JPH07126661A - Catalytic cracking of heavy hydrocarbon oil - Google Patents

Abstract

PURPOSE:To obtain a liquid product in high yield by reduced formation of L, H2 and coke, by catalytically cracking heavy hydrocarbon oil including Ni, V or the like in the presence of a specific catalyst having a specific SiO2/Al2-O3 molar ratio, a specific unit lattice dimension and a specific molar ratio of Al in the zeolite skeletal. CONSTITUTION:In the catalytic cracking of heavy hydrocarbon oil including one or both of Ni and V, smooth catalytic cracking of the heavy hydrocarbon oil including these metals contaminating the cracking catalyst can be done by using the catalyst comprising crystalline aluminosilicate salt which causes the results such as 5.5 to 6.9 SiO2/Al2O3 molar ratio in bulk according to the chemical analysis, 24.34 to 24.46Angstrom unit lattice dimension, 0.2 to 0.4 molar ratio of the Al in a zeolite skeletal to the total Al calculated according to the equation I (a0 is the unit lattice dimension in nm; NAl is the number of Al atoms per the unit lattice), formula II and formula III and exhibiting Y type of the major X-ray diffraction pattern of the zeolite and the inorganic oxide matrix, in the case where the catalyst is contaminated with one or both of 3,000 to 13,000ppm of nickel and vanadium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for catalytically cracking heavy hydrocarbon oil, and more particularly to a state in which nickel or vanadium pollutes a catalyst in the catalytic cracking of heavy hydrocarbon oil containing nickel or vanadium. When using a catalytic cracking catalyst consisting of a crystalline aluminosilicate that exhibits specific physical properties and an inorganic oxide matrix, high cracking activity, low hydrogen and coke generation, gasoline fraction and light cracking fraction ( The present invention relates to a catalytic cracking method capable of obtaining a liquid product such as LCO) in high yield.

[0002]

2. Description of the Related Art Generally, catalytic cracking is a technique aimed at producing cracked gasoline in good yield by cracking hydrocarbon oil by contacting it with a catalyst. At the same time, by the catalytic cracking of hydrocarbon oil, a gasoline fraction can be obtained in a high yield and
It is also important to increase the yield of desirable liquid products such as CO.

Conventionally, vacuum gas oil (VGO) has been mainly used as a feedstock for the catalytic cracking. However, due to recent crude oil circumstances and market trends of petroleum products, atmospheric distillation residue oil and vacuum distillation are used. Residual oil (hereinafter referred to as residual oil) is inevitably used as a raw material oil.

By the way, these residual oils contain a much larger amount of metals such as nickel and vanadium than those in VGO, and these metals are deposited on a catalyst that is circulated and used as a catalyst. It is known to significantly reduce the decomposition activity of bisphenol, and also increase the production of hydrogen and coke, thereby decreasing the yield of liquid products.

In order to reduce the pollution of the catalyst by nickel or vanadium, a method is used in which a part of the catalyst which is circulated is withdrawn and a new catalyst is replenished. However,
In this method, as the content of nickel or vanadium contained in the heavy hydrocarbon oil increases, the catalyst for recycling (hereinafter,
The effect of catalyst contamination by nickel and vanadium cannot be avoided unless the withdrawal amount of the equilibrium catalyst) and the replenishment amount of the new catalyst are increased. I can't say.

Regarding a catalyst aiming at improving the decomposability of residual oil by suppressing the adverse effects of these metals, a method of improving the inorganic oxide matrix, which is one of the constituent elements, is as follows.
It has been proposed in the past.

For example, a method of catalytically cracking heavy oil containing nickel and vanadium in an amount of 0.5 ppm or more by using a catalyst in which alumina-magnesia is used as an inorganic oxide matrix and which is mixed with crystalline aluminosilicate is used. Proposed (JP-A 64-47449, JP-A 1-111446, 1-207138, 2-2)
73544 and 4-200641).

Further, a catalyst has been proposed in which silica-alumina, γ-alumina, boehmite or the like is used as a matrix, and this is mixed with a stabilized Y-type zeolite (see JP-A-58-163439).

