JPH07323229A - Catalytic composition for fluidized catalytic cracking of hydrocarbon - Google Patents

Abstract

PURPOSE:To provide a catalytic composition for fluidized catalytic cracking of hydrocarbons excellent in capturing ability for sulfur oxide and metal resistance and small in the lowering of octane number (RON) of a resultant gasoline. CONSTITUTION:The catalytic composition for fluidized catalytic cracking of hydrocarbons is formed by dispersing a crystalline aluminosilicate zeolite and a particulate manganese dioxide compound in an inorganic oxide matrix.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons, and more particularly to a fluid catalytic cracking of hydrocarbons, especially heavy hydrocarbons containing sulfur compounds and metal contaminants such as vanadium. The present invention relates to a catalyst composition for hydrocarbon fluid catalytic cracking, which is excellent in metal resistance and sulfur oxide scavenging ability without lowering the octane number of produced gasoline, has high activity and is excellent in gasoline selectivity.

[0002]

2. Description of the Related Art Conventionally, in catalytic cracking of heavy hydrocarbons containing metal contaminants such as vanadium, vanadium deposited on the catalyst destroys the crystal structure of crystalline aluminosilicate zeolite which is an active ingredient. , Is known to cause a significant decrease in catalyst activity, and also contains various compounds as metal scavengers to deactivate metal contaminants such as vanadium deposited on the catalyst, and Various catalysts having improved properties have been proposed (for example, JP-A 61-149241 and JP-A 62-38242). However, although the alkaline earth metal compound has an excellent effect of inactivating metal pollutants, in the catalyst composition in which it is dispersed in the inorganic oxide matrix as a metal scavenger, the alkaline earth metal is catalytically decomposed. It migrates during use in the reaction, lowering the thermal stability of the crystalline aluminosilicate zeolite and destroying the crystal structure, which lowers the activity of the catalyst. Alternatively, there is a problem that the octane number (RON) of the gasoline product obtained by the catalytic cracking reaction is lowered because it is incorporated into the crystalline aluminosilicate zeolite by ion exchange. Further, depending on the alkaline earth metal species of the metal scavenger, the alkaline earth metal is eluted when mixed with the inorganic oxide matrix precursor and ion-exchanged with the crystalline aluminosilicate zeolite. Alternatively, there is a problem that the properties of the obtained catalyst composition are adversely affected by reacting with the inorganic oxide matrix precursor. In order to solve this problem, the present applicant has made alumina exist in a block form in the catalyst (Japanese Patent Laid-Open No. 61-227843),
By treating the catalyst with an aqueous solution containing phosphate ions at the time of producing the catalyst (Japanese Patent Laid-Open No. 4-200744), the disadvantages of the alkaline earth metal can be obtained without impairing the advantages of the alkaline earth metal as a metal scavenger. A method for producing an improved catalyst composition for catalytic cracking of hydrocarbons is proposed. On the other hand, in the catalytic cracking of hydrocarbons containing sulfur compounds, a method of reducing the SOx component in the combustion gas discharged from the regeneration tower of the fluid catalytic cracking (FCC) device (Japanese Patent Publication No. 56-56).
-9196) and a catalyst composition (JP-A-56-
No. 111047) is also proposed. Sulfur compounds in heavy hydrocarbons adhere to the catalyst along with coke, and become SOx by the following reaction in the regeneration tower of the FCC unit. Then, the SOx generated in the regeneration tower reacts with the metal oxide and is trapped in the catalyst, and S + O ₂ → SO ₂ + SO ₃ 2SO ₂ + O ₂ → 2SO ₃ metal oxide (MO) + SO ₃ → MSO in the coke. _{In the 4} reaction tower, 2MSO ₄ + 8H ₂ → MS + MO + H ₂ S + 7H ₂ O In the stripper, it is converted into MS + H ₂ O → MO + H ₂ S hydrogen sulfide by the following reaction, separated and recovered, and SOx in the combustion gas is collected. The ingredients are decreasing. Conventionally, it is known that a manganese component has a sulfur oxide trapping ability (for example, Japanese Patent Publication No. 56-9196), but a solution containing a manganese component is contacted with a catalyst (including impregnation or ion exchange). In the catalyst composition supported in the catalyst by the method described above, manganese moves during use of the catalytic decomposition reaction of the catalyst composition or during preparation of the catalyst, and is incorporated into the crystalline aluminosilicate zeolite by ion exchange, so that the catalytic decomposition reaction is performed. There was a problem that the octane number (RON) of the obtained gasoline product was lowered.

