance of zeolites or reduce the octane number of gasoline produced, probably because of their basicity. There is a problem of causing. SiO ₂ -La ₂ O that was attached bind silica to the lanthanum oxide core in JP-A-6-198174
_It is described that the catalyst containing the solid acid substance consisting of ₃ has a small amount of coke precipitation and a high yield of gasoline and middle distillate in the catalytic cracking of heavy oil such as desulfurized vacuum gas oil (DSVGO). I have.

[0006]

The object of the present invention can be used for the catalytic cracking of hydrocarbon oils such as vacuum gas oils. However, particularly in the catalytic cracking of heavy residual oil, the amount of gas and coke generated To provide a catalytic cracking catalyst composition that can effectively decompose heavy residual oil with low metal content, and has high metal resistance and an extended catalyst life, and a catalytic cracking method using the catalyst composition. is there.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the inactivating ability of various compounds and compound composites for heavy metals and the decomposition characteristics of heavy residual oil. It has been found that a catalyst containing a solid substance consisting of an alkali metal rare earth metal complex sulfate and silica as a catalyst component is a very excellent catalyst having a high ability to decompose heavy residual oil and a small amount of gas and coke.

[0008] The first aspect of the present invention relates to a catalytic composition for catalytic cracking of hydrocarbon oil, which comprises a solid substance comprising an alkali metal rare earth metal composite sulfate and silica as a catalyst component. The alkali metal rare earth metal composite sulfate may be a composite sulfate composed of an alkali sulfate and a rare earth sulfate. For example, M.RE. (SO ₄ ) ₂
Alternatively, there is a crystalline compound represented by the chemical formula of 2M ₂ SO ₄ .RE ₂ (SO ₄ ) ₃ , and in particular, the former M.RE. (SO
₄ ) The crystalline compound represented by ₂ is preferred. Here, M is an alkali metal ion, but is generally a Na ion. The rare earth component is not particularly limited, but a mixed rare earth containing cerium or lanthanum as a main component is generally used. However, cerium, lanthanum or another rare earth metal may be used alone, and two or more of these rare earth metals may be used. It may be a combination. The solid substance constituting the catalytic cracking catalyst composition of the present invention preferably has the following properties (a) to (f). (A) the weight ratio of the silica / alkali metal rare earth metal composite sulfate of the solid substance composed of the alkali metal rare earth metal composite sulfate and silica is 0.05 to 2.50, and (b) the specific surface area is 0.5 to 15 m ^2. / G, (c) total acid amount is 5 to 40 μmo
1 / g, (d) the ratio of the strong acid amount to the total acid amount is 55 to 85.
%, (E) the density of the total acid content is 5 to 15 μmol / m
² (f) The X-ray diffraction pattern has the following specific values of (1) and / or (2): lattice spacing d (A) 2θ (degrees) Relative intensity (strong = s, medium = m, weak = W) (1) 2.86 31.3 s 3.29 27.1 m 3.52 25.3 s 4.72 18.8 m 4.92 18.0 m 6.11 14.5 m (2 ) 2.86 31.3 s 3.05 29.3 s 3.29 27.1 m 3.52 25.3 s 4.72 18.8 m 6.11 14.5 m or less; (F) The requirements will be described.

[Requirement (a)] When the weight ratio of silica / alkali metal rare earth metal composite sulfate is less than 0.05, the amount of silica is so small that the form of alkali metal rare earth metal composite sulfate cannot be maintained by calcination. Sometimes
Further, most of the rare earth metal in the solid substance becomes a rare earth metal oxide, and the rare earth metal oxide captures and passivates metals such as Ni and V, so that the amount of gas and coke generated is reduced. Since the density of all acid sites and the ratio of strong acid sites of the catalyst containing the solid substance are increased, the ability to selectively decompose residual oil is sometimes reduced, which is not preferable. Conversely, when the weight ratio is higher than 2.50, the total acid amount of the catalyst is reduced, and the ability to decompose residual oil may be reduced, which is not preferable. A particularly preferred range is 0.50-2.
00.