Furthermore, a catalyst containing bayerite and eta-alumina as matrix components (Japanese Patent Laid-Open No. 2-2
No. 77548), crystalline calcium aluminate, and a catalyst in which crystalline calcium silicate is dispersed in an inorganic oxide matrix (JP-A-3-293037).
JP-A-3-293038), a catalyst containing a metal oxide treated with a phosphorus compound (Japanese Patent Laid-Open No. 4-20074).
No. 4), a method for catalytically cracking heavy oil has been proposed.

In addition, a method has been proposed in which the surface of the catalyst is coated with a rare earth element or a refractory metal oxide to supplement the contaminating metal in the feedstock oil used for catalytic cracking (Japanese Patent Laid-Open No. 1-1999). 258742 and 4-310239).

However, when a heavy hydrocarbon oil is catalytically cracked by using a catalyst using silica-alumina or γ-alumina as a matrix component, the amount of hydrogen and coke produced increases, such as gasoline and LCO. There is a tendency that the yield of the desired liquid product decreases, and there is a problem that the operation of the apparatus becomes difficult, such as an excessive load on the catalyst regeneration tower constituting the catalytic cracking apparatus.

When another substance is added to the catalyst or the surface of the catalyst is coated, the number of steps for producing the catalyst increases, which is not preferable in terms of production amount and cost.

Therefore, the present inventors have previously proposed a catalyst comprising a crystalline aluminosilicate having a unique physical property obtained by applying a thermal load to the stabilized Y-type zeolite and an inorganic oxide matrix. Excellent contact resolution of hydrocarbon oils, especially residual oils, which can increase the yield of middle distillates (LCO) equivalent to gasoline, kerosene and light oil, and effectively suppress the production of hydrogen and coke. It has been found that it is possible to make various proposals (Japanese Patent Laid-Open No. 4-5).
9616, 4-305248 and 5-17860.
See Japanese Patent Publication No. 9, hereinafter, these may be referred to as "previous proposals").

In view of the above facts, the present invention provides a method in which a catalyst is contaminated with a large amount of nickel or vanadium.
To provide a method for catalytically cracking a hydrocarbon oil, particularly a heavy hydrocarbon oil containing a residual oil, by using a specific catalyst capable of exerting an excellent effect when catalytically cracking the hydrocarbon oil. The purpose is.

[0015]

Means and Actions for Solving the Problems As a result of intensive investigations by the present inventors,
The crystalline SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis, the molar ratio of Al in the zeolite skeleton to the total Al, and the crystalline aluminum silicate showing specific values in the unit cell size, and an inorganic oxide matrix. When catalytic cracking of a heavy hydrocarbon oil was carried out under conditions where the catalyst for catalytic cracking, which is a mixture, contained a large amount of nickel and vanadium, which are catalytic pollutants, the cracking activity was high, and hydrogen and coke were not produced. The present invention has been completed based on the finding that a small amount of liquid products such as gasoline fraction and LCO can be obtained in high yield.

That is, the present invention is a method for catalytically cracking a heavy hydrocarbon oil containing one or both of nickel and vanadium.
In the state of being contaminated by one or both of nickel and vanadium of 00 ppm, the bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 5.5 to 6.9, and the unit cell size is 24.34 to 24. 46Å, the molar ratio of Al in the zeolite skeleton to the total Al is 0.2 to 0.4 as calculated by the following formulas (1) to (3), crystalline alumino having a main X-ray diffraction pattern of Y-type zeolite The gist is a catalytic cracking method characterized by using a catalyst composed of a silicate and an inorganic oxide matrix.

[0017]

[Equation 2]

The above equation (1) is based on H.264. K. Be
yer et al. J. Chem. Soc. , Fa
rayad Trans. 1,1985, (81), 2
The formula described in 899 is adopted.

Further, in the present invention, as the above-mentioned catalyst, at least one metal selected from the group consisting of rare earth metals and alkaline earth metals is used as an oxide in an amount of 0.01 to 5% by weight based on the catalyst. It is also characterized in that the one contained is used.

The present invention will be specifically described below. First,
The crystalline aluminosilicate used for the catalyst used in the catalytic cracking method of the present invention will be described in detail.

