JPH05112785A - Treatment of heavy hydrocarbon oil - Google Patents

Abstract

PURPOSE:To provide the title process whereby a naphtha fraction and a kerosene and gas oil fraction can be obtained efficiently in high yields from a heavy hydrocarbon oil. CONSTITUTION:The title process comprises subjecting a heavy hydrocarbon oil to hydrotreatment comprising successively performing hydrodemetallizing 1, hydrocracking 2 and hydrodesulfurization and hydrodenitrogenation 3 in the presence of catalysts, subjecting the treated oil to distillation 4 and subjecting the residual oil to fluidized bed catalytic cracking 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a heavy hydrocarbon oil, and more particularly, a heavy hydrocarbon oil is treated in combination with a hydrotreating treatment and a fluidized bed catalytic cracking treatment to obtain a naphtha fraction and The present invention relates to an efficient treatment method for heavy hydrocarbon oil, which is capable of obtaining a kerosene oil fraction with a high yield.

[0002]

2. Description of the Related Art Applications of petroleum include fuels (especially for heating and transportation) and petrochemical raw materials. Although it is expected that the demand for heating will be replaced by other energy sources in the future, the demand for gasoline, light oil, and jet fuel oil, which are fuel oils for transportation, is expected to grow quite rapidly. In addition, in recent years, as crude oil prices have risen, crude oil has become heavier, and demand for light hydrocarbons has increased, residual oil consisting of heavy hydrocarbon oils is cracked and processed, and naphtha fractions and light oil are used as transportation fuels. It is desired to develop a technique capable of efficiently producing a fraction. And in particular, the flexibility of production, which can change the product composition depending on the season and the place, is an important factor for responding to changes in demand. For this,
Various processes have already been proposed. For example, first
There has been proposed a method of treating atmospheric residual oil in combination with a direct desulfurization treatment step (RH) and a fluidized bed catalytic cracking treatment step (R-FCC). However, this method has a drawback that R-FCC having a large processing capacity is required because decomposition by RH is small. Further, there is a disadvantage that catalytic cracking gas oil of low value, that is, catalytic cracking gas oil that has a low cetane index and does not serve as direct transportation gas oil (for example, diesel engine fuel) is produced in large quantities. Further, after the atmospheric residual oil is distilled under reduced pressure and fractionated, the resulting reduced pressure gas oil is hydrotreated with the reduced pressure residual oil to be hydrodesulfurized together with the reduced pressure gas oil, and this processed oil is subjected to R-FCC treatment. Methods have also been proposed. This method can process relatively heavy feedstocks, but has a drawback that the main product is FCC gasoline, and at the same time, low-value catalytic cracking gas oil and catalytic cracking residual oil are co-produced. And, there is a drawback that it is not possible to produce a high-quality gas oil fraction other than FCC gasoline. Furthermore, a method has also been proposed in which the same vacuum distillation residue oil as described above is desulfurized in a fixed bed and then subjected to R-FCC. In this method, there is a problem in operating the desulfurization treatment in a fixed bed for a long period of time, and since it is a cracked product oil obtained by using vacuum distillation residue oil as a raw material, the reactivity in the R-FCC treatment remarkably decreases. Is concerned. further,
Other than FCC gasoline, there is a drawback that a large amount of low-quality catalytically cracked gas oil and catalytically cracked residual oil are co-produced. As described above, the fact that there is no satisfactory technology capable of efficiently producing a naphtha fraction or a light oil fraction as a fuel for transportation by decomposing residual oil, and the development of the technique Is strongly desired.

[0003]

Therefore, the present inventors have
A method for treating heavy hydrocarbon oil capable of solving the above-mentioned conventional problems and performing stable operation with simple management, and efficiently obtaining a naphtha fraction and a kerosene gas oil fraction with a high yield. We have earnestly researched for development. As a result, it is possible to achieve the above object by skillfully combining the fluidized bed catalytic cracking treatment with the hydrodemetallizing treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment in sequence. I found it. The present invention has been completed based on such findings.

That is, according to the present invention, heavy hydrocarbon oil is hydrotreated in the presence of a catalyst in the order of hydrodemetallizing treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment. The present invention provides a method for treating heavy hydrocarbon oil, which comprises subjecting the resulting hydrotreated oil to distillation separation, and then subjecting the residual oil to fluidized bed catalytic cracking treatment.

