JP5220456B2 - Decomposition method of atmospheric distillation residue oil - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for decomposing atmospheric distillation residue oil, and more specifically, a method for decomposing atmospheric distillation residue oil by hydrocracking crude oil atmospheric distillation residue oil and subjecting the resulting product oil to fluid catalytic cracking treatment. It is about.

Atmospheric distillation residue oil of crude oil is hydrodesulfurized in a heavy oil direct desulfurization apparatus (hereinafter referred to as “direct desulfurization apparatus”) to produce distillate oil and desulfurized heavy oil such as desulfurized naphtha, desulfurized kerosene and desulfurized light oil. This desulfurized heavy oil is used as boiler fuel for electric power as a low sulfur C heavy oil. At the same time, desulfurized heavy oil is also used as a raw material for fluid catalytic cracking (FCC) equipment, catalytic cracking gasoline (hereinafter referred to as “FCC gasoline”), catalytic cracking light oil (hereinafter referred to as “LCO”: light cycle oil), LPG Light fractions such as fractions are produced.
In recent years, crude oil that can be used in oil refining has become heavier, and crude oil containing a large amount of heavy oil tends to increase. In addition, the amount of heavy oil used is decreasing, such as a decrease in demand for heavy oil for power generation and boilers. In addition, the demand for the LCO fraction from the fluid catalytic cracker is also decreasing. On the other hand, demand for gasoline is expanding, and demand for LPG fractions and naphtha fractions used as raw materials for many petrochemical products such as propylene, butene, BTX such as benzene, toluene, and xylene is also increasing. Therefore, technological development for producing a large amount of light fractions such as gasoline, naphtha fraction and LPG fraction from heavy oil such as atmospheric distillation residue oil has become an important issue.

From such a situation, desulfurized heavy oil, desulfurized heavy gas oil, etc. obtained by hydrodesulfurization treatment of heavy oil in hydrodesulfurization equipment such as direct desulfurization equipment, intermediate desulfurization equipment, etc. are further decomposed, Hydrocracking methods have been developed to increase production of desulfurized kerosene and desulfurized light oil. In addition, the above-mentioned desulfurized heavy oil and desulfurized heavy gas oil are catalytically cracked at a high cracking rate in a fluid catalytic cracking device to convert them into light fractions such as LPG fraction, FCC gasoline fraction, and LCO fraction. It has been broken.
For example, by hydrocracking atmospheric distillation residue oil, the yield of desulfurized kerosene gas oil fraction and desulfurized naphtha fraction is increased to reduce desulfurized heavy oil, and the desulfurized heavy oil is removed by fluid catalytic cracking equipment. There has been proposed a method in which a residual oil is totally reduced and a light oil fraction is increased by producing an LPG fraction, an FCC gasoline fraction, and an LCO fraction (see, for example, Patent Document 1).
However, in this method, the property of desulfurized heavy oil obtained by hydrocracking atmospheric distillation residue oil is poor, the yield of LCO fraction obtained by fluid catalytic cracking using it as a feedstock is high, and the LPG fraction The yield of light fractions with high demand such as FCC gasoline fractions is not sufficient.
Therefore, each fraction of desulfurized naphtha, desulfurized kerosene, desulfurized gas oil, etc. obtained by hydrocracking heavy oil such as atmospheric distillation residue oil, and LPG fraction obtained by catalytic cracking in a fluidized catalytic cracker following this A heavy oil cracking method that can increase production of light fractions such as FCC gasoline fractions and suppress production of LCO fractions with low demand is expected.

Japanese Patent Laid-Open No. 5-112785

  The present invention has been made under such circumstances, and the yield of each fraction of crude oil atmospheric distillation residue oil, such as desulfurized naphtha, desulfurized kerosene, desulfurized gas oil, etc. is increased, and the yield of desulfurized heavy oil is increased. Atmospheric distillation residue that can be decomposed to reduce and desulfurized heavy oil that is the residual oil can be decomposed so that the yield of LPG fraction and FCC gasoline fraction is high and the yield of LCO fraction is low It aims at providing the decomposition method of oil.

  As a result of intensive research to achieve the above object, the present inventors have obtained a hydrocracking treatment of crude oil atmospheric distillation residue using a specific catalyst, and further obtained by hydrocracking. It has been found that the above problem can be solved by subjecting the mixture of the obtained desulfurized heavy oil and the specific distillate to fluid catalytic cracking. The present invention has been completed based on such findings.