[Requirement (b)] When the specific surface area of the solid substance is less than 0.5 m ² / g, the amount of the acid point of the composite compound is too small, and the ability to decompose residual oil may decrease. It is not preferable. On the other hand, if the specific surface area of the solid substance is higher than 15 m ² / g, the amount of solid acid points of the solid substance is too large and the ability to decompose residual oil is too high to increase the amount of gas and coke generated. It is not preferable because it may cause A particularly preferred range is from 1.0 to 10.0 m ² / g.
It is.

[Requirement (c)] If the total acid content of the solid substance is less than 5 μmol / g, the amount of solid acid sites is too small, and the ability to decompose residual oil is undesirably reduced. Conversely, the total acid content of the solid substance is 40 μm
When the amount is higher than ol / g, the amount of solid acid sites is too large and the ability to decompose residual oil is too high, so that the production of gas and coke is undesirably increased. A particularly preferred range is 1
0 to 20 μmol / g.

[Requirement (d)] When the amount of strong acid in the total acid amount of the solid substance is less than 55%, the decomposition rate of the total residue oil decreases because the hardly decomposable residue oil cannot be decomposed. It is not preferable because it may cause If it is higher than 85%, the ability to decompose residual oil is too high, and the production of gas and coke may increase, which is not preferable. A particularly preferred range is 65-75%.

[Regarding requirement (e)] If the density of all solid acid sites of the composite compound is less than 5 μmol / m ^{2, the} ability to decompose residual oil may be undesirably reduced. If it is higher than 15 μmol / m ² , the amount of gas and coke generated by the hydrogen transfer reaction may increase, which is not preferable. A particularly preferred range is 8 to 10 μmol.
/ M ² .

[(F) Requirements] Here, (1) is N
aLa (SO ₄ ) ₂ X-ray diffraction pattern, (2) is an NaCe (SO ₄ ) ₂ X-ray diffraction pattern, and at least (1) or (2) in a solid substance The case where it is not detected is a case where the alkali metal rare earth metal composite sulfate constituting the solid substance of the present invention is extremely small or not generated at all, and is not preferable because the effect of the present invention may not be exhibited.

Even if the solid substance constituting the catalytic cracking catalyst composition of the present invention satisfies only the above requirement (a), the desired effects of the present invention can be sufficiently exhibited. , In addition to the requirements of (a),
More preferably, at least one of the requirements (f) is satisfied, and more preferably, all of the requirements (a) to (f) are satisfied.

The solid substance can be produced, for example, as follows. First, rare earth chloride is dissolved to have a concentration of 5 to 40 wt%, preferably 1 as rare earth oxide (RE ₂ O ₃ ).
A 5-25 wt% rare earth chloride aqueous solution is prepared. Then
The pH of the rare earth chloride aqueous solution is adjusted with a mineral acid, preferably hydrochloric acid, to adjust the pH to 1.0 to 5.5, preferably 2.5 to 3.5. Separately, sulfuric acid is added to a water glass solution having a concentration of 3 to 15% by weight, preferably 11 to 13% by weight as silica, and pH is adjusted.
A silica sol containing a sodium salt adjusted to a range of 1.0 to 2.0, preferably 1.4 to 1.8 is prepared.
Next, the silica sol is aged at a temperature of 20 to 60 ° C., preferably 25 to 45 ° C., for 1 to 10 minutes, preferably 3 to 7 minutes, and then mixed with the previously prepared rare earth chloride aqueous solution. At 60 ° C, preferably 25-45 ° C, 1
The mixture is stirred for 20 to 20 minutes, preferably for 5 to 15 minutes to prepare an aqueous mixture composed of silica and the alkali metal rare earth metal composite sulfate. Next, it is granulated by spray drying at a temperature of 120 to 200 ° C, preferably 140 to 160 ° C. The resulting dried particles have a temperature of 400-700 ° C., preferably 500
Calcination is performed at ６００600 ° C. in air for 1 to 7 hours, preferably 3 to 5 hours. Next, the calcined particles are adjusted to a pH of 5 to 9, preferably 7.0 to 8.5 with ammonia water, at a temperature of 40 to 80 ° C, and preferably at a concentration of 10 w at 50 to 70 ° C.
After washing with a t% aqueous solution of ammonium sulfate and further washing with warm water, solid particles were separated by filtration and the temperature was 80 to 150.
C., preferably at 100 to 140.degree. C., and if necessary, pulverization to prepare a solid substance comprising silica and an alkali metal rare earth metal composite sulfate.