The catalyst used in the catalytic cracking process of the present invention is a mixture of crystalline aluminosilicate and an inorganic oxide matrix. This crystalline aluminosilicate has a bulk SiO ₂ / Al ₂ O ₃ molar ratio of 5.5 to 6.9 and a unit cell size of 24.34 to ₂ by chemical composition analysis.
The ratio is 4.46Å, the molar ratio of Al in the zeolite skeleton to the total Al is 0.2 to 0.4, and the main X-ray diffraction pattern of Y-type zeolite is obtained. In addition,
This crystalline aluminosilicate has an ignition weight loss rate of 0.5.
It is preferably ˜20% by weight.

Examples of the crystalline aluminosilicate having the above-mentioned properties include Y-type zeolite, and ultra-stable Y-type zeolite and stabilized Y-type zeolite obtained by dealumination of ordinary Y-type zeolite by various methods. Examples of the zeolite include a zeolite obtained by applying a thermal load, and a zeolite obtained by applying a thermal load to a stabilized Y-type zeolite is particularly preferable.

An example of applying a thermal load to the stabilized Y zeolite will be described in detail. The stabilized Y-type zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 5.5 to
6.9, the unit cell size is about 24.50 to 24.69Å.

The thermal load may be applied at about 400 to 1200 ° C. for about 5 to 300 minutes. If the temperature is too low or the firing time is too short, a crystalline aluminosilicate having the above-mentioned predetermined properties cannot be obtained. Conversely, if the temperature is too high or the firing time is too long, the above-mentioned predetermined properties will not be obtained. The crystalline aluminosilicate possessed cannot be obtained.

The thermal load may be applied in an electric furnace or a firing furnace under an air or nitrogen atmosphere or under a steam atmosphere. It should be noted that suitable humidity facilitates dealumination, so that a crystalline aluminosilicate having the above-described predetermined characteristics can be obtained even at a low temperature within the above temperature range.

When applying a thermal load, the stabilized Y-type zeolite as a raw material may be placed in the calcining furnace after reaching the above temperature, or after the stabilized Y-type zeolite is placed in the calcining furnace, The temperature may be gradually raised from room temperature to reach the predetermined temperature.

The crystalline aluminosilicate can be obtained by the thermal load as described above and has the following predetermined characteristics. That, _SiO 2 / _Al 2 _{O 3} molar ratio in the bulk by chemical composition analysis is a 5.5 to 6.9.

The unit cell size is 24.34-2.
It is 4.46Å, preferably 24.36 to 24.44Å, more preferably 24.36 to 24.41Å. This unit cell size measurement is according to ASTM D-3942 / 85.
It can be calculated using the peak of X-ray diffraction.

The molar ratio of Al in the zeolite skeleton to the total Al is calculated using the above formulas (1) to (3), and the SiO ₂ / Al ₂ O ₃ molar ratio and unit are determined by the above chemical composition analysis. A value calculated from the grid size, 0.2 to
0.4, preferably 0.25 to 0.35, and more preferably 0.25 to 0.30 (the above-mentioned H. K. Bey.
er et al. J. Chem. Soc. , Far
day Trans. 1,1985, (81), 28
99). The molar ratio of Al in the zeolite skeleton to the total Al can be calculated by other formulas, but when other formulas are used, the above values are not obtained.

When the bulk SiO ₂ / Al ₂ O ₃ molar ratio is the same, if the molar ratio of Al in the zeolite skeleton to the total Al is too large, it is easily affected by nickel and vanadium, and the activity is reduced due to metal contamination. Can be seen. On the other hand, if this molar ratio is too small, the catalytic activity tends to be low although the influence of metal contamination is small.

On the other hand, when the unit cell size is almost the same, if the bulk SiO ₂ / Al ₂ O ₃ molar ratio measured by chemical analysis is too large, the activity is lowered due to metal contamination of nickel or vanadium, and this molar ratio is small. If it is too much, the catalytic activity tends to decrease.