[0005] First, the feedstock to be used in the present invention is various heavy hydrocarbon oils, for example, crude oil at atmospheric distillation residue oil and vacuum distillation residue oil, heavy gas oil, vacuum gas oil, solvent dewatering. Examples include heavy hydrocarbon oils such as asbestos oil, demetallized oil, catalytic cracking residual oil, visbreaking oil, tar sand oil, and shell oil. In the present invention,
These heavy hydrocarbon oils are first mixed with hydrogen and hydrotreated in the presence of a catalyst. That is, in the presence of a catalyst, heavy hydrocarbon oil is subjected to hydrodemetalization treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment in this order for hydrotreatment. Here, in the hydrodemetallizing treatment, heavy hydrocarbon oil and hydrogen gas are mixed, and this mixture is sent to a hydrodemetallizing apparatus for treatment. The hydrodemetallizing treatment is carried out by an apparatus composed of one to a plurality of reaction towers. This hydrodemetallization process is carried out in fixed bed, boiling bed,
It does not matter whether it is a moving bed, upflow, downflow, solvent extraction, etc. In this case, in the fixed bed, each reaction tower is divided into a plurality of catalyst beds, and a fluid is introduced into each catalyst bed to cool the reactants. The hydrodemetallizing catalyst used in the case of a fixed bed uses a porous inorganic oxide such as alumina, silica, silica-alumina or sepiolite as a carrier, and a metal or metal of Group VIA and Group VIII of the periodic table. It may be any of commercially available demetallization catalysts in which one or a plurality of compounds (hereinafter, sometimes referred to as a metal) are supported in an oxide state. And, as the processing condition of this hydrodemetallizing treatment, the reaction temperature is from 300 to 45.
0 ℃, hydrogen partial pressure 30 ~ 200kg / cm ² G, hydrogen / oil ratio 30
0-2,000 Nm ³ / kl, LHSV (liquid hourly space velocity) = 0.
^{1 to} 10 hr ^-1 , preferably a reaction temperature of 360 to 420 ° C,
Hydrogen partial pressure 100 to 180 kg / cm ² G, hydrogen / oil ratio 500 to
1,000 Nm ^{3 /} kl, LHSV = 0.3 to 5.0 hr ⁻¹ .

Next, the effluent oil that has been hydrodemetallized is sent to the hydrocracking process. The hydrocracking process is carried out by an apparatus composed of one to a plurality of reaction towers. Then, in the case of a fixed bed, each reaction tower is divided into a plurality of catalyst beds, and a fluid is introduced into each catalyst bed in order to cool the reactants. The catalyst used in this hydrocracking treatment is alumina, silica, alumina boria, zeolite or the like as a carrier, and one or more metals of Group VIA and Group VIII of the Periodic Table are supported in an oxide state. It is a thing. In addition, Japanese Examined Patent Publication No. 61-24433 and Japanese Patent Publication No. 3-
Metals of Group VIA and Group VIII of the Periodic Table on a carrier composed of 20 to 80% by weight of iron-containing zeolite and 80 to 20% by weight of inorganic oxides, which is produced by the technique disclosed in Japanese Patent No. 21484. It is also possible to use one in which one or more of them are supported in an oxide state. Furthermore, JP-A-2
-289419, a carrier composed of 10 to 90% by weight of an iron-containing zeolite and 90 to 10% by weight of an inorganic oxide, and a metal of Group VIA or VIII of the Periodic Table prepared by the technique disclosed in JP-A-289419. It is also possible to use one in which one or more of them are supported in an oxide state. In particular, when the iron-containing aluminosilicate obtained by treating steaming steaming zeolite with an aqueous solution of iron salt, which is disclosed in JP-A-2-289419, is used,
It is very effective in increasing the decomposition rate from a fraction of 43 ° C or higher to a fraction of 343 ° C or lower. Where VI of the Periodic Table
Mo and W are preferable as the group A metal. Also, the same
Ni and Co are preferable as the Group VIII metal. The processing conditions for this hydrocracking treatment are as follows: reaction temperature 300 to 450 ° C., hydrogen partial pressure 30 to 200 kg / cm ² G, hydrogen / oil ratio 300 to 2,000 Nm ³ / kl, LHSV = 0.1 to
2.0 hr ^-1 , preferably reaction temperature 380 to 420 ° C, hydrogen partial pressure 100 to 180 kg / cm ² G, hydrogen / oil ratio 500 to 1.0
00 Nm ^{3 /} kl, LHSV = 0.2 to 1.0 hr ⁻¹ . As a result of this hydrocracking treatment, a high-quality naphtha fraction and kerosene gas oil fraction can be obtained at a high rate by cracking from a fraction at 343 ° C or higher to a fraction at 343 ° C or lower.