The catalyst composition of the present invention may be used alone as the above-mentioned solid substance, but it is preferable that the catalyst is a catalyst obtained by incorporating the solid substance into a usual catalytic composition for catalytic cracking of hydrocarbon oil. In the latter case, it is composed of the solid substance of the present invention, a commonly used porous inorganic oxide, and if necessary, a commonly used zeolite. In that case, the amount of the solid substance of the present invention in the catalyst composition is from 1 to 20.
A range of wt% is desirable. A more desirable range is 3-1.
0 wt%. Here, the wt% of the solid substance is based on the total weight of the catalyst composition. For example, it is configured to contain the solid substance, a generally used porous inorganic oxide, and, if necessary, zeolite. In this case, if the content of the solid substance is less than 1 wt% with respect to the total weight of the catalyst composition, the effect of the present invention is not sufficiently exhibited, and if the content exceeds 20 wt%, the effect of the present invention is further enhanced. Since the abrasion resistance and bulk density of the catalyst may decrease without increasing, the amount of the solid substance is preferably 1 to 20% by weight, more preferably 3 to 10% by weight.
% Range. That is, the amount of this solid substance is 1-2.
At 0 wt%, the catalyst composition has an appropriate density of all solid acid sites, the ratio of strong acid sites is also suitable, the residual oil can be selectively decomposed, and an amount sufficient to passivate the metal. As a result, the formation of gas and coke is also suppressed, so that favorable results can be obtained in the catalytic cracking of heavy oil.

As the zeolite used in combination with the solid substance, various types of conventionally known crystalline aluminosilicates and crystalline metallosilicates can be used. In particular, synthetic Y-type zeolites and ultra-stabilized Y-type zeolites are preferable, and those obtained by proton and / or rare-earth metal cation exchange are particularly preferable. It is preferable that the skeleton aluminum is removed by hydrothermal treatment and / or acid treatment to adjust the unit cell size and / or mesopore. The amount of the zeolite is preferably in the range of 10 to 40 wt%. 10wt
% Is not preferable because the cracking rate is low, the cracking of the residual oil does not proceed sufficiently, and the gasoline yield may decrease.
On the other hand, if it is higher than 40 wt%, the decomposition rate becomes too high, so that gas and coke may increase, and the abrasion resistance and bulk density of the catalyst may undesirably decrease. In particular, the range of 20 to 35 wt% is preferable.

As the porous inorganic oxide used in combination with the above-mentioned solid substance, those usually used as catalytic cracking catalysts such as silica, alumina, zirconia, titania, silica-alumina, silica-magnesia and the like can be used. It is also possible to use a metal catcher, such as particles, together. As the clay mineral, kaolin, halloysite, montmorillonite and the like can be used.

The average particle size of the catalyst composition of the present invention may be the same as that generally used for fluid catalytic cracking,
The range is preferably from 70 to 70 μm, and a particularly preferable range is 5 to 70 μm.
5 to 65 μm. The specific surface area is 150 to 350
m ² / g is preferred, and a more preferred range is 200
３００300 m ² / g.

The catalyst composition of the present invention as described above can be produced by a general method for producing a catalyst for fluid catalytic cracking. For example, the solid substance is prepared by mixing a crystalline aluminosilicate zeolite with a porous inorganic oxide. Preparing an aqueous slurry mixed with a precursor of the product and / or a clay mineral;
It can be manufactured by spray drying and further washing and drying. Further, in the catalytic cracking method of hydrocarbon oil using the catalyst, it can be carried out by employing the conditions of ordinary catalytic cracking method of hydrocarbon oil, and the conditions are, for example, described below. Conditions are preferably employed.