That is, the present invention
[1] A method for decomposing atmospheric distillation residue oil by hydrocracking atmospheric distillation residue oil and subjecting the resulting product oil to fluid catalytic cracking treatment,
(A) The catalyst used for the hydrocracking treatment is a catalyst in which a metal is supported on a support composed of a mixture of crystalline aluminosilicate 45 mass% to 70 mass% and porous inorganic oxide 55 mass% to 30 mass%. And (b) the raw material of the fluid catalytic cracking treatment is a mixture of the residual oil obtained by the hydrocracking treatment and a distillate having a boiling point of 120 to 400 ° C., and the mixing ratio of the distillate in the mixture is 1-30% by volume,
A method for decomposing atmospheric distillation residue oil,
[2] The pore distribution of the catalyst used for the hydrocracking treatment is such that the total pore volume of pores having a pore diameter of 500 to 10,000 mm is smaller than the total pore volume of pores having a pore diameter of 50 to 10,000 mm. Is a method for decomposing atmospheric distillation residue oil according to [1], wherein the total pore volume of pores having a pore diameter of 100 to 200 mm is 25% or more,
[3] The method for decomposing atmospheric distillation residue oil according to the above [1] or [2], wherein the crystalline aluminosilicate is USY zeolite or metal-supported USY zeolite, and the porous inorganic oxide is alumina; 4] The method for decomposing atmospheric distillation residue oil according to any one of [1] to [3] above, wherein the crystalline aluminosilicate is an iron-supported USY zeolite,
Is to provide.

  According to the present invention, crude oil atmospheric distillation residue oil is decomposed so that the yield of each fraction of desulfurized naphtha, desulfurized kerosene, desulfurized gas oil, etc. is increased and the yield of desulfurized heavy oil is reduced, and the residue It is possible to provide a method for decomposing atmospheric distillation residue oil that can decompose desulfurized heavy oil, which is an oil, so that the yield of LPG fraction and FCC gasoline fraction is high and the yield of LCO fraction is low. .

The present invention is a method for decomposing atmospheric distillation residue oil by hydrocracking atmospheric distillation residue oil and subjecting the resulting product oil to fluid catalytic cracking treatment,
(A) The catalyst used for the hydrocracking treatment is a catalyst in which a metal is supported on a support composed of a mixture of crystalline aluminosilicate 45 mass% to 70 mass% and porous inorganic oxide 55 mass% to 30 mass%. And (b) the raw material of the fluid catalytic cracking treatment is a mixture of the residual oil obtained by the hydrocracking treatment and a distillate having a boiling point of 120 to 400 ° C., and the mixing ratio of the distillate in the mixture is 1 to 30% by volume.

  The hydrocracking treatment in the present invention is carried out under conditions of high pressure of hydrogen by performing hydrodesulfurization reaction, hydrodenitrogenation reaction, hydrodemetallation reaction and the like simultaneously with the hydrocracking reaction. As a device for performing such a hydrocracking reaction under high pressure, a direct desorption device is usually used.

The conditions for hydrocracking in the present invention are not particularly limited, and may be performed under the reaction conditions conventionally used in hydrocracking or hydrodesulfurization of heavy oils. Usually, the reaction temperature is preferably from 320 to 550 ° C., more preferably 350-430 ° C., hydrogen partial pressure is preferably 1-30 MPa, more preferably 5-17 MPa, hydrogen / oil ratio is preferably 100-2000 Nm ³ / kiloliter, more preferably 300-1000 Nm ³ / Kiloliter, liquid hourly space velocity (LHSV) is preferably selected within the range of preferably 0.1 to 5 h ⁻¹ , more preferably 0.2 to 2.0 h ⁻¹ .
Atmospheric distillation of heavy oil such as vacuum residue oil, coker oil, synthetic crude oil, extracted crude oil, heavy gas oil, vacuum gas oil, LCO, HCO (heavy cycle oil), CLO (clarified oil), GTL oil, wax, etc. It can also be hydrocracked by mixing with residual oil.

The catalyst used in the hydrocracking treatment of the present invention needs to be a catalyst in which a metal is supported on a carrier made of a mixture of crystalline aluminosilicate and porous inorganic oxide.
Various crystalline aluminosilicates can be used, such as hydrogen-type faujasite, USY zeolite, metal-supported USY zeolite, etc. Among them, USY zeolite and metal-supported USY zeolite are preferable. Supported USY zeolite is preferred.
The metal-supported USY zeolite is preferably a metal-supported USY zeolite in which one or more metals selected from Group 3 to 16 of the periodic table are supported on USY zeolite. Zeolite is preferred.