[0003]

OBJECT OF THE INVENTION The object of the present invention is to capture sulfur oxides,
Another object of the present invention is to provide a catalyst composition for fluidized catalytic cracking of hydrocarbons, which is excellent in metal resistance and has a small decrease in octane number (RON) of produced gasoline.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a catalytic composition for hydrocarbon fluid catalytic cracking, characterized in that a crystalline aluminosilicate zeolite and a particulate manganese compound are dispersed in an inorganic oxide matrix.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The catalyst composition for fluidized catalytic cracking of hydrocarbons according to the present invention comprises 5 to 50 crystalline aluminosilicate zeolite.
% By weight, preferably 5-40% by weight, 0.1-20% by weight of the particulate manganese compound, preferably 0.5-10.
% By weight, 20-95% by weight of inorganic oxide matrix,
It is desirable that the content is preferably in the range of 30 to 95% by weight. If the content of the particulate manganese compound is small, the desired effect cannot be obtained, and if it is large, the wear resistance (At
t. Res. ) Tends to decrease.

The particulate manganese compound in the present invention may be any compound particle containing a manganese component, and for example, in addition to oxides such as MnO, Mn ₂ O ₃ , MnO ₂ and Mn ₂ O ₄ , Examples thereof include compound particles such as MnSO ₄ , MnP and MnSiO ₃ . In particular, dimanganese trioxide (Mn ₂ O ₃ ) particles that can be detected by X-ray are suitable because they show an excellent effect in terms of catalyst performance. The dimanganese trioxide particles are produced as naturally occurring brown ore, and
It can be obtained by firing electrolytic manganese dioxide, which is widely used as a raw material for dry batteries, in air, or by firing manganese earth or manganese nodules.

The particulate manganese compound of the present invention has an average particle size of 60 μm or less, preferably 0.1 to 30 μm.
It is desirable to be in the range of m. When the particle size exceeds 60 μm, it is not desirable as a catalyst for a fluidized bed because of the relationship with the average particle size of the finally obtained catalyst composition.

The crystalline aluminosilicate zeolite used in the present invention includes X-type zeolite, Y-type zeolite,
It is possible to use mordenite, ZSM type zeolite, natural zeolite and the like, which are used in a form ion-exchanged with a cation selected from hydrogen, ammonium and polyvalent metals as in the case of a usual catalytic cracking catalyst composition. To be done. Y-type zeolite, particularly ultra-stable Y-type zeolite, is preferable because it has excellent hydrothermal stability.

Further, the inorganic oxide matrix of the present invention usually acts as a binder such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. It is a conventional matrix component used in the catalytic cracking catalysts. Inorganic oxides other than manganese, such as kaolin, halloysite, and montmorillonite, can also be contained in such a matrix component.

The catalyst composition for fluidized catalytic cracking of hydrocarbons of the present invention may contain a conventional metal scavenger in combination.

The catalyst composition of the present invention can be produced by mixing the crystalline aluminosilicate zeolite and the particulate manganese compound with the inorganic oxide matrix precursor and spray drying.

The catalyst composition of the present invention is obtained by adding a crystalline aluminosilicate zeolite and a particulate manganese compound to a precursor of the above-mentioned inorganic oxide matrix, such as silica hydrosol, silica-alumina hydrogel, etc., to uniformly disperse it. It can be produced by spray-drying the obtained mixture slurry in a conventional manner. And
The spray-dried particles are washed as needed, and after washing, dried or dried and calcined again.

The catalyst composition of the present invention is particularly suitable for use in the catalytic cracking of heavy hydrocarbons containing metal contaminants such as sulfur compounds and vanadium, but the catalytic cracking of hydrocarbons containing no metallic contaminants. The catalytic cracking using the catalyst composition may be carried out under ordinary catalytic cracking conditions.

The catalyst composition of the present invention can be used for catalytic cracking of a wide range of petroleum fractions from kerosene / light oil to high-boiling deasphalted oil.