(Raw oil) As the raw oil hydrocarbon oil used in the present invention, vacuum distilled light oil can be used, and in particular, heavy residual oil such as atmospheric distillation residual oil, vacuum distilled residual oil, or the like, or Heavy residual oils and the like obtained by hydrogenating them are also preferable in that the amount of generated gas and coke is small and the heavy residual oils can be effectively decomposed. The amount of metal in the feedstock is (Ni +
V) as 0.1 ppm to 50 ppm, the amount of residual carbon is 0.1 wt% to 15 wt%, and the specific gravity is 0.85 to 0.95.
Those in the range described above can be suitably used.

(Reaction temperature) The preferred range of the reaction temperature for catalytic cracking of the hydrocarbon oil is from 450 to 600 ° C, more preferably from 470 to 550 ° C. Reaction temperature 45
If the temperature is lower than 0 ° C., the reaction temperature is too low, and the heavy residual oil may not be sufficiently decomposed, which is not preferable. Reaction temperature 60
If the temperature is higher than 0 ° C., over-decomposition occurs to increase the production of gas and coke, and the yield of gasoline is undesirably reduced.

(Reaction pressure) (catalyst / oil weight ratio) (contact time) In general, the reaction pressure when catalytically cracking a hydrocarbon oil is preferably in the range of about 1 to 3 kg / m ² , catalyst/
The preferred range of the oil weight ratio is 2.5-7.0, more preferably 3.0-6.0, and the preferred range of contact time is 1
0-60 hrs ^{~ 1} , more preferably 15-50 hrs ^{~ 1}
It is.

By the catalytic cracking method of the present invention, inferior raw material hydrocarbon oil such as vacuum distillation residue is converted into hydrocarbon oil containing a large amount of gasoline, light cycle oil (LCO) fraction and the like.

[0026]

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

Example 1 [SiO ₂ / M · RE · (SO ₄ )]
_{2 with} a weight ratio of 1.7 and a catalyst using the same] To 953 g of a crude rare earth chloride aqueous solution having a concentration of 21 wt% as RE ₂ O ₃ , 18 wt% of hydrochloric acid was added to obtain a pH 2.0 solution.
Was obtained. The type and ratio of the rare earth elements in the used coarse rare earth chloride were La ₂ O ₃ 22w as oxides.
t%, CeO ₂ 50 wt%, Pr ₆ O ₁₁ 5 wt%, Nd
₂ O ₃ 20wt%, it was Sm ₂ O ₃ 3wt%. Separately, silica sol 64 adjusted to pH 1.6 by adding 25 wt% sulfuric acid to a No. 3 water glass aqueous solution (Na ₂ O.3SiO ₂ ) having a concentration of 12.5 wt% as SiO _2.
00 g were obtained. Next, the silica sol was aged at 36 ° C. for 4 minutes, and the crude rare earth aqueous solution prepared previously was added at a rate of 150 ml / min while stirring, and further 36 times.
Aged at 3 ° C for 3 minutes. The aqueous mixture is then brought to a temperature of 15
Spray dried at 0 ° C, baked in 550 ° C air, and then adjusted to pH 7.8 with aqueous ammonia at 60 ° C
4800g of 10% by weight ammonium sulfate aqueous solution
After washing with water and drying at a temperature of 140 ° C., and then pulverized, a solid substance A-1 was prepared. The properties of the solid substance A-1 are shown in Table 1, and the SiO ₂ / M · RE · (SO ₄ ) ₂
Was 1.7 and the specific surface area was 1.1 m ² / g. The total acid amount was 9.5 μmol / g, the density of all acid sites was 8.6 μmol / m ² , and the ratio of strong acid sites in the total acid amount was 6
8%. Next, the concentration as SiO ₂ is 12.5 w
No. 3 water glass aqueous solution (pH 12.0)
By adding sulfuric acid of wt%, a silica sol having a pH of 1.6 was obtained. Next, kaolin 476 was added to 1600 g of this silica sol.
g, 54 g of activated alumina having a specific surface area of 300 m ² / g,
329 g of ultra-stable Y-type zeolite, solid substance (A-1) 7
After dispersing 7 g, it was spray-dried and then washed and dried to obtain a catalytic cracking catalyst A having an average particle diameter of 65 μm. Catalyst A
Contains 30% by weight of zeolite, 40% by weight of kaolin, 20% by weight of silica, 5% by weight of activated alumina and 5% by weight of solid substance (A-1). Table 2 shows the properties of the catalyst.
It was shown to.