The USY zeolite and metal-supported USY zeolite can be produced, for example, by the following method.
As a raw material for USY zeolite, the ratio of silica to alumina (molar ratio), that is, SiO ₂ / Al ₂ O ₃ is 4.5 or more, preferably 5.0 or more, and Na ₂ O is 2.4% by mass. Hereinafter, Y-type zeolite of 1.8% by mass or less is preferably used.
First, the above Y-type zeolite is steamed to form USY zeolite. Here, the conditions for the steaming treatment may be appropriately selected according to various situations, but the treatment is preferably performed in the presence of water vapor at a temperature of 510 to 810 ° C. Water vapor may be introduced from the outside, or physically adsorbed water or crystal water contained in the Y-type zeolite may be used. Further, by adding a mineral acid to the USY zeolite obtained by the steaming treatment, and mixing and stirring, the aluminum falling from the zeolite structure skeleton is removed and the aluminum dropped off is washed and removed by the steaming and mineral acid treatment.
Examples of such mineral acids include various types of acids such as hydrochloric acid, nitric acid, and sulfuric acid, but also phosphoric acid, perchloric acid, peroxodisulfonic acid, dithionic acid, sulfamic acid, and nitrososulfonic acid. Inorganic acids such as formic acid, trichloroacetic acid, organic acids such as trifluoroacetic acid, and the like can also be used. The amount of mineral acid to be added is 0.5 to 20 mol, preferably 3 to 16 mol, per kg of USY zeolite. The mineral acid concentration is 0.5 to 50% by mass solution, preferably 1 to 20% by mass solution. The treatment temperature is room temperature to 100 ° C, preferably 50 to 100 ° C. The processing time is 0.1 to 12 hours.

  Subsequently, a metal salt solution is added to the system to support the metal on the USY zeolite. Examples of the supporting method include mixed stirring treatment, dipping method, and impregnation method, and mixed stirring treatment is preferable. Examples of metals include yttria, lanthanum, group 4 zirconia, titanium, group 5 vanadium, niobium, thallium, group 6 chromium, molybdenum, tungsten, group 7 manganese, rhenium, Group 8 iron, ruthenium, osmium, Group 9 cobalt, rhodium, iridium, Group 10 nickel, palladium, platinum, Group 11 copper, Group 12 zinc, cadmium, Group 13 aluminum, gallium , Group 14 tin, Group 15 phosphorus, antimony, Group 16 selenium, and the like. Among these, titanium, iron, manganese, cobalt, nickel, palladium, and platinum are preferable, and iron is particularly preferable.

As the salts of various metals, sulfates and nitrates are preferable. When the metal salt solution treatment is performed, it cannot be determined uniquely depending on the situation, but the treatment temperature is usually 30 to 100 ° C., preferably 50 to 80 ° C., the treatment time is 0.1 to 12 hours, preferably 0. The loading of these metals is preferably carried out simultaneously with dealumination from the zeolite structure skeleton, and is appropriately selected and carried out within a pH range of 2.0 or less, preferably 1.5 or less. Examples of the iron salt include ferrous sulfate and ferric sulfate, and ferric sulfate is preferable. Although this iron sulfate can be added as it is, it is preferably added as a solution. The solution at this time may be any solution that dissolves the iron salt, but water, alcohol, ether, ketone and the like are preferable. The concentration of iron sulfate to be added is usually 0.02 to 10.0 mol / liter, preferably 0.05 to 5.0 mol / liter.
In addition, when the crystalline aluminosilicate is treated by adding the mineral acid and iron sulfate, the slurry ratio, that is, the treatment solution volume (liter) / aluminosilicate weight (kg) is in the range of 1-50. Convenient, 5-30 is particularly preferred.
The iron-supporting crystalline aluminosilicate obtained by the above-described treatment is further washed and dried as necessary.
As described above, USY zeolite and metal-supported USY zeolite can be produced.

  On the other hand, examples of the porous inorganic oxide mixed with the crystalline aluminosilicate to constitute the carrier include alumina, silica-alumina, alumina-boria, alumina-zirconia, and alumina-titania. As alumina, boehmite gel, alumina sol Or the alumina manufactured from these is used. Of these, alumina is preferable in that the active metal can be supported in a highly dispersed manner.