The embodiments of the present invention are listed below. (1) A catalyst composition for fluid catalytic cracking of hydrocarbons, characterized in that a crystalline aluminosilicate zeolite and a particulate manganese compound are dispersed in an inorganic oxide matrix. (2) The catalyst composition for fluid catalytic cracking of hydrocarbon according to the above (1), wherein the particulate manganese compound is dimanganese trioxide that can be detected by X-ray. (3) The above-mentioned item (1) or (2) in which the compounding ratio of each of the components is: crystalline aluminosilicate zeolite 5 to 50% by weight, particulate manganese compound 0.1 to 20% by weight, inorganic oxide matrix 20 to 95% by weight. ). The catalyst composition for fluidized catalytic cracking of hydrocarbons as described above. (4) The catalyst composition for hydrocarbon fluid catalytic cracking according to item (3), wherein the particulate manganese compound is 0.5 to 10% by weight in the blending ratio of each component. (5) The hydrocarbon fluid catalytic cracking catalyst composition according to the above (3) or (4), wherein the crystalline aluminosilicate zeolite is contained in an amount of 5 to 40% by weight in the blending ratio of each of the above components. (6) The above-mentioned items (3) and (4), wherein the inorganic oxide matrix is 30 to 95% by weight in the blending ratio of each component.
Alternatively, the catalyst composition for fluid catalytic cracking of hydrocarbon according to (5). (7) The average particle diameter of the particulate manganese compound is 60.
(1), (2), (3), (4),
The catalyst composition for fluid catalytic cracking of hydrocarbon according to (5) or (6). (8) The average particle size of the particulate manganese compound is 0.
The catalyst composition for fluidized hydrocarbon catalytic cracking according to item (7), which has a particle size of 1 to 30 μm.

[0016]

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

Reference Example-Preparation of dimanganese trioxide-The dimanganese trioxide used in this example was prepared by firing a commercially available electrolytic manganese dioxide powder in air at 750 ° C for 15 hours. The X-ray diffraction pattern of this powder is shown in FIG. The average particle size of the electrolyzed manganese dioxide powder is 20.
was μm.

Example 1 Y-type crystalline aluminosilicate zeolite (NH ₄ Y zeolite) was prepared by adding ammonium sulfate to 4000 g of silica hydrosol containing 5 wt% of SiO ₂ prepared by adding sulfuric acid to water glass at an exchange rate of 95%. ) 350 g (dry basis), 350 g of kaolin clay (dry basis) and 50 g of alumina particles (dry basis) obtained by air-flow firing of gibbsite having an average particle size of 30 μm were added, and the average particle size prepared in Reference Example was 20 microns. Dimanganese trioxide 5
0 g (oxide dry basis) was added to obtain a mixed slurry. The mixed slurry was spray-dried, washed, and then dried to obtain the catalytic composition for catalytic cracking of the present invention. This catalytic composition for catalytic cracking contains 35% by weight of NH ₄ Y zeolite,
It contained 5% by weight of dimanganese trioxide (on a dry oxide basis) and 5% by weight of alumina particles, and had an average particle size of 68 microns. This catalyst composition is referred to as catalyst D. In the same manner as the above-mentioned preparation method, catalysts were prepared by changing the addition amount of dimanganese trioxide. That is, kaolin is used as a balance substance, and the addition amount is 0, 0.5, 1.5, 1 respectively.
Dimanganese trioxide was added so as to be 0,20% by weight (dry basis). The catalysts are all NH ₄ Y zeolite 3
Contains 5% by weight. These catalysts are referred to as catalyst A,
The properties of the catalysts are shown in Tables 1 and 2 as B, C, E, and F.
The manganese content of the particulate dimanganese trioxide is M
It was 91.77% by weight as n ₂ O ₃ .

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

Example 2 Manganese was added to MnO ₂ in the same manner as in Example 1 except that the electrolytic method manganese dioxide powder used as a starting material for dimanganese trioxide was used as it was without firing.
As a result, a catalyst G containing 49% by weight (dry basis) was prepared.
Table 3 shows the properties of the catalyst G. The X-ray diffraction pattern of this powder is shown in FIG.

Comparative Example 1 Manganese chloride containing 25.5% by weight of spherical fine particles washed after spray drying the catalyst A containing no dimanganese trioxide particles obtained in Example 1 After being immersed in the aqueous solution at 60 ° C., washed, dried, and prepared as catalyst M containing 1.75% by weight of manganese as MnO ₂ existing in a uniformly dispersed state. Table 3 shows the properties of the catalyst H.
Shown in.

Comparative Example 2 The particulate Mn ₂ O ₃ -free catalyst A obtained in Example 1
The sprayed and dried washed spherical microparticles were immersed in the manganese chloride aqueous solution used in Comparative Example 1 at 60 ° C., and then 5% NH ₃ water was added with stirring to add manganese in the form of hydroxide. It was deposited on the catalyst. Then, the spherical fine particles on which manganese hydroxide was deposited were dehydrated and washed, and then 1
Catalyst I was prepared by drying at 20 ° C. for 16 hours. The obtained catalyst I contained manganese as MnO _{2 in an amount} of 3% by weight (on an oxide dry basis). Table 3 shows the properties of the catalyst I.