Example 2 [SiO_Two/ M ・ RE ・ (SO_Four)
_TwoSolid material having a weight ratio of 0.5 and a catalyst using the same] RE_TwoO_ThreeRare earth chloride aqueous solution with a concentration of 21 wt%
To 3240 g of hydrochloric acid having a concentration of 18 wt% was added to adjust the pH to 2.
0 was obtained. Separately, SiO_TwoAs
No. 3 water glass aqueous solution with a concentration of 12.5 wt% 25 wt%
Silica sol 6 adjusted to pH 1.6 by adding sulfuric acid
400 g were obtained. Then, the silica sol is heated at 36 ° C. for 4 minutes.
After standing aging, the crude rare earth chloride previously prepared with stirring
An aqueous solution was added at a rate of 150 ml / min, and
Aged at 6 ° C for 3 minutes. The aqueous mixture is then brought to temperature
Spray dried at 150 ° C and fired in 550 ° C air
And then adjusted to pH 7.8 with aqueous ammonia at a temperature of 6
Aqueous ammonium sulfate solution 480 at a concentration of 0 ° C. and 10 wt%
After washing with 0 g and washing with water, drying at a temperature of 140 ° C. and grinding
Thus, a solid substance B-1 was prepared. This solid substance B-1
The properties are shown in Table 1._Two/ M ・ RE ・ (SO_Four)
_TwoHas a weight ratio of 0.5 and a specific surface area of 1.9 m.^Two/ G
there were. The total acid content is 11.5 μmol / g,
The degree is 6.1 μmol / m^Two, The proportion of strong acid sites in the total acid
73%. Next, SiO_TwoConcentration as 12.5
Concentration of 2 in aqueous solution of No. 3 water glass (pH 12.0)
5 wt% sulfuric acid is added to form a silica sol having a pH of 1.6.
Obtained. Next, kaolin 476 was added to 1600 g of this silica sol.
g, specific surface area is 300m^Two/ G activated alumina 54 g,
329 g of ultra-stable Y-type zeolite, solid substance (B-1) 7
After dispersing 7g, spray dry, then wash and dry
A catalyst B for catalytic cracking having an average particle diameter of 65 μm was obtained. Catalyst B
Contains 30 wt% zeolite, 40 wt% kaolin,
Power 20 wt%, activated alumina 5 wt% and solid material
(B-1) 5 wt% is contained. Table 2 shows the properties of the catalyst.
It was shown to.