The catalyst carrier used in the hydrocracking step of the present invention is a mixture of crystalline aluminosilicate and porous inorganic oxide such as the above-mentioned USY zeolite and metal-supported USY zeolite. The mixing ratio is required to be 45% by mass or more and 70% by mass or less of crystalline aluminosilicate and 55% by mass or less and 30% by mass or more of the porous inorganic oxide. If the proportion of crystalline aluminosilicate in the mixture of crystalline aluminosilicate and porous inorganic oxide is too small, a high reaction temperature is required to obtain the desired decomposition rate, light fraction and middle fraction, and as a result Adversely affects the life of the catalyst. On the other hand, if the proportion of crystalline aluminosilicate is too high, the decomposition activity is improved, but the gas content increases due to overdecomposition and the selectivity of the desired light fraction and middle fraction is lowered.
On the other hand, porous inorganic oxides such as alumina disperse the active metal supported to a high degree, so if the proportion of porous inorganic oxide is large, the hydrogenation activity is high, and desulfurization activity, denitrogenation activity, decarburization activity Although the deasphaltenic activity and the demetallizing activity are improved, the proportion of crystalline aluminosilicate is reduced, and it becomes difficult to obtain a desired decomposition rate, light fraction and middle fraction. Moreover, when the ratio of a porous inorganic oxide is small, hydrogenation activities, such as a desulfurization activity, a denitrification activity, a decarburization activity, a deasphalten activity, a demetalization activity, will fall. Therefore, the mixing ratio of the catalyst containing crystalline aluminosilicate and the porous inorganic oxide is more preferably composed of 45 to 65% by mass of crystalline aluminosilicate and 55 to 35% by mass of porous inorganic oxide. What consists of 45-55 mass% of porous aluminosilicate and 55-45 mass% of porous inorganic oxides is suitable.

In addition, in order to produce a catalyst carrier for use in the hydrocracking treatment of the present invention, crystalline aluminosilicates such as the above USY zeolite and metal-supported USY zeolite should be used as a slurry containing water after washing with water. Is preferred. Then, the crystalline aluminosilicate and the porous inorganic oxide are sufficiently mixed with a kneader (kneader) under a sufficient water content.
The porous inorganic oxide is in the form of a gel or sol, but is mixed with the crystalline aluminosilicate in the form of a slurry by adding water in the same manner as in the crystalline aluminosilicate. The water content in each slurry state is preferably 30 to 80% by mass, more preferably 40 to 70% by mass in the crystalline aluminosilicate slurry. In the porous inorganic oxide slurry, 50 to 90% by mass is preferable, and 55 to 85% by mass is more preferable.
After mixing and kneading the above crystalline aluminosilicate and porous inorganic oxide, it is molded into a diameter of 1/12 inch to 1/32 inch and a length of 1.5 mm to 6 mm, cylindrical, three-leaf type, four-leaf type A molded product of the shape is obtained. The molded product is dried at 30 to 200 ° C. for 0.1 to 24 hours, and then calcined at 300 to 750 ° C. (preferably 450 to 700 ° C.) for 1 to 10 hours (preferably 2 to 7 hours) to obtain a carrier. .

Next, at least one metal of Group 6, Group 8, Group 9, and Group 10 metals is supported on the carrier. Here, the metal belonging to Group 6 of the periodic table is preferably molybdenum or tungsten, and the metal belonging to Groups 8 to 10 is preferably nickel or cobalt. Examples of the combination of the two kinds of metals include nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, cobalt-tungsten, etc., among which cobalt-molybdenum and nickel-molybdenum are preferable, and nickel-molybdenum is particularly preferable.
The supported amount of the metal as the active ingredient is not particularly limited and may be appropriately selected according to various conditions such as the type of the raw material oil and the desired yield of the naphtha fraction. Is 0.5-30% by mass of the total catalyst, preferably 5-20% by mass, and Group 8-10 metals are 0.1-20% by mass, preferably 1-10% by mass of the total catalyst.

The method for supporting the metal component on the carrier is not particularly limited, and for example, known methods such as an impregnation method, a kneading method, and a coprecipitation method can be employed.
The above metal component supported on a carrier is usually dried at 30 to 200 ° C. for 0.1 to 24 hours, and then at 250 to 700 ° C. (preferably 300 to 650 ° C.) for 1 to 10 hours (preferably Is calcined for 2-7 hours and finished as a catalyst.

The catalyst used for the hydrocracking of the present invention preferably satisfies the following requirements.
(1) Pore Volume The hydrocracking catalyst used in the present invention has a pore volume of 10 to 10 pores with a pore size of 500 to 10,000 pores with respect to the total pore volume of pores of 50 to 10,000 pores. % Or more is preferable. The pore volume of pores having a pore diameter of 100 to 200 mm is preferably 25% or more with respect to the total pore volume of pores having a pore diameter of 50 to 10,000 mm, and pores having a pore diameter of 50 to 500 mm More preferably, it is 50% or more of the pore volume.
The catalyst having such a pore distribution can easily control high molecular weight hydrocarbons such as asphaltenes in the residual oil, and can facilitate hydrogenation and decomposition of heavy oil.
The pore volume is a value obtained by mercury porosimetry using a mercury porosimeter.
(2) hydrocracking catalysts used in the specific surface area present invention preferably has a specific surface area of ^{200~600m 2 / g, 350~500m 2 /} g is more preferable. If the specific surface area is 200 m ² / g or more, a sufficient amount of decomposition active sites suitable for heavy oil decomposition can be arranged on the catalyst surface, and if it is 600 m ² / g or less, it is sufficient for diffusion of heavy oil molecules. Can have large pores. In addition, a specific surface area is the value measured by the BET 1 point method by nitrogen gas.
(3) Total pore volume The total pore volume of the catalyst according to the nitrogen gas adsorption method is preferably 0.4 cc / g or more, and more preferably 0.5 cc / g or more. If the total pore volume is 0.4 cc / g or more, the diffusion of heavy oil molecules can be enhanced.

  The hydrocracking catalyst obtained in the above production method and physical property range has improved hydrogenation activity, high cracking activity of residual oil (a fraction having a boiling point of 343 ° C. or higher), and decarburization activity. It has high desulfurization activity, denitrogenation activity, deasphaltenic activity and demetallization activity and is suitable for lightening heavy oil fractions, and the yield of desulfurized naphtha fraction and desulfurized kerosene oil oil fraction to be produced is also increased.

  In the hydrocracking treatment of the present invention, the catalyst of the present invention may be used alone, or a combination with a general hydrotreating catalyst may be used. As a combination pattern, for example, the demetalization catalyst is 10 to 40% by volume in the first stage, the desulfurization catalyst is 0 to 50% by volume in the second stage, and the present invention is in the third stage with respect to the total catalyst charge. The hydrocracking catalyst is preferably 10 to 70% by volume, and the fourth stage is preferably a filling pattern of 0 to 40% by volume as the finishing desulfurization catalyst. These can have various filling patterns depending on the properties of the feedstock. A descaling catalyst for removing scales such as iron powder and inorganic oxide contained in the raw material oil may be filled before the first stage demetallation catalyst.

In the present invention, the atmospheric distillation residue oil is hydrocracked using such a catalyst, and fluid catalytic cracking treatment is performed using a mixed oil of the obtained residual oil and distillate as a raw material.
In this case, a distillate having a boiling point of 120 to 400 ° C. is suitable as the distillate. Distillate with a boiling point of less than 120 ° C does not yield a decomposition product with a good boiling range, while distillate with a boiling point of more than 400 ° C has the effect of mixing the distillate and the effect of increasing FCC gasoline, etc. May not be enough. Therefore, as the distillate oil, those having a boiling range of 150 to 350 ° C are more preferable.
Moreover, the mixing ratio of the distillate oil in the raw material of fluid catalytic cracking process needs to be 1-30 volume%. If the mixing ratio of the distillate is less than 1% by volume, the effect of increasing the LPG fraction or FCC gasoline fraction is not sufficient. On the other hand, if it exceeds 30% by volume, the yield of the LPG fraction or FCC gasoline fraction is insufficient. There is a risk that the gas content will increase. A preferable mixing ratio is 3 to 20% by volume.
In addition, as a method of mixing the distillate oil with the residual oil, the residual oil may be mixed with a pipe for introducing into the fluid catalytic cracking apparatus, or the distillate oil may be cut into the residual oil in the distillation equipment of the direct desorption apparatus. You may back.

  In the present invention, the catalytic cracking treatment is performed using the above raw materials. The catalytic cracking treatment is not particularly limited and may be performed by a known method and conditions. For example, using an amorphous catalyst such as silica-alumina or silica-magnesia or a zeolite catalyst such as faujasite type crystal aluminosilicate, the reaction temperature is 450 to 650 ° C, preferably 480 to 580 ° C, the regeneration temperature is 550 to 760 ° C, The reaction pressure may be appropriately selected within the range of 0.02 to 5 MPa, preferably 0.2 to 2 MPa.

In the cracking treatment of atmospheric distillation residue oil of the present invention, the product of the fluid catalytic cracking, which is the final step, is useful as a raw material for fuel and petrochemical products, and the proportion of FCC gasoline fraction and LPG fraction is high. The ratio of the LCO fraction with a small amount can be reduced.
In addition, the yield of kerosene oil fraction, which is a so-called middle distillate, and fusa fraction, which is a light distillate, is high in the hydrocracking products such as direct desulfurization equipment that is an intermediate process. Can be used as

EXAMPLES Next, although an Example demonstrates this invention concretely, it is not restrict | limited to these Examples at all.
In Examples and Comparative Examples, Arabianite atmospheric distillation residue oil having the properties and fraction distribution shown in Table 1 was used as a raw material.

Moreover, the preparation of the hydrocracking catalyst used in the examples and the evaluation of its physical properties were performed as follows.
1. Preparation of catalyst [hydrocracking catalyst I]
(1) Preparation of crystalline aluminosilicate Na—Y zeolite (Na ₂ O content: 13.3 mass%, SiO ₂ / Al ₂ O ₃ (molar ratio): 5.0) was subjected to ammonium ion exchange, and NH ₄ -Y zeolite (Na ₂ O content: 1.3% by mass) was obtained. This was steamed at 650 ° C. to obtain a steaming Y-type zeolite. After 10 kg of steamed Y-type zeolite was suspended in 115 liters of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Next, 63.7 kg of 10 mass% sulfuric acid solution was added to this suspension over 35 minutes, and 11.5 kg of ferric sulfate solution having a concentration of 0.57 mol / liter was added over 10 minutes. After stirring, the mixture was filtered and washed to obtain an iron-supported USY zeolite slurry I having a solid content concentration of 30.5% by mass. The lattice constant determined by the X-ray diffraction method was 24.30 Å.
(2) Preparation of Alumina Slurry 80 kg of sodium aluminate solution (Al ₂ O ₃ equivalent concentration: 5.0 mass%) and 240 g of 50 mass% gluconic acid solution were put in a container and heated to 60 ° C. Next, 88 kg of aluminum sulfate solution (Al ₂ O ₃ equivalent concentration: 2.5 mass%) was prepared in a separate container, and the aluminum sulfate solution was added so that the pH became 7.2 in 15 minutes to obtain an aluminum hydroxide slurry. . Aging was performed for 60 minutes while maintaining the temperature at 60 ° C. Next, the aluminum hydroxide slurry was filtered and dehydrated and washed with aqueous ammonia to obtain an alumina cake. A part of the alumina cake was purified water and 15% by mass of ammonia water to obtain a slurry having an alumina concentration of 12.0% by mass and a pH of 10.5. The slurry was placed in an aging tank and aged at 95 ° C. for 8 hours with stirring. Next, pure water was added to the aging slurry, diluted to an alumina concentration of 9.0% by mass, transferred to an autoclave equipped with a stirrer, and aged at 145 ° C. for 5 hours. Further, the mixture was heated and concentrated so that the concentration in terms of Al ₂ O ₃ was 20% by mass, and deammoniated at the same time to obtain alumina slurry A.

(3) Preparation of catalyst 1,230 g of iron-supported USY zeolite slurry I (30.5 mass% concentration) and 1,875.8 g of alumina slurry A (20 mass% concentration) were added to a kneader while heating and stirring. After concentration to an extrudable concentration, it was extruded into a four-leaf type pellet of 1/18 inch size. Subsequently, after drying at 110 degreeC for 16 hours, it baked at 550 degreeC for 3 hours, and obtained the support | carrier I of 50/50 by the iron carrying | support USY zeolite / alumina (solid content conversion mass ratio).
Next, a suspension of molybdenum trioxide and nickel carbonate in pure water was heated to 90 ° C., and then malic acid was added and dissolved. The solution I was impregnated on the support I so that the total amount of the catalyst was 10.0% by mass as MoO _{3 and} 4.25% by mass as NiO, then dried, calcined at 550 ° C. for 3 hours, and hydrogenated. A cracking catalyst I was obtained. This catalyst had a specific surface area of 473 m ² / g and a total pore volume of 0.61 cc / g. Moreover, the pore volume with a pore diameter of 500-10,000 to 11% was 11% with respect to the pore volume with a pore diameter of 50 to 10,000 with a mercury porosimeter. Furthermore, the pore volume with a pore diameter of 100 to 200 ５９ was 59% of the pore volume with a pore diameter of 50 to 10,000 、 and 65% of the pore volume with a pore diameter of 50 to 500 Å. The composition and physical properties of the catalyst are shown in Table 2.

[Hydrocracking catalyst II]
In preparation of the hydrocracking catalyst I, the iron-supported USY zeolite slurry I (30.5% by mass concentration) was 1,476 g, and the alumina slurry A (20% by mass concentration) was 1,500 g, which was added to the kneader. Was prepared in the same manner to obtain 60/40 carrier II of iron-supported USY zeolite / alumina (solid content equivalent mass ratio).
Subsequently, a suspension of molybdenum trioxide and nickel carbonate in pure water was heated to 90 ° C., and then malic acid was added and dissolved. This solution was impregnated on the carrier II so that the total amount of the catalyst was 10.0% by mass as MoO _{3 and} 4.25% by mass as NiO, then dried, calcined at 550 ° C. for 3 hours, and hydrogenated. Cracking catalyst II was obtained. This catalyst had a specific surface area of 517 m ² / g and a total pore volume of 0.56 cc / g. According to the mercury porosimeter, the pore volume with a pore diameter of 500 to 10,000 kg was 32% with respect to the pore volume with a pore diameter of 50 to 10,000 kg. Furthermore, the pore volume with a pore diameter of 100 to 200 ４３ was 43% of the pore volume with a pore diameter of 50 to 10,000 、 and 63% of the pore volume with a pore diameter of 50 to 500 Å. The composition and physical properties of the catalyst are shown in Table 2.

2. Evaluation method of physical properties of catalyst [Measurement of physical properties of iron-supported USY zeolite]
(1) Lattice constant: The dried iron-supported USY zeolite and the silicon internal standard powder were mixed well, pulverized, and filled into a sample holder for X-ray powder diffraction. This was measured by a step scan with a Cu tube, an applied voltage of 40 KV, and an applied current of 40 mA, and the lattice constant (UD) of the iron-supported USY zeolite was calculated from the obtained peak angle.
[Measurement of physical properties of catalyst]
(1) Pore volume: The pore distribution and pore volume of the catalyst were determined by mercury porosimetry using a mercury porosimeter.
(2) Specific surface area and total pore volume: The specific surface area was measured by the BET one-point method by nitrogen gas adsorption. The total pore volume was measured from the amount of nitrogen adsorbed when the equilibrium vapor pressure P (P / P ₀ ) of nitrogen gas relative to the saturated vapor pressure P ₀ of nitrogen gas at the liquid nitrogen temperature was 0.99.

[Evaluation of hydrocracking activity of catalyst]
The molded catalyst pellets were charged into a high-pressure fixed bed reactor and subjected to sulfurization treatment. Then, the reaction temperature was 395 ° C. in terms of weight average temperature (WAT) using Arabianlite atmospheric distillation residue as a raw material oil. Hydrocracking treatment was performed under the conditions of a liquid space velocity (LHSV) of 0.2 h ⁻¹ , a hydrogen partial pressure of 12.8 MPa, and a hydrogen / oil ratio of 900 Nm ³ / kiloliter.
The resulting product oil is analyzed by a distillation gas chromatography method, the boiling point is 343 ⁺ ° C. fraction (fraction having a boiling point higher than 343 ° C.) decomposition rate, the kerosene oil fraction (boiling point range 150 to 343 ° C.) as the middle fraction The yield was determined and the hydrocracking activity of the atmospheric distillation residue was evaluated.

Example 1
(1) 24% by volume of a commercially available demetallized catalyst (CDS-DM5C: manufactured by Catalytic Chemical Industry) in the first stage, and 20% by volume of a commercially available desulfurization catalyst A (CDS-R25N: manufactured by Catalysts Chemical Industry) in the second stage. The hydrocracking catalyst I is packed in 28 stages by volume in the third stage, and the commercially available desulfurization catalyst B (CDS-R35N: produced by Catalyst Kasei Kogyo Co., Ltd.) in the fourth stage in the order of 28 volume% in series in four stages. After charging into a fixed bed reactor and sulfiding, hydrocracking treatment is performed under the following conditions using Arabianlite atmospheric distillation residue oil as a raw material oil, and desulfurized kerosene oil fraction (boiling point range: 150-343 ° C distillation) Minute) yield (mass%) was measured. The results are shown in Table 3.
Hydrocracking conditions Reaction temperature (WAT) 395 ° C
Liquid space velocity (LHSV) 0.2h ^-1
Hydrogen partial pressure 12.5 MPa (128 kg / cm ² )
Hydrogen / oil ratio 900 Nm ³ / kiloliter The reaction temperature of each catalyst layer was 386 ° C. for the first stage, 383 ° C. for the second stage, 401 ° C. for the third stage, and 406 ° C. for the fourth stage.

(2) The product oil obtained by the hydrocracking treatment of (1) is distilled based on a distillation test method using a rectifying tower with 15 theoretical plates of JIS K 2601, and the gas content (C ₄ ⁻ ) is desulfurized. Naphtha fraction (boiling range C _{5 to} 150 ° C.), desulfurized kerosene fraction (boiling range 150 to 250 ° C.), desulfurized gas oil fraction (boiling range 250 to 343 ° C.) and desulfurized heavy oil fraction (343 ⁺ (Centigrade).
Next, among these fractions, a mixture of desulfurized heavy oil and desulfurized gas oil fraction (boiling range: 250 to 343 ° C.) (mixing ratio of desulfurized gas oil fraction is 5% by volume) is used as a raw material, and a commercially available equilibrium catalyst is used. The fluid catalytic cracking treatment was performed under the conditions of a reaction temperature of 530 ° C. and a catalyst / raw material ratio = 5.0 (mass ratio).
About the reaction product of fluid catalytic cracking treatment, gas fraction by gas chromatography, PP fraction (propane, propylene), BB fraction (butane, butylene), FCC gasoline fraction (boiling point C ₅ -185 ° C fraction) ), LCO fraction (boiling range: 185-370 ° C. fraction), and residual oil fraction (cracked heavy oil: HCO + CLO) yield (volume%) was measured. The results are shown in Table 3.
HCO is heavy cycle oil and CLO is clarified oil.

Example 2
Hydrocracking treatment and fluid catalytic cracking treatment were performed in the same manner as in Example 1 except that the mixing ratio of the desulfurized gas oil fraction (boiling range: 250 to 343 ° C.) was 3% by volume in Example 1. The results are shown in Table 3.

Example 3
Hydrocracking treatment and fluid catalytic cracking treatment were carried out in the same manner as in Example 1 except that the mixing ratio of the desulfurized gas oil fraction (boiling range: 250 to 343 ° C.) was 15 vol% in Example 1. The results are shown in Table 3.

Example 4
Hydrocracking treatment and fluid catalytic cracking treatment were performed in the same manner as in Example 1 except that the hydrocracking catalyst I was changed to the hydrocracking catalyst II in Example 1. The results are shown in Table 3.

Comparative Example 1
In Example 1 of the present invention, the hydrocracking treatment and the hydrocracking treatment were performed in the same manner as in Example 1 except that the third stage catalyst was changed to the same desulfurization catalyst A as the second stage without charging the hydrocracking catalyst I. Fluidized catalytic cracking treatment was performed. The results are shown in Table 3.

Comparative Example 2
In Example 1 of the present invention, hydrocracking treatment and fluid contact in the same manner as in Example 1 except that only the residual oil was used without mixing the desulfurized gas oil fraction (boiling range: 250 to 343 ° C.). Decomposition was performed. The results are shown in Table 3.

Comparative Example 3
In Example 1 of the present invention, hydrocracking treatment and fluid catalytic cracking treatment were performed in the same manner as in Example 1 except that the mixing ratio of the desulfurized gas oil fraction (boiling range: 250 to 343 ° C.) was 40% by volume. . The results are shown in Table 3.

From Table 3, the decomposition method (Examples 1 to 4) of the atmospheric distillation residue oil of the present invention is an intermediate by hydrocracking treatment as compared with the method of Comparative Example 1 that does not use the hydrocracking catalyst of the present invention. It can be seen that the yield of the fraction (desulfurized kerosene fraction) is high. Further, in the oil produced by fluid catalytic cracking treatment, the yield of FCC gasoline fraction and LPG fraction is high, and the yield of LCO fraction is low.
On the other hand, as in the method of Comparative Example 2, as a raw material for fluid catalytic cracking treatment, when using only residual oil without mixing distillate oil, or as in the method of Comparative Example 3, fluid catalytic cracking When the ratio of the distillate fraction is increased to 40% by volume as the raw material, the yield of the FCC gasoline fraction is low and the yield of the LCO fraction is high.

  According to the cracking method of atmospheric distillation residue oil of the present invention, the production ratio of kerosene oil fraction, which is a middle distillate in hydrocracking, is high, and FCC gasoline fraction or LPG which is a light fraction in fluid catalytic cracking. The production of the fraction can be increased and the production of the LCO fraction can be reduced. Therefore, it can be effectively used as a method capable of increasing the production of gasoline base materials and basic raw materials for petrochemical products used for gasoline fuel.

Claims (4)

A method for decomposing atmospheric distillation residue oil by hydrocracking atmospheric distillation residue oil and subjecting the resulting product oil to fluid catalytic cracking treatment,
(A) The catalyst used for the hydrocracking treatment is a catalyst in which a metal is supported on a support composed of a mixture of crystalline aluminosilicate 45 mass% to 70 mass% and porous inorganic oxide 55 mass% to 30 mass%. And (b) the raw material of the fluid catalytic cracking treatment is a mixture of the residual oil obtained by the hydrocracking treatment and a distillate having a boiling point of 120 to 400 ° C., and the mixing ratio of the distillate in the mixture is 1-30% by volume,
A method for decomposing atmospheric distillation residue oil characterized by the above. The pore distribution of the catalyst used for the hydrocracking treatment is 10% of the total pore volume of the pores having a pore diameter of 500 to 10,000 to the total pore volume of the pores having a pore diameter of 50 to 10,000 The method for decomposing atmospheric distillation residue oil according to claim 1, wherein the total pore volume of pores having a pore diameter of 100 to 200 mm is 25% or more.   The method for decomposing atmospheric distillation residue oil according to claim 1 or 2, wherein the crystalline aluminosilicate is USY zeolite or metal-supported USY zeolite, and the porous inorganic oxide is alumina.   The method for decomposing atmospheric distillation residue oil according to any one of claims 1 to 3, wherein the crystalline aluminosilicate is an iron-supported USY zeolite.