The reason for this is not clear, but
Amount of total Al in the entire crystalline aluminosilicate represented by bulk SiO ₂ / Al ₂ O ₃ molar ratio and Al in the skeleton
The ratio of the amount of Al in the skeleton (in other words, the ratio of Al outside the skeleton) represented by the molar ratio of / total Al is related to the metal resistance as well as the catalytic activity. If the amount of Al outside the skeleton increases, the metal resistance increases. However, it is considered that a catalyst using a crystalline aluminosilicate having a large amount of extra-framework Al causes a decrease in the activity of the crystalline aluminosilicate itself, which is the main active species of catalytic decomposition.

Further, the ignition weight reduction rate is about 0.5-2.
It is 0% by weight, preferably about 1-10% by weight, more preferably about 1.5-8% by weight. This ignition weight reduction rate is obtained by the formula shown in Formula 3.

[0034]

[Equation 3]

If this value is too large, the crystalline aluminosilicate tends to retain water, resulting in a decrease in hydrothermal stability, resulting in sufficient decomposition activity in the catalytic decomposition method of the present invention. There is a problem that there is no.

The crystalline aluminosilicate having the above-mentioned properties and used in the present invention is typically obtained by subjecting the stabilized Y-type zeolite to a constant thermal load, as described above. However, the major feature is that the unit cell size is about 24.34 to 24.46Å, which is smaller than about 24.50 to 24.69Å of stabilized Y zeolite, and the total Al The molar ratio of Al in the zeolite skeleton with respect to is about 0.2 to 0.4. The properties of the above crystalline aluminosilicates are summarized in Table 1.

[0037]

[Table 1]

The crystalline aluminosilicate used in the present invention has substantially the X-ray diffraction pattern shown in FIG. In FIG. 1, 1, 2 and 3 are peaks of the lattice spacing (d) showing the strongest diffraction, and are 14.1 ±
0, 2Å, 5.61 ± 0.1Å and 3.72 ± 0.1
It is Å. Then, the X-ray diffraction diagram of FIG. 1 has values as shown in Table 2 as a typical example.

[0039]

[Table 2]

Further, the crystalline aluminosilicate used in the present invention has an alkali metal content of about 0.02 to 2% by weight, preferably about 0.05 to 1% by weight in terms of oxide.
Are preferred. When the content of the alkali metal is less than about 0.02% by weight in terms of oxide, the crystal structure may easily collapse. On the contrary, when a large amount of alkali metal is present, the decomposition activity of the catalyst using the crystalline aluminosilicate used in the present invention may be lowered, and
When nickel or vanadium adheres to the catalyst, there is a problem that the activity tends to deteriorate.

Next, the inorganic oxide matrix used for the catalyst will be described in detail. The inorganic oxide matrix used in the present invention includes, for example, silica, alumina, boria, 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, which is used for a usual catalytic cracking catalyst that acts as a binder between particles.

The matrix component may further contain at least one clay mineral such as kaolin, montmorillonite, halloysite, bentonite and attapulgite.

When the inorganic oxide is used, depending on the type, for example, alumina may have an effect such as an increase in the amount of hydrogen and coke produced. Therefore, select the one suitable for the purpose of use. is necessary.

The method for producing the catalyst used in the present invention will be described in detail. As the catalyst, for example, an aqueous slurry of silica-alumina hydrogel, silica sol, alumina sol or the like is used as an inorganic oxide matrix, the above-described crystalline aluminosilicate is added thereto, and the mixture is thoroughly stirred and mixed, and the resulting mixture slurry is spray-dried. Can be manufactured.

In this preparation, the crystalline aluminosilicate in the mixed catalyst is about 10 to 50% by weight, preferably about 15 to 45% by weight, and the inorganic oxide matrix is about 50 to 90% by weight, preferably Of the crystalline aluminosilicate and the inorganic oxide matrix are mixed in an amount of about 55 to 85% by weight. If the amount of crystalline aluminosilicate is less than about 10% by weight, the decomposition activity required in the present invention cannot be obtained. On the contrary, if it is more than about 50% by weight, the amount of the inorganic oxide matrix becomes relatively too small. As a result, the strength of the catalyst is lowered, and problems such as scattering of the catalyst and mixing of the produced oil with the operation of the apparatus occur.