Comparative Example 1 (Preparation of SiO ₂ -RE ₂ O ₃ having a SiO ₂ / RE ₂ O ₃ weight ratio of 1.08 and a catalyst using the same) Crude chloride having a concentration as RE ₂ O ₃ of 21 wt% An aqueous solution of ammonium hydroxide having a concentration of 15 wt% was added to 3240 g of the rare earth aqueous solution to prepare a hydrogel slurry of a rare earth hydroxide having a pH of 7.5. Separately, the concentration as SiO ₂ is 12.
6400 g of silica sol adjusted to pH 1.6 by adding 20 wt% hydrochloric acid of 5 wt% aqueous solution of No. 3 water glass was added. Next, the silica sol was aged at 36 ° C. for 4 minutes, and the hydrogel slurry of rare earth hydroxide prepared above was added at a rate of 150 ml / min with stirring, and further aged at 36 ° C. for 3 minutes to obtain a silica sol. An aqueous mixed slurry of rare earth hydroxide hydrogel was prepared. Next, the aqueous mixed slurry was spray-dried at a temperature of 150 ° C.
Calcination in air at 0 ° C. and then with aqueous ammonia at pH 7.8
After washing with 4800 g of an aqueous solution of ammonium sulfate having a concentration of 10% by weight at a temperature of 60 ° C.
Dried ° C., to prepare a SiO ₂ -RE ₂ O ₃ composite oxide C-1 having the same Si / RE atomic ratio as in Example 2 was ground. The properties of C-1 are shown in Table 1. The specific surface area is 9.8 m ² / g, the total acid amount is 32.5 μmol / g, the density of all acid sites is 3.3 μmol / m ² , The proportion of strong acid sites in the amount was 72%. Also, from the X-ray diffraction pattern,
The composite sulfate [M.RE. (SO ₄ ) ₂ ] according to the present invention was not present, but was mainly composed of oxides La ₂ O ₃ and CeO ₂ . Next, a 25 wt% concentration was added to a No. 3 water glass aqueous solution (pH 12.0) having a concentration of 12.5 wt% as SiO _2.
Was added to obtain a silica sol having a pH of 1.6. Then, 1600 g of kaolin, 54 g of activated alumina having a specific surface area of 300 m ² / g and 1600 g of this silica sol,
After dispersing 329 g of type zeolite and 77 g of the composite oxide (C-1), the mixture was spray-dried, then washed and dried to obtain a catalytic cracking catalyst C having an average particle diameter of 65 μm. Catalyst C was composed of 30% by weight of zeolite, 40% by weight of kaolin, and 20% of silica.
wt%, activated alumina 5 wt% and composite oxide (C-
1) Contains 5 wt%. The properties of the catalyst are shown in Table 4.

Comparative Example 2 (Catalyst not using the solid substance of the present invention) An aqueous solution of water glass having a SiO ₂ content of 12.5 wt% (p
H12.0), sulfuric acid having a concentration of 25 wt%
1.6 silica sol was obtained.
536 g of kaolin to 00 g, specific surface area of 300 m ² / g
Activated alumina 54 g, ultra-stable Y-type zeolite 329 g
Was dispersed, spray-dried, and then washed and dried to obtain a catalytic cracking catalyst D having an average particle diameter of 65 μm. Catalyst D was composed of 30 wt% zeolite, 45 wt% kaolin, silica 2
The catalyst contains 0 wt% and 5 wt% of activated alumina and does not contain the solid substance of the present invention. The properties of the catalyst are shown in Table 4.

Example 3 (Evaluation of catalyst) Measurement of solid acid strength distribution The solid acid strength distributions of the solid substances, composite oxides and catalysts prepared in Examples 1 and 2 and Comparative Example 1 were measured. For the principle and method for measuring the solid acid strength distribution, see the Catalyst Lecture, Separate Volume: Catalyst Experiment Handbook, edited by the Catalysis Society of Japan, published by Kodansha, p.173. B differential adsorption heat measurement), and specifically performed as follows. Each sample was evacuated for 1.5 hours at a temperature of 400 ° C. and 1 × 10 ⁻⁵ Torr for 4 hours, and then ammonia gas was adsorbed pulsed at 27 ° C. The amount of heat generated by each pulse was measured, that is, the amount of differential adsorption of ammonia was measured. The total amount of ammonia adsorbed when the heat of adsorption is 70 kJ / mol or more is defined as the total acid amount, and the heat of adsorption is 8
5 kJ / mol or more was taken as the strong acid point, and the cumulative ammonia adsorption amount of 85 kJ / mol or more was taken as the strong acid point. The density of all acid sites was calculated by dividing the total amount of acid by the specific surface area of each sample. The results are shown in Tables 1, 2 and 4.