Example 3 (Performance Test) The catalyst particles A to I obtained in Examples and Comparative Examples were subjected to performance evaluation using a catalyst circulation regeneration type Midget-2 pilot plant. The Midget-2 pilot plant is shown schematically in FIG. In the figure, 1 is a reactor, 2 is a stripper, 3 is a catalyst regenerator, 4 is a condenser, 5 is a fractionator, 6 is a receiver,
7 is a cat trap, 8 is a separator, 9 is a movable tube, 1
0 is an air cooling pipe, 11 is an N ₂ inlet, 12 is a fuel oil inlet,
13 is an N ₂ and H ₂ O outlet, 14 is an N ₂ inlet, 15 is an air inlet, 16 is a transfer pipe, and 17 is a smoke-conducting gas outlet. The reaction in the reactor of No. 1 is 2MSO ₄ + 8H ₂ → MS + MO + H ₂ S + 7H ₂ O 2 in the stripper, the reaction of MS + H ₂ O → MO + H ₂ S 3 in the catalyst regenerator is Sin come + O ₂ → SO ₂ + SO ₃ 2SO ₂ + O ₂ → 2SO ₃ metal oxide (MO) + SO ₃ → MSO ₄ .

The operating conditions are as follows. Feedstock: Desulfurized atmospheric residual oil (40%) and desulfurized vacuum gas oil (6
Mixed oil with a feed oil S content 0.26 wt% weight hourly space velocity 25 hr ^-1 catalyst / oil 7 weight ratio reaction temperature 520 ° C regenerator temperature 670 ° C stripping temperature 500 ° C coke on regenerated catalyst 0. 05 wt%

In evaluating the performance, the catalyst was subjected to the following pseudo-equilibrium treatment. Nickel and vanadium are added to each catalyst.
2000 and 4000 ppm respectively were deposited. That is, after each catalyst was previously calcined at 600 ° C. for 1 hour, a predetermined amount of a solution of nickel naphthenate and vanadium naphthenate was absorbed by each catalyst, then dried at 110 ° C. and then 600 ° C.
It was baked for 1.5 hours. Since each catalyst is pseudo-equilibrium, 8
After fluidizing steam treatment at 10 ° C. for 6 hours, the cracking performance of heavy oil was evaluated using the apparatus of FIG. The results are shown in Tables 4-6.
Shown in. After the operation reaches a steady state, the gas discharged from the smoke-conducting gas outlet 17 in the regenerator is S
The results of analyzing O ₂ , CO and CO ₂ are shown in Tables 4 to 6.

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6] * ¹⁾ Gasoline: C _{5 to} 216 ° C. LCO: 216 to 343 ° C. HCO: 343 ° C.

[0031]

【effect】

(1) Since the catalyst of the present invention has improved catalyst deSOx ability,
If this is used as a catalyst, the amount of SOx in the exhaust gas can be further reduced. (2) The catalyst of the present invention not only has high metal resistance and high hydrothermal stability, but also hardly lowers the octane number of the produced gasoline. (3) When the catalyst of the present invention is used, there is little coke and dry gas, and the gasoline selectivity is high.

[Brief description of drawings]

FIG. 1 shows a diffraction X-ray pattern of MnO ₂ and Mn ₂ O ₃ .

FIG. 2 is a schematic diagram of a Midget-2 pilot plant used in an evaluation test of the catalyst of the present invention.

[Explanation of symbols]

1 Riser Reactor 2 Stripper 3 Regenerator 4 Condenser 5 Refractor 6 Receiver 7 Cat Trap 8 Separator 9 Movable Probe 10 Air Coil 11 N ₂ Inlet 12 Fuel Oil Inlet 13 N ₂ , H ₂ O Inlet 14 N ₂ Inlet 15 Air inlet 16 Transfer line 17 Smoke gas outlet

Claims (2)

[Claims] 1. A catalyst composition for fluid catalytic cracking of hydrocarbons, characterized in that a crystalline aluminosilicate zeolite and a particulate manganese compound are dispersed in an inorganic oxide matrix. 2. A catalyst composition for hydrocarbon fluid catalytic cracking according to claim 1, wherein the particulate manganese compound is dimanganese trioxide that can be detected by X-ray.