Further, the inclusion of rare earth metal and alkaline earth metal in the catalyst used in the present invention will be described in detail. It is also one of the features of the present invention that the catalyst containing at least one metal selected from the group consisting of rare earth metals and alkaline earth metals is used as the catalyst.

As the rare earth metal, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, etc. are used, and these are used alone or as a mixture of two or more.

As the alkaline earth metal, beryllium,
Magnesium, calcium, strontium, barium and radium are used, either alone or in 2
It is used as the above mixture and is preferably magnesium or calcium alone or as a mixture.

At least one kind of these rare earth elements and at least one kind of alkaline earth metal can be mixed and used, but the rare earth element is preferable.

As a mode of containing the above-mentioned rare earth metal or alkaline earth metal in the above catalyst, a part or all of the crystalline aluminosilicate, which is one of the constituents of the catalyst, is ion-exchanged with these metals. Or a so-called metal-modified crystalline aluminosilicate in which these metals are supported on a crystalline aluminosilicate, or the above catalyst itself is ion-exchanged with these metals, or The mode of carrying the metal of is adopted.

When the crystalline alumina silicate or the catalyst is ion-exchanged with the above metal, or when the crystalline aluminosilicate or the catalyst is loaded with the above metal, a conventionally known method can be used.

For example, in any case of ion exchange and loading, chlorides of rare earth metals and alkaline earth metals, nitrates,
By impregnating the crystalline aluminosilicate or the catalyst with an aqueous solution containing one or more compounds such as sulfates and acetates, or by immersing them in these aqueous solutions and heating them if necessary. It can be carried out.

In both cases of ion exchange and loading, the above-mentioned amount of metal is about 0.01 as an oxide based on the mixed catalyst of crystalline aluminosilicate and inorganic oxide matrix.
%, Preferably about 0.05 to 4% by weight, more preferably about 0.1 to 3% by weight. By ion exchange or loading of the above metal, a high decomposition activity can be obtained, but if the amount of metal is too small, this effect does not appear,
If too much, this effect does not improve so much.

In addition, regarding the catalytic decomposition method of the present invention,
The details will be described. The heavy hydrocarbon oil cracked by the catalytic cracking method of the present invention means a light oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil, atmospheric distillation residual oil, vacuum distillation residual oil, direct degenerated oil, or these. Of mixed oil, of course,
It also includes coker gas oil, solvent deasphalted oil, solvent deasphalted asphalt, tar sand oil, shale oil, and coal liquefied oil. Moreover, one or both of nickel and vanadium are contained as metal contaminants in an amount of 0.5 ppm or more.
In particular, a heavy hydrocarbon oil in which the residual oil containing a large amount of nickel or vanadium, the directly degenerated oil, or the like is mixed in whole or in part is also included.

Catalytic cracking on a commercial scale is usually carried out by continuously catalytically cracking the above-described catalyst in a catalytic cracking apparatus consisting of two vessels, a vertically installed cracking reactor and a catalyst regenerator. It is circulated in. The hot regenerated catalyst coming out of the regenerator is mixed with the heavy hydrocarbon oil to be cracked and guided upward in the cracking reactor. Due to the reaction in the cracking reactor, carbonaceous material generally called coke is deposited on the catalyst,
Although the catalyst is in a deactivated state, the catalyst is separated from the decomposition products, stripped, and transferred to a regenerator. The spent catalyst transferred to the regenerator is regenerated by removing the coke on the catalyst by air calcination, and is recycled to the cracking reactor for reuse.

When a heavy hydrocarbon oil containing nickel or vanadium is catalytically cracked, the catalyst is contaminated with nickel or vanadium and the catalytic activity is lowered. Therefore, a regenerated catalyst obtained by air-calcining coke, that is, an equilibrium catalyst is usually used. A part of it is extracted and new catalyst is supplied as a supplement.

The amount of nickel or vanadium deposited on the equilibrium catalyst is related to the amount of nickel or vanadium in the heavy hydrocarbon oil and the supply amount of the new catalyst. The larger the amount and the smaller the amount of new catalyst supplied, the larger the amount of nickel and vanadium on the equilibrium catalyst. Regarding this relationship, Vol. 5, No. 1, "Petrotech" published by Japan Petroleum Institute (1982)
p. 82-83.