X-Ray Diffraction Measurement The X-ray diffraction pattern of the solid substance obtained in Example 1 was measured using RINT 1000 manufactured by Rigaku Corporation, and the results are shown in FIG. Identification was performed with reference to ASTM Card. Note that NaCe (SO ₄ ) ₂ is ASTM NO.
21-1109, NaLa (SO ₄ ) ₂ is ASTM N
O. 35-1173. In addition, No. 28-026
6 is an example of a mixed rare earth oxide. FIG. 1 shows that the solid substance of Example 1 contains a mixture of NaCe (SO ₄ ) ₂ and NaLa (SO ₄ ) ₂ .

Evaluation by reaction of catalyst The catalysts obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were Mic
The reaction was performed under the following evaluation conditions using a ro Activity Test (MAT) apparatus and evaluated. Before the reaction, the following pretreatment (pseudo equilibrium: steaming at a high temperature so as to show a reaction characteristic close to that of the actual apparatus) And inactivate appropriately). Each catalyst contains 2000 ppm of vanadium (V) and 1000 p of nickel (Ni).
The solution was impregnated with a benzene solution of vanadium naphthenate and nickel naphthenate so as to obtain a pm pressure, the solvent was removed, and the mixture was baked. Then, a pretreatment by steam treatment was performed at 750 ° C. for 13 hours in a 100% steam atmosphere. The properties after the steam treatment are shown in Tables 3 and 5.

Evaluation Conditions (1) Feedstock: Hydrodesulfurized atmospheric distillation residue (DSAR)
Hydrodesulfurization vacuum distilled light oil (DSVGO) 6 with 40 wt%
A 0 wt% mixed oil was used. At this time, the amount of metal in the feed oil was 5.2 ppm for Ni, 7.9 ppm for V, 5.2 wt% for residual carbon, and 0.9% for specific gravity (15/4 ° C.).
330, sulfur is 0.28 wt%. (2) Reaction temperature: 510 ° C. (3) Reaction pressure: normal pressure (4) Catalyst / oil weight ratio: 3 to 5 (5) Contact time: 40 hrs ^-1

Evaluation results by catalyst reaction Tables 3 and 5 show the reaction results when the conversion was 64.0 wt%. Conversion rate (wt%) = (ab) / a × 100 Gas yield (wt%) = c / a × 100 The lower the better, the better the gasoline yield (wt%) = d / a × 100 The higher the better LCO yield (wt%) = e / a × 100 Higher is better HCO yield (wt%) = f / a × 100 Lower is better Coke yield (wt%) = g / a × 100 Lower is more preferable a is Weight b of feed oil b is the weight of the fraction having a boiling point of 216 ° C. or higher in the product oil c is the total weight of hydrogen in the product gas, C ₁ and C ₂ gas d is gasoline in the product oil (boiling point range C _{5 to} 216) E) The weight of LCO (boiling point range 216-343 ° C) in the product oil f The weight of HCO (boiling point range 343 ° C or more) in the product oil g The weight of coke deposited on the catalyst

The catalyst A has a low gas and coke generation amount, a high liquid yield of gasoline and light cycle oil (LCO) and is extremely excellent in selectivity, and has a small amount of high-boiling fraction heavy cycle oil (HCO) remaining. It is a catalyst with high oil resolution. Catalyst B also has a low gas and coke generation amount, a high gasoline and LCO liquid yield, a very high selectivity, a low remaining high boiling fraction HCO and a high residual oil resolving power. Catalyst C is as excellent as catalysts A and B in that the amount of gas and coke generated is small and the gasoline yield is high, but in the point that the amount of remaining high boiling fraction HCO is large and the amount of LCO generated is small. As in the case of the general catalyst D, no improvement in the resolution of the residual oil was observed.

[0037]

[Table 1] ○: Satisfies structural requirements * SiO ₂ / RE ₂ O ₃ weight ratio ×: Does not satisfy structural requirements

[0038]

[Table 2]

[0039]

[Table 3] ◎ indicates that the effect is larger than that of the conventional catalyst (Comparative Example 2).