The effluent that has been hydrodemetallized and then hydrocracked is further hydrodesulfurized and hydrodenitrogenated. The hydrodesulfurization and hydrodenitrogenation treatments are carried out by an apparatus composed of one to a plurality of reaction towers. Then, in the case of a fixed bed, each reaction tower is divided into a plurality of catalyst beds, and a fluid is introduced into each catalyst bed in order to cool the reactants. The catalyst used for the hydrodesulfurization and hydrodenitrogenation treatment may be the one usually used for hydrodesulfurization treatment. For example, periodic table VI of Mo, W, etc.
One or more of Group A metals and Group VIII metals such as Co and Ni, specifically Co-Mo or Ni-Mo, are supported on a carrier such as alumina, silica, zeolite or a mixture thereof. It is a thing. The treatment conditions for the hydrodesulfurization and hydrodenitrogenation treatment include a reaction temperature of 300 to 4
50 ℃, hydrogen partial pressure 30-200kg / cm ² G, hydrogen / oil ratio 3
00-2,000 Nm ^{3 /} kl, LHSV 0.1-2.0 hr ^-1 , preferably reaction temperature 360-420 ° C, hydrogen partial pressure 100
~ 180kg / cm ² G, hydrogen / oil ratio 500 ~ 1,000Nm ³ /
kl, LHSV 0.1 to 0.5 hr. As a result of this hydrodesulfurization and hydrodenitrogenation treatment, it is possible in particular to improve the quality of the cuts above 343 ° C.

The above hydrodemetallizing treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment are contained in the feed oil when the inlet temperature of each treatment step is arbitrarily changed to 300 to 420 ° C. 20 fractions with a boiling point of 343 ° C or higher
˜70% by weight can be decomposed into fractions with a boiling point of 343 ° C. or less.

As described above, the effluent oil that has exited the reaction step after completion of the hydrotreating treatment such as hydrodemetallizing treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment is subjected to a separation process according to a conventional method. It is introduced and processed into a plurality of separation tanks to be separated into a gas portion and a liquid portion. Among them, the gas portion is subjected to a treatment such as hydrogen purity improvement after removing hydrogen sulfide, ammonia, etc., and is recycled to the reaction process together with the newly supplied hydrogen gas.

On the other hand, the liquid portion separated in the separation step is
It is introduced into the distillation step and fractionated (separated) into each fraction according to a conventional method. The conditions for this fractional distillation include, for example,
In atmospheric distillation, that is, in atmospheric distillation, the cut temperature of the naphtha fraction is 145 to 190 ° C, the cut temperature of the kerosene fraction is 235 to 265 ° C, and the cut temperature of the light oil fraction is 343 to 3 ° C.
By using the residual oil at 80 ° C. and 380 ° C. or higher, it is possible to separate into a naphtha fraction, a kerosene fraction, a light oil fraction and a residual oil fraction. The obtained naphtha fraction is supplied to the feedstock oil of the catalytic reformer, and it is possible to produce reformed gasoline with a high octane number. The distillation fractionation may be performed by vacuum distillation.

The residual oil fraction (residual oil) thus separated in the distillation column is used in the fluidized bed catalytic cracking process after this or this residual oil fraction is partially mixed with the light oil fraction. , Fluidized catalytic cracking treatment. The fluidized bed catalytic cracking treatment step is composed of, for example, a reaction tower and a regeneration tower provided with a riser. The residual oil fraction is fed together with the regenerated catalyst from the regeneration tower. In this riser, the cracking reaction of the residual oil fraction is carried out, while in the reaction tower, the cracking reaction product and the catalyst are separated. The catalyst separated from the reaction tower is steam stripped and then sent to the regeneration tower. In the regeneration tower, coke is burned, the catalyst is reactivated, and then reused for fluid catalytic cracking. As the carrier of the catalyst used in this fluid catalytic cracking treatment, silica, alumina, silica-alumina, alumina-magnesia, silica-titania, alumina-titania, various clays, various crystalline aluminosilicates or a mixture thereof, etc. It can be mentioned as a suitable one. The processing conditions of the fluid catalytic cracking process vary depending on the specifications of the processing apparatus, the properties of the residual oil to be processed, and the like, and may be appropriately selected depending on the situation. For example, the riser outlet temperature 480 to 530 C, catalyst / oil ratio 4.0-6.5 wt / wt, preferably riser outlet temperature 500-525 C, catalyst / oil ratio 4.3-5.9 wt / wt.