On the other hand, the decomposition products are dry gas and LP.
G, gasoline fraction, and, for example, light cycle oil (LC
O), heavy cycle oil (HCO) or slurry oil and separated into one or more heavy fractions. Of course, it is also possible to further promote the cracking reaction by recycling these heavy fractions to the cracking reactor.

The operating conditions of the above catalytic cracking apparatus are not particularly limited, but for example, the reaction temperature is about 450 to 570.
° C., preferably from about four hundred and seventy to five hundred fifty ° C., a reaction pressure of about atmospheric pressure ~5kg / cm ^2, the catalyst / feedstock heavy weight ratio of the hydrocarbon oil from about 2 to 20 parts by weight / parts by weight, preferably about 4 to 15 Weight part / weight part, contact time is about 0.3 to 6 seconds, and catalyst regeneration temperature is about 550 to 850 ° C.

In the catalytic cracking method of the present invention, when a catalytic cracking catalyst composed of the crystalline aluminosilicate having the above-mentioned specific physical properties and the inorganic oxide matrix is used, nickel or nickel contained in the heavy hydrocarbon oil can be used. Due to vanadium, the equilibrium catalyst is about 3000 to 13 in total amount of these metals.
000 ppm, preferably about 3000-10000 pp
m Deterioration performance is suppressed in a contaminated state,
The effect is to reduce hydrogen and coke, ie to increase the yield of the desired liquid product. If the pollution by nickel or vanadium is less than about 3000 ppm, these effects are small, but if it exceeds about 3000 ppm, the effect of suppressing the decomposition performance deterioration and the reduction effect of hydrogen and coke become remarkable as the pollution amount increases. However, these effects are satisfactorily exhibited until the contamination with nickel or vanadium reaches about 13000 ppm, preferably about 10000 ppm.

[0061]

【Example】

[Production Example of Crystalline Aluminosilicate] Example 1 SiO ₂ / Al ₂ O ₃ molar ratio was 6.0, unit cell size was 24.62Å, and alkali metal content was 0.
6 wt% of stabilized Y-type zeolite was calcined in an electric furnace at 750 ° C. for 20 minutes under atmospheric pressure and atmospheric pressure to produce crystalline aluminosilicate (hereinafter, HZ-1). When this HZ-1 was analyzed, the major X of Y-type zeolite
It showed a line diffraction pattern and had the physical properties shown in Table 3.

[0062]

[Table 3]

Example 2 The same stabilized Y-type zeolite as that used in Example 1 was calcined in the same manner as in Example 1 except that the calcining temperature was 850 ° C. to give a crystalline aluminosilicate (hereinafter, HZ-2)
Was manufactured. When this HZ-2 was analyzed, it showed the main X-ray diffraction pattern of Y-type zeolite and had the physical properties shown in Table 4.

[0064]

[Table 4]

Example 3 The same stabilized Y-type zeolite as that used in Example 1 was calcined in the same manner as in Example 1 except that the calcining temperature was 650 ° C. to give a crystalline aluminosilicate (hereinafter HZ-3)
Was manufactured. When this HZ-3 was analyzed, it showed a main X-ray diffraction pattern of Y-type zeolite and had the physical properties shown in Table 5.

[0066]

[Table 5]

Comparative Example 1 The same stabilized Y-type zeolite as that used in Example 1 was calcined in the same manner as in Example 1 except that the calcining temperature was 540 ° C., and a crystalline aluminosilicate (hereinafter, HZ-4)
Was manufactured. When this HZ-4 was analyzed, it showed the main X-ray diffraction pattern of Y-type zeolite and had the physical properties shown in Table 6.

[0068]

[Table 6]

Comparative Example 2 SiO ₂ / Al ₂ O ₃ molar ratio was 5.3, unit cell size was 24.68Å, and alkali metal content was 0.
7% by weight of stabilized Y-type zeolite with a calcination temperature of 700
A crystalline aluminosilicate (hereinafter, HZ-5) was produced by firing in the same manner as in Example 1 except that the temperature was set to be ° C. This HZ
When -5 was analyzed, it showed the main X-ray diffraction pattern of Y-type zeolite and had the physical properties shown in Table 7.

[0070]

[Table 7]

Comparative Example 3 The SiO ₂ / Al ₂ O ₃ molar ratio was 7.4, the unit cell size was 24.59Å, and the alkali metal content was 0.
4% by weight of stabilized Y-type zeolite with a calcination temperature of 800
A crystalline aluminosilicate (hereinafter referred to as HZ-6) was manufactured by firing in the same manner as in Example 1 except that the temperature was set to be ° C. This HZ
When -6 was analyzed, it showed the main X-ray diffraction pattern of Y-type zeolite and had the physical properties shown in Table 8.

[0072]

[Table 8]

[Preparation Example of Catalyst] Example 4 2315 g of water and 2335 g of silica sol having a concentration of 30% by weight
And were mixed by stirring, and sulfuric acid was added thereto to adjust the pH to 1.8. Kaolin was then dried on a dry basis of 1681 g, and HZ-1 obtained in Example 1 was dried on a dry basis of 1121 g and water of 4000.
g and further mixed with stirring. The obtained mixture was dried and atomized with a spray dryer, and 25 liters (hereinafter,
It was washed with distilled water of L). The dried finely granulated product after washing,
It was dried in air at 115 ° C. for 16 hours to obtain a catalyst used in the present invention (hereinafter referred to as catalyst A).

Example 5 A catalyst used in the present invention (hereinafter referred to as catalyst B) was obtained in the same manner as in Example 4 except that HZ-2 obtained in Example 2 was used instead of HZ-1.

Example 6 A catalyst used in the present invention (hereinafter referred to as catalyst C) was obtained in the same manner as in Example 4 except that HZ-3 obtained in Example 3 was used instead of HZ-1.

Example 7 The dried finely-divided product after the spray dryer obtained in the same manner as in Example 4 was used as a catalyst precursor, and the total amount of this precursor was 10
Ion exchange was performed using 30 L of an aqueous rare earth chloride solution containing 10 g of rare earth chloride per 0 ml (hereinafter, mL). As the rare earth chloride, one having the composition shown in Table 9 was used (hereinafter, the rare earth chloride having this composition was used). Ion exchange was carried out by immersing in the above aqueous solution heated to 90 ° C. for 30 minutes. After the immersion, it was filtered, washed with water, and then dried in air at 115 ° C. for 16 hours to obtain a catalyst used in the present invention (hereinafter referred to as catalyst D). The rare earth metal content in this catalyst D was 1.43% by weight based on the catalyst as an oxide.

[0077]

[Table 9]

Comparative Example 4 A comparative catalyst (hereinafter referred to as catalyst E) was obtained in the same manner as in Example 4 except that HZ-4 obtained in Comparative Example 1 was used instead of HZ-1.

Comparative Example 5 A comparative catalyst (hereinafter referred to as catalyst F) was obtained in the same manner as in Example 4 except that HZ-5 obtained in Comparative Example 2 was used instead of HZ-1.

Comparative Example 6 A comparative catalyst (hereinafter referred to as catalyst G) was obtained in the same manner as in Example 4 except that HZ-6 obtained in Comparative Example 3 was used instead of HZ-1.

Comparative Example 7 A comparative catalyst (hereinafter referred to as catalyst H) was obtained in the same manner as in Example 7 except that HZ-4 obtained in Comparative Example 1 was used instead of HZ-1. The rare earth metal content of this catalyst H was 1.58% by weight based on the catalyst as an oxide.

[Bench Scale Plant Test Example] A bench scale plant, which is a circulating fluidized bed reactor equipped with a cracking reactor and a catalyst regenerator, is used which is a commercial scale catalytic cracking unit scaled down. Then, catalytic cracking of heavy hydrocarbon oil was tested using the above catalysts A to H.

Prior to the test, each catalyst was dried at 500 ° C. for 5 hours so that each catalyst contained a pollutant metal. Then, each catalyst had a weight ratio of Ni to V of 1: 2 and a total of Ni + V. To a concentration of 4000 ppm and 9000 ppm, a cyclohexane solution containing nickel naphthenate and vanadium naphthenate is absorbed, dried, and dried at 500 ° C.
Was baked for 5 hours. Then, each catalyst
A simulated equilibrated catalyst was obtained by treating at 785 ° C for 6 hours in a 0% steam atmosphere.

The test was carried out by using 75% by weight of desulfurized vacuum gas oil and 25% by weight of directly-degenerated oil having the properties shown in Table 10 as the feed oil.
Using a mixed oil of, and changing the catalyst / feed oil (weight ratio) to 4, 7, 9.5, 12.5 under the conditions of a reaction temperature of 510 ° C. and a catalyst circulation rate of 60 g / min. went. The decomposition activity was compared based on the conversion rate of the raw oil of 60%. The evaluation results are summarized in Tables 11 to 14.

Further, with respect to the catalyst A and the catalyst E, a simulated equilibrated catalyst was obtained by the same method as described above except that the total of Ni + V was 1500 ppm, and the same test method as above was used for the test. And The results are shown in Table 1.
It is shown collectively in 5.

[0086]

[Table 10]

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

As a result of the above test, when decomposing a feedstock oil containing nickel or vanadium, which is a contaminant metal of the catalyst,
According to the examples of the present invention using the crystalline aluminosilicate having specific physical properties, it is clear that the decomposition activity is high as compared with the comparative example using the crystalline aluminosilicate having other physical properties. . The physical properties _(SiO 2 / _Al 2 _{O 3} molar ratio, unit cell dimensions, skeleton in Al / total Al molar ratio) the relationship between the degradation activity, shown in FIGS. Further, the selectivity of the catalyst A of the present invention and the comparative catalyst E (results shown in Tables 11 to 15) are collectively shown in FIGS. In addition, (A)-(G) in FIGS. 2-6 shows catalyst A-catalyst G.

[0093]

As described in detail above, according to the catalytic cracking method of the present invention, when the catalyst used is catalytically cracked in a heavy hydrocarbon oil in a state where it is contaminated with a large amount of nickel or vanadium. It is possible to exert excellent effects, suppress deterioration of decomposition performance, reduce generation of hydrogen and coke, and increase yield of desired liquid product. Further, the above-mentioned catalyst used in the catalytic cracking method of the present invention has an easy production process, a good production amount, and a low production cost and material cost. Furthermore, the catalytic cracking method of the present invention does not cause a situation in which the operation of the apparatus is difficult. As a result, the present invention can be said to be a catalytic cracking method suitable for recent petroleum circumstances and market trends of petroleum products.

[Brief description of drawings]

FIG. 1 is a diagram showing an X-ray diffraction pattern of a crystalline aluminosilicate used in the present invention.

FIG. 2 Physical properties of crystalline aluminosilicate (SiO ₂ / Al
₂ is a graph showing the relationship between ₂ O ₃ molar ratio) and decomposition activity.

[Fig. 3] Physical properties of crystalline aluminosilicate (unit cell size)
It is a graph which shows the relationship between and decomposition activity.

FIG. 4 is a graph showing the relationship between the physical properties of crystalline aluminosilicate (Al skeleton / total Al molar ratio) and decomposition activity.

FIG. 5 is a graph showing the effect of the present invention.

FIG. 6 is a graph showing the effect of the present invention.

Claims (2)

[Claims] 1. A method for catalytically cracking a heavy hydrocarbon oil containing one or both of nickel and vanadium, wherein the equilibrium catalyst is contaminated with 3000 to 13000 ppm of nickel or vanadium on average or both, The bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 5.5 to 6.9, the unit cell size is 24.34 to 24.46Å, and the molar ratio of Al in the zeolite skeleton to the total Al is as follows. Use of a catalyst composed of a crystalline aluminosilicate having a main X-ray diffraction pattern of Y-type zeolite and an inorganic oxide matrix, calculated from (1) to (3) is 0.2 to 0.4. A method for catalytically cracking heavy hydrocarbon oil, comprising: [Equation 1] 2. The catalyst contains 0.01 to 5% by weight as an oxide of at least one metal selected from the group consisting of rare earth metals and alkaline earth metals, based on the catalyst. The method of claim 1.