[0040]

[Table 4]

[0041]

[Table 5]

Hereinafter, embodiments of the present invention will be described. 1. A catalytic composition for catalytic cracking of hydrocarbon oils, comprising a solid component comprising an alkali metal rare earth metal composite sulfate and silica as a catalyst component. 2. The catalyst composition for catalytic cracking of hydrocarbon oil according to 1, wherein the solid substance satisfies at least one requirement selected from the group consisting of (a) to (f).

3. 3. The catalytic cracking catalyst composition of the above 1-2, wherein the solid substance satisfies the requirement (a). (3) The catalytic cracking catalyst composition according to (3), wherein the solid substance further satisfies at least one requirement selected from the group consisting of (b) to (f). 5. (1) The catalytic composition for catalytic cracking according to (1), wherein the solid substance satisfies all of the requirements (a) to (f).

6. A catalytic cracking catalyst composition further comprising at least one solid substance selected from the group consisting of the above-mentioned 1 to 5 solid substances and a porous inorganic oxide. 7. The catalyst composition for catalytic cracking according to the above item 6, further comprising a zeolite.

8. Catalytic cracking of hydrocarbon oils in the presence of at least one catalytic cracking catalyst composition selected from the group consisting of the catalytic cracking catalyst compositions of 1 to 7 above. Law. 9. The method for catalytic cracking of hydrocarbon oil according to the above item 8, wherein the hydrocarbon oil is a heavy residual oil.

[0046]

The solid substance of the present invention is composed of alkali metal rare earth metal composite sulfate and silica and has a special solid acid property and specific surface area. The catalyst of the present invention has excellent residual oil decomposition properties, metal resistance and It has hydrothermal resistance, and has good results in high gasoline and LCO liquid yields and low gas, coke and HCO generation in catalytic cracking of hydrocarbon oils, especially atmospheric distillation residue oil, vacuum distillation residue oil, etc. Can be

[Brief description of the drawings]

FIG. 1 shows solid substance A-1 and NaCe as a standard substance.
(SO ₄ ) ₂ (ASTM No. 21-1109), Na
La (SO ₄ ) ₂ (ASTM No. 35-1173) and mixed rare earth oxide Ce 0.75 Nd 0.25
It is a figure which shows the line diffraction pattern of O1.875 (ASTM No. 28-0266).

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10G 11/06 C10G 11/06 11/18 11/18

Claims (4)

[Claims] 1. A catalytic composition for catalytic cracking of hydrocarbon oils, which comprises a solid substance comprising an alkali metal rare earth metal complex sulfate and silica as a catalyst component. 2. The catalytic composition for catalytic cracking according to claim 1, wherein the weight ratio of silica / alkali metal rare earth metal composite sulfate is 0.05 to 2.50. 3. The catalytic composition for catalytic cracking of hydrocarbon oil according to claim 1, wherein the solid substance satisfies all of the following requirements (a) to (f). (A) the weight ratio of the silica / alkali metal rare earth metal composite sulfate of the solid substance composed of the alkali metal rare earth metal composite sulfate and silica is 0.05 to 2.50, and (b) the specific surface area is 0.5 to 15 m ^2. / G, (c) total acid amount is 5 to 40 μmo
1 / g, (d) the ratio of the strong acid amount to the total acid amount is 55 to 85.
%, (E) the density of the total acid content is 5 to 15 μmol / m ² (f) the X-ray diffraction pattern has the following specific values of (1) and / or (2), and the lattice spacing d (A) 2θ (degrees) Relative intensity (strong = s, medium = m, weak = w) (1) 2.86 31.3 s 3.29 27.1 m 3.52 25.3 s 4.72 18.8 m 4.92 18.0 m 6.11 14.5 m (2) 2.86 31.3 s 3.05 29.3 s 3.29 27.1 m 3.52 25.3 s 4.72 18. 8 m 6.11 14.5 m 4. A method for catalytically cracking a hydrocarbon oil, comprising catalytically cracking a hydrocarbon oil in the presence of the catalytic cracking catalyst according to claim 1, 2, or 3.