JPH10337475A - Catalyst composition for catalystic decomposition of hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance resistance to metal and bottom decomposition property, etc., and to decrease production quantities of coke and gas by incorporating activated clay in which a crystalline aluminosilicate zeolite quantity and a MgO quantity are in a specific range. SOLUTION: A catalyst composition suitable to fluidized catalystic decomposition of heavy hydrocarbon incorporating a metal contamination product such as Vd, and a sulfur compound, is adjusted to incorporate the activated clay in which the crystalline aluminosilicate zeolite quantity and the MgO quantity are in a 0.5-3 wt.% range. At this time, a mol ratio of MgO/SiO2 in the activated clay is preferably set in a range of 0.01-0.10. The activated clay is preferred to be in a range of 150-400 m<2> /g specific surface area and in a range of 0.2-0.5 ml/g pore volumes in <=600Å pore sizes. Besides, the activated clay is desired to have <= about 60 μm average particle size, though the size is especially not confined, and preferably desired to be in a range of about 0.1-30 μm.

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 catalytic cracking of hydrocarbons, and more particularly, to the fluid catalytic cracking of hydrocarbons, especially heavy hydrocarbons containing metal contaminants such as nickel and vanadium and sulfur compounds. The present invention relates to a catalyst composition for catalytic cracking of hydrocarbon, which is excellent in metal resistance, bottom decomposition property, etc., and generates little coke and gas.

[0002]

2. Description of the Related Art A catalyst used for catalytic cracking of hydrocarbons must have high cracking activity, high gasoline selectivity, and low coke and gas generation characteristics. Further, some refineries are required to have a high yield of a light gas oil fraction (light cycle oil). The recent deterioration in petroleum circumstances has caused a situation in which low-grade crude oil has to be passed through a normal-pressure distillation unit (topper), and the normal boiling point generated from the topper is 650 °.
As a result, the ratio of the residual oil of F or more is increased.
For this reason, such residual oil cannot be used as a raw material for catalytic cracking, and therefore, an oil catalyst composition for catalytic cracking is increasingly required to have a performance of decomposing heavy fractions.

Hitherto, various techniques have been proposed for catalytic cracking catalyst compositions excellent in cracking heavy oil components. And, in such catalysts, clay materials such as kaolin were generally used as extenders. Particularly, catalysts using a clay substance as an active ingredient include the following.

In Japanese Patent Application Laid-Open No. 63-270545, crystalline aluminosilicate zeolite is used in an amount of 3 to 40 watts.
t-%, containing a matrix composed of alumina, magnesia and smectite-type clay minerals in an amount of 60 to 97 wt%,
And the alumina content in the matrix is 5 to 80 wt.
%, A magnesia content of 2 to 40 wt% and a smectite type clay mineral content of 10 to 90 wt% are disclosed.

In Japanese Patent Application Laid-Open No. Hei 8-59228, a cation-exchangeable smectite clay mineral containing Mg and Si as main components is subjected to at least magnesium removal treatment and introduction of aluminum by cation exchange. An Mg / Si ratio (molar ratio) of 0.40 to
A clay composition which is adjusted in the range of 0.65 and the amount of introduced aluminum is adjusted to 0.001 or more and less than 0.08 in terms of Al / Si ratio (molar ratio), and this clay composition And a method for catalytically cracking petroleum hydrocarbons in a fluidized bed using this catalyst.

[0006] Further, in Japanese Patent Application Laid-Open No. 5-202366, a catalytic cracking method for petroleum hydrocarbons is characterized in that a composition containing cation-exchanged stevensite is used as a catalyst in catalytic cracking of petroleum hydrocarbons. Is described.

[0007] However, these conventional catalysts are not always satisfactory with respect to the cracking performance of heavy fractions (sometimes called bottoms), and improvements have been desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to use heavy hydrocarbons for catalytic cracking, particularly for fluid catalytic cracking.
An object of the present invention is to provide a catalyst composition for catalytic cracking of hydrocarbons which is excellent in metal resistance, bottom decomposability, etc., generates a small amount of coke and gas, and contains a specific clay substance as an active ingredient.

[0009]

According to the present invention, a crystalline aluminosilicate zeolite and an amount of MgO of 0.5 to 3 watts are provided.
The present invention relates to a catalyst composition for catalytic cracking of hydrocarbons containing activated clay in the range of t%.

The activated clay of the present invention is prepared by acid-treating an acidic clay composed mainly of montmorillonite to reduce the amount of MgO to 0.5-3.
It can be prepared and manufactured in the range of wt%. The amount of MgO in the activated clay can be changed depending on the degree of acid treatment of the acid clay.