The decomposition reaction product separated in the reaction tower of the fluid catalytic cracking treatment step is fed to the distillation step and, similarly to the above, fractionated (separated) into each fraction according to a conventional method. As conditions for this fractional distillation, for example, under atmospheric pressure, that is, in atmospheric distillation, the cut temperature of the gasoline fraction is C ₅ to
When the cut temperature of 180 ° C. and the gas oil fraction is 180 to 360 ° C. and the fraction having a temperature of 360 ° C. or higher is used as the residual oil, it can be separated into a gasoline fraction, a gas oil fraction and a residual oil fraction. The distillation fractionation may be performed by vacuum distillation.

FIG. 1 is an explanatory view showing the basic concept of the method of the present invention. FIG. 2 shows an example of a basic device configuration for carrying out the present invention. In the figure, 1 is a hydrodemetallization treatment tower, 2 is a hydrocracking treatment tower, 3 is a hydrodesulfurization and hydrodenitrification treatment tower, and these constitute a hydrotreatment step. Numeral 4 is an atmospheric distillation column, which separates the effluent oil that came out of the hydrotreating process after hydrotreating into naphtha fraction, kerosene fraction, gas oil fraction and residual oil fraction. Can be separated into minutes. 5 is a reaction tower for fluid catalytic cracking treatment of the residual oil fraction separated by atmospheric distillation in the atmospheric distillation tower 4, and is equipped with a riser 6 7 is a regeneration tower, and the waste catalyst after the fluid catalytic cracking treatment of the reaction tower is regenerated here and reused in the fluid catalytic cracking treatment. Further, 8 is an atmospheric distillation column, and similarly to 4, the reaction decomposition product in the reaction column is separated into each fraction.

[0014]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
Will be explained in detail. In addition, in Example 1 and Comparative Example,
Heavy hydrocarbon oil as a feedstock is the next Arabian snake.
-Atmospheric distillation residue oil was used. Properties Specific gravity 0.9852 Kinematic viscosity (50 ℃) 2,018cSt Sulfur content 4.14% by weight Nitrogen content 2,430ppm Vanadium content 95.4ppm Nickel content 30.1ppm Residual carbon 15.1% by weight Also, hydrogenation treatment After the atmospheric distillation, the gas content (~ C_Five),
Light naphtha fraction (C _Five~ 82 ℃, Heavy naphtha (8
2-150 ℃), kerosene light oil fraction (150-343 ℃), residual
Separated with oil (343 ° C. and above). Also, after fluid catalytic decomposition
Atmospheric pressure distillation is based on the gasoline fraction (C_Five~ 180 ℃), gas oil distillate
Separation by minutes (180-360 ℃) and residual oil (360 ℃ or higher)
did. The evaluation was obtained by 1,000 hours.
It

Example 1 1) Hydrotreating Hydrodemetallizing catalyst γ-alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Hydrogenolysis catalyst Iron-containing aluminosilicate carrier (special Kosho 61-2443
No. 3, gazette of the preparation method described in Example 1), cobalt oxide 4 wt%, molybdenum oxide 10 wt% hydrodesulfurization and denitrification catalyst γ-alumina carrier, molybdenum oxide 11 wt%, cobalt oxide 1 wt%, Nickel oxide 1% by weight Catalytic hydrotreating condition Treatment temperature 390-410 ° C Hydrogen partial pressure 130 kg / cm ² G Hydrogen / oil ratio 1,200 Nm ³ / kl LHSV 0.2 hr ^-1 20 hydrogen demetalization catalyst catalyst capacity %, Hydrocracking catalyst 60% by volume and hydrodesulfurization and hydrodenitrogenation catalyst 20
The volume% was loaded in this order into a fixed bed 1 liter reactor. Then, the arabian heavy atmospheric distillation residual oil was treated under the above treatment conditions. The Arabian heavy atmospheric distillation residue oil was passed downward at 200 cc / hr. The spilled oil was treated according to a conventional method, and then the liquid portion was subjected to atmospheric distillation according to a conventional method to separate each fraction. The results of the distillation separation are shown in Table 1.