The amount of MgO in the activated clay is 0.5 wt.
%, The effect is small in terms of metal resistance of the catalyst composition, and a high conversion cannot be obtained when metal contaminants such as nickel and vanadium are deposited on the catalyst composition. When the amount of MgO in the activated clay is more than 3% by weight, the amount of solid acid in the activated clay is small and sufficient bottom decomposition performance may not be obtained. The MgO content in the activated clay is preferably in the range of 1.0 to 2.5 wt%.

In the present invention, the activated clay is MgO /
It is preferred that the molar ratio of SiO ₂ is in the range of 0.01 to 0.10. If the MgO / SiO ₂ molar ratio in the activated clay is less than 0.01, the effect may not be sufficient in terms of the metal resistance of the catalyst composition. MgO / SiO
_{If the 2} molar ratio is greater than 0.10, Mg in a state where the severity of steaming during catalyst regeneration is high
May move to the ion-exchange site of the zeolite as the active component, poisoning the solid acid as the active site, resulting in poor hydrothermal resistance.

Further, the activated clay according to the present invention preferably has a specific surface area of 150 to 400 m ² / g and a pore volume of 600 Å or less in a range of 0.2 to 0.5 ml / g. If the specific surface area of the activated clay is smaller than 150 m ² / g, the amount of solid acid in the activated clay is small and sufficient bottom decomposability may not be obtained. May decrease. When the specific surface area is larger than 400 m ² / g, when the added amount of the activated clay in the catalyst is increased, the bulk ratio (ABD) of the catalyst is reduced, and the abrasion resistance (attrition) may be deteriorated.

Further, the pore volume of the activated clay is 0.2 ml /
g or less, the internal surface area of the microbore region becomes small, and the physical adsorption ability may be reduced.
If it is larger, the ABD of the catalyst becomes lighter and the attrition may worsen if the amount of activated clay added in the catalyst increases.

The above-mentioned activated clay has an average particle size of 60 μm.
m, preferably in the range of 0.1 to 30 μm. If the average particle size exceeds 60 μm, it is not desirable as a catalyst for a fluidized bed in relation to the average particle size of the finally obtained catalyst composition. Such activated clay is
Acid clay can be obtained by treating it with an acid such as sulfuric acid, and commercially available activated clay can be used as long as it has the above-mentioned properties. Since the activated clay has a solid acid of a strong acid and a weak acid, and has an appropriate pore volume, the catalyst composition of the present invention containing the activated clay has a high decomposition activity, and generates less coke and gas. .

As the crystalline aluminosilicate zeolite in the present invention, zeolites used in ordinary catalyst compositions for catalytic cracking of hydrocarbons can be used. For example, X-type zeolites, Y-type zeolites, mordenite,
Examples thereof include ZSM-type zeolites and natural zeolites, and are used in the form of being ion-exchanged with cations selected from hydrogen, ammonium and polyvalent metals, as in the case of ordinary catalyst compositions for catalytic cracking. Y-type zeolites, particularly ultra-stable Y-type zeolites, are preferred because of their excellent hydrothermal resistance.

In the catalyst composition for catalytic cracking of hydrocarbons of the present invention, the above-mentioned crystalline aluminosilicate zeolite and the above-mentioned activated clay are dispersed in an inorganic oxide matrix.
%, Preferably 15 to 35% by weight and the activated clay in a range of 1 to 20% by weight, preferably 2 to 15% by weight.

If the content of the activated clay is less than 1% by weight, the desired effect cannot be obtained, and if it exceeds 20% by weight, the abrasion resistance of the catalyst tends to decrease.

As the above-mentioned inorganic oxide matrix,
A matrix component used for a usual catalyst for catalytic cracking that also acts as a binder, such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, and silica-zirconia can be used. In addition, the matrix component, conventional clay substances,
A metal scavenger such as alumina or a manganese compound may be used in combination.

The catalyst composition of the present invention is prepared by adding the above-mentioned crystalline aluminosilicate zeolite and activated clay to the above-mentioned inorganic oxide matrix precursor such as silica hydrosol or silica-alumina hydrosol and dispersing the mixture uniformly. The resulting mixture slurry can be produced by a usual method of spray drying. The particles obtained by spray drying are washed as necessary, and after the washing, they are dried or fired again.

The catalyst composition of the present invention is suitable for the catalytic cracking of heavy hydrocarbons containing metal contaminants such as nickel and vanadium, but is also suitable for the catalytic cracking of hydrocarbons containing no metal pollutants. It can be used and can be used for catalytic cracking of a wide range of petroleum fractions, from lamps and light oils to high boiling degreasing oils. In the catalytic cracking using the catalyst composition, ordinary catalytic cracking conditions can be adopted.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, commercially available activated clay was used. Table 1 shows the properties of the activated clay.

[0023]

[Table 1] Activated clay types 1 to 5 include SiO ₂ , Al ₂ O ₃ , M
In addition to the components of gO, all of them contain Fe ₂ O ₃ and a small amount
_It contained ₂ O, K ₂ O, TiO ₂ , and CaO.

Example 1 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
875 g (dry basis) of kaolin clay, 250 g (dry basis) of activated alumina, and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 125 g (dry basis) of activated clay type 1 having the properties shown in Table 1 were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. This catalytic composition for catalytic cracking contained 10% by weight of activated alumina, 30% by weight of NH ₄ Y zeolite, and 5% by weight of activated clay type 1 and had an average particle diameter of 63 μm. This catalytic cracking catalyst composition is designated as A. The properties of the catalyst are shown in Table 2.

Example 2 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
875 g (dry basis) of kaolin clay, 250 g (dry basis) of activated alumina, and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 125 g (dry basis) of activated clay type 2 (see Table 1) were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. This catalytic composition for catalytic cracking contains 10% by weight of activated alumina, 30% by weight of NH ₄ Y zeolite, and 5% by weight of activated clay type 2;
Its average particle size was 63μ. This catalytic composition for catalytic cracking is referred to as B. The properties of the catalyst are shown in Table 2.

Example 3 12.5% by weight of SiO 2 prepared by adding water glass to sulfuric acid
750 g of kaolin clay (dry basis), 250 g of activated alumina (dry basis), and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 250 g (dry basis) of activated clay type 2 (see Table 1) were added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. The catalytic composition for catalytic cracking contained 10% by weight of activated alumina, 30% by weight of NH ₄ Y zeolite, and 10% by weight of activated clay type 2 and had an average particle size of 62 μm. This catalytic cracking catalyst composition is designated as C. The properties of the catalyst are shown in Table 2.

Example 4 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
500 g of kaolin clay (dry basis), 250 g of activated alumina (dry basis) and 4000 g of ammonium ion-exchanged Y at a conversion rate of 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 500 g (dry basis) of activated clay type 2 (see Table 1) were added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. This catalytic composition for catalytic cracking contained 10% by weight of activated alumina, 30% by weight of NH ₄ Y zeolite, and 20% by weight of activated clay type 2 and had an average particle size of 62 μm. This catalytic cracking catalyst composition is designated as D. The properties of the catalyst are shown in Table 2.

Example 5 12.5% by weight SiO 2 prepared by adding water glass to sulfuric acid
875 g (dry basis) of kaolin clay, 250 g (dry basis) of activated alumina, and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 125 g (dry basis) of activated clay type 3 (see Table 1) were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition of the present invention. This catalytic composition for catalytic cracking contains 10% by weight of activated alumina, 30% by weight of NH ₄ Y zeolite, and 5% by weight of activated clay type 3;
Its average particle size was 62μ. This catalytic cracking catalyst composition is designated as E. The properties of the catalyst are shown in Table 3.

Comparative Example 1 12.5% by weight of SiO 2 prepared by adding water glass to sulfuric acid
1000 g of kaolin clay (dry basis), 250 g of activated alumina (dry basis) in 4000 g of silica hydrosol containing ₂ and ammonium ion-exchanged Y-type crystalline aluminosilicate (NH ₄ Y zeolite) at an exchange rate of 90%
750 g (dry basis) was added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking-free catalytic composition containing no activated clay. This catalytic composition for catalytic cracking contained 10% by weight of activated alumina and 30% by weight of NH ₄ Y zeolite, and had an average particle size of 63 μm. This catalytic cracking catalyst composition is designated as F. The properties of the catalyst are shown in Table 3.

Comparative Example 2 12.5% by weight of SiO 2 prepared by adding water glass to sulfuric acid
875 g (dry basis) of kaolin clay, 250 g (dry basis) of activated alumina, and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 125 g (dry basis) of activated clay type 4 (see Table 1) were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition. This catalytic composition for catalytic cracking,
10% by weight of activated alumina and 30% of NH ₄ Y zeolite
5% by weight of activated clay type 4 and an average particle size of 63 μm. This catalytic composition for catalytic cracking is called G
And The properties of the catalyst are shown in Table 3.

Comparative Example 3 12.5% by weight of SiO 2 prepared by adding water glass to sulfuric acid
875 g (dry basis) of kaolin clay, 250 g (dry basis) of activated alumina, and ammonium ion-exchanged Y at an exchange rate of 90% are added to 4000 g of silica hydrosol containing ₂
-Type crystalline aluminosilicate (NH ₄ Y zeolite) 7
50 g (dry basis) and 125 g (dry basis) of activated clay type 5 (see Table 1) were added to prepare a mixed slurry, and this mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles were washed and dried to obtain a catalytic cracking catalyst composition. This catalytic composition for catalytic cracking,
10% by weight of activated alumina and 30% of NH ₄ Y zeolite
5% by weight of activated clay type 5 and an average particle size of 63 μm. This catalytic cracking catalyst composition is treated with H
And The properties of the catalyst are shown in Table 3.

[0032]

[Table 2]

[0033]

[Table 3]

Example 6 <Performance Test> The catalysts A, B, C, D and D prepared in Examples and Comparative Examples
E, F, G and H were evaluated for performance by ASTM MAT (small activity test device). The MAT evaluation conditions are as follows. Feedstock: desulfurized vacuum gas oil (60%) and desulfurized atmospheric residue (4
0%) mixed oil Weight hourly space velocity: 40 hr ^-1 catalyst / oil: 5 weight ratio Reaction temperature: 510 ° C

In evaluating the performance, each catalyst contains 4000 ppm and 2000 ppm of vanadium and nickel, respectively.
They were deposited and then steamed to give a pseudo-equilibrium treatment. Specifically, after firing each catalyst at 600 ° C. in advance,
A predetermined amount of vanadium naphthenate and nickel naphthenate solution were absorbed, then dried at 110 ° C., baked at 600 ° C. for 1.5 hours, and then steamed at 780 ° C. for 13 hours, and then subjected to a performance test. . Table 4 ~
5 is shown.

[0036]

[Table 4] * 1) conversion: 100- (LCO + HCO) * 2) gasoline boiling ^{_{range: C 5 -204 ℃ * 9 *}} 3) LCO boiling range: 204 ℃ -343 ℃ * 4) HCO boiling range: 343 ° C. or higher * 5) K (secondary reaction rate constant) = conversion / (100-conversion) * 6) represents a hydrogen selective * 7) represents the coke selectivity * 8) represents the bottom degradable * 9) C ₅ -204 ° C. Means that it contains from hydrocarbons having 5 carbon atoms to hydrocarbons having a boiling point of 204 ° C.

[0037]

[Table 5] * 1) conversion: 100- (LCO + HCO) * 2) gasoline boiling _{range: C 5 -204 ℃ * 3)} LCO boiling range: 204 ℃ -343 ℃ * 4) HCO boiling range: 343 ° C. or higher * 5) K ( Second-order reaction rate constant) = conversion / (100-conversion) * 6) Indicates hydrogen selectivity * 7) Indicates coke selectivity * 8) Indicates bottom decomposition

According to the above measurement results, the activated clay-containing catalysts A, B, C, D and E of the present invention exhibited high conversion under hydrothermal treatment conditions at high temperatures containing nickel and vanadium at high concentrations. . This indicates that the catalyst of the present invention has a MgO content of 3.0 wt% in the ordinary catalyst F and activated clay.
G, H using activated clay containing a large amount beyond
It can be seen that they are superior in metal resistance and hydrothermal resistance as compared with. Despite the high conversion, the amount of hydrogen generated,
The results showed that the amount of coke and the amount of bottom formed were low and the light cycle oil yield was high. This can be said to be the result of the fact that activated clay having a weak solid acid contributed to the crude decomposition of the high molecular hydrocarbons, and promoted the decomposition of the bottom while keeping the amount of coke low.

[0039]

[Results] When the catalyst of the present invention is used for catalytic cracking of hydrocarbons, especially heavy hydrocarbons, the amount of coke and dry gas generated is small, and gasoline and light cycle oil (LCO)
Liquid yield is high.

Claims (3)

[Claims] 1. A catalyst composition for catalytic cracking of hydrocarbons comprising crystalline aluminosilicate zeolite and activated clay having an amount of MgO in the range of 0.5 to 3 wt%. 2. MgO / SiO ₂ in said activated clay
The catalyst composition for catalytic cracking of hydrocarbons according to claim 1, wherein the molar ratio is in the range of 0.01 to 0.10. 3. The activated clay has a specific surface area of 150.
The catalyst composition for catalytic cracking of hydrocarbons according to claim 1 or 2, wherein the pore volume of ４００400 m ² / g and 600 Å or less is in the range of 0.2-0.5 ml / g.