[0016]

[Table 1]

2) Fluid catalytic cracking treatment Properties of distillation residual oil Specific gravity 0.923 Kinematic viscosity (50 ° C) 217cSt Sulfur content 0.46% by weight Nitrogen content 1,290ppm Vanadium content 0.7ppm Nickel content 2.1ppm Residual Carbon 7.48% by weight fluid catalytic cracking catalyst USY type residual oil FCC equilibrium catalyst (Al ₂ O ₃ 23% by weight, surface area 156 m ² / g, USY:
Steaming-treated Y-type zeolite) Fluid catalytic cracking conditions Reaction temperature 500 to 525 ° C. Regeneration temperature 750 to 850 ° C. Catalyst / oil ratio 5 to 7 Feed oil feed rate 1 liter / hr Circulating fluidized bench equipment Catalytic cracking products are According to a conventional method, atmospheric distillation was carried out to separate each fraction. The results of the distillation separation are shown in Table 2.

[0018]

[Table 2]

The total yield obtained by the combined treatment of the hydrotreatment and the fluid catalytic cracking treatment is shown in Table 3.

[0020]

[Table 3]

Example 2 As a heavy hydrocarbon oil as a raw material oil, the following Arabian heavy atmospheric distillation residual oil was used. Properties Specific gravity 0.9798 Kinetic viscosity (50 ℃) 1,098cSt Sulfur content 4.13% by weight Nitrogen content 2,500ppm Vanadium content 85ppm Nickel content 26ppm Residual carbon 15% by weight 1) Hydrotreatment Hydrodemetalization catalyst γ Alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Hydrogenolysis catalyst Iron-containing aluminosilicate carrier (JP-A-2-28941)
9 prepared in Example 1), cobalt oxide 4% by weight,
Molybdenum oxide 10% by weight Hydrodesulfurization and denitrification catalyst γ-alumina carrier, molybdenum oxide 11% by weight, cobalt oxide 1% by weight, nickel oxide 1% by weight Catalytic hydrogenation conditions Treatment temperature 390-410 ° C Hydrogen partial pressure 160 kg / cm ² G hydrogen / oil ratio 800 Nm ³ / kl LHSV 0.16 hr ^-1 21% by volume of the above hydrodemetallization catalyst catalyst, 36% by volume of hydrocracking catalyst and hydrodesulfurization and hydrodenitrogenation catalyst 43
The volume% was loaded in this order into a fixed bed 1 liter reactor. Then, the arabian heavy atmospheric distillation residual oil was treated under the above treatment conditions. The Arabian heavy atmospheric distillation residue oil was passed downward at 200 cc / hr. The spilled oil was treated according to a conventional method, and then the liquid portion was subjected to atmospheric distillation according to a conventional method to separate each fraction. The results of the distillation separation are shown in Table 4.

[0022]

[Table 4]

2) Fluid catalytic cracking treatment Properties of distillation residual oil Specific gravity 0.930 Kinematic viscosity (50 ° C) 180cSt Sulfur content 0.47% by weight Nitrogen content 1,320ppm Vanadium content 0.9ppm Nickel content 2.5ppm Residual Carbon 7.69 wt% Fluid catalytic cracking catalyst USY type residual oil FCC equilibrium catalyst (Al ₂ O ₃ 23 wt%, surface area 156 m ² / g, USY:
Steaming-treated Y-type zeolite) Fluid catalytic cracking conditions Reaction temperature 500 to 525 ° C. Regeneration temperature 750 to 850 ° C. Catalyst / oil ratio 5 to 7 Feed oil feed rate 1 liter / hr Circulating fluidized bench equipment Catalytic cracking products are According to a conventional method, atmospheric distillation was carried out to separate each fraction. The results of the distillation separation are shown in Table 5.

[0024]

[Table 5]

Table 6 shows the total yield obtained by the combined treatment of the hydrotreatment and the fluid catalytic cracking treatment.

[0026]

[Table 6]

Comparative Example A stock oil was subjected to demetalization treatment and direct desulfurization treatment under the following conditions, and then distilled under atmospheric pressure according to a conventional method. The results of the distillation separation are shown in Table 7. Demetalization catalyst γ-alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Desulfurization catalyst γ-alumina carrier, molybdenum oxide 11% by weight, cobalt oxide 1% by weight, nickel oxide 1% by weight treatment Conditions Treatment temperature 390-410 ° C Reaction partial pressure 130kg / cm ² G LHSV 0.2hr ^-1 Reactor fixed bed 1 liter (Demetalization 20% by volume, Desulfurization 80% by volume)

[0028]

[Table 7]

After the atmospheric distillation, the residual oil fraction was subjected to fluid catalytic cracking treatment in the same manner as in Example 1. The catalytic decomposition product was distilled under atmospheric pressure according to a conventional method and separated into each fraction. The results of the distillation separation are shown in Table 8. Fluid catalytic cracking treatment Properties of distillation residual oil Specific gravity 0.937 Kinematic viscosity (50 ℃) 165cSt Sulfur content 0.49% by weight Nitrogen content 1,705ppm Vanadium content 1.5ppm Nickel content 3.9ppm Residual carbon 7.09weight % Fluidized catalytic cracking catalyst USY type residual oil FCC equilibrium catalyst (Al ₂ O ₃ 23% by weight, surface area 156 m ² / g, USY:
Steaming-treated Y-type zeolite) Fluid catalytic cracking conditions Reaction temperature 500 to 525 ° C. Regeneration temperature 750 to 850 ° C. Catalyst / oil ratio 5 to 7 Feed oil feed rate 1 liter / hr Circulating fluidized bench equipment Catalytic cracking products are According to a conventional method, atmospheric distillation was carried out to separate each fraction. The results of the distillation separation are shown in Table 8.

[0030]

[Table 8]

Table 9 shows the overall yield obtained by the two-stage treatment of hydrodemetalization, hydrodesulfurization and denitrification, followed by fluid catalytic cracking.

[0032]

[Table 9]

Comparing the example of the present invention with the comparative example,
Since the comparative example is a production centered on FCC gasoline, the yield of FCC gasoline is almost double that of the example, but light oil is about half or less, and hydrogenated only by desulfurization. The quality is not good because there is no. The quality of light oil is shown in Table 10.

[0034]

[Table 10]

That is, the light oils in the examples are characterized by low sulfur content and nitrogen content, and low clogging point and pour point.
On the other hand, the light oil obtained by the direct desulfurization treatment of the comparative example needs to be hydrotreated again when it is used as light oil for transportation. Further, in the comparative example, about 25% of catalytically cracked gas oil having a large amount of polycyclic aromatics and a low cetane index is produced, so that the comparative example is a low-value cracking system. Further, in the embodiment, since the reformed gasoline raw material and the FCC gasoline are produced almost equally, gasoline and light oil are produced almost equally. Furthermore, by changing the cracking rate level of hydrocracking, the ratio of gasoline to light oil and the ratio of reformed gasoline feedstock to FCC gasoline in the gasoline fraction can be changed, which makes it easier to meet market needs. Also in this respect, it is understood that the example is superior to the comparative example producing only FCC gasoline.

[0036]

As described above, according to the present invention, a heavy hydrocarbon oil is subjected to hydrotreatment and fluidized contact consisting of a hydrodemetallization step, a hydrocracking step, a hydrodesulfurization step and a hydrodenitrogenation step. By carrying out a combination of cracking treatments, it is possible to efficiently obtain a naphtha fraction and a kerosene gas oil fraction from a heavy hydrocarbon oil with a high yield. Therefore, the present invention provides
Heavy hydrocarbon oil that was conventionally used as fuel for boilers, etc. can be effectively used as a resource for obtaining more valuable naphtha fraction and kerosene gas oil fraction, so its industrial utility value is There is an extremely large one.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing the basic concept of the method of the present invention.

FIG. 2 shows an example of a basic device configuration for carrying out the present invention.

[Explanation of symbols]

 1: Hydrodemetalization treatment tower 2: Hydrocracking treatment tower 3: Hydrodesulfurization treatment and hydrodenitrogenation treatment tower 4: Atmospheric pressure distillation tower 5: Reaction tower 6: Riser 7: Regeneration tower 8: Atmospheric pressure distillation Tower

[Procedure amendment]

[Submission date] October 5, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art Applications of petroleum include fuels (especially for heating and transportation) and petrochemical raw materials. Although it is expected that the demand for heating will be replaced by other energy sources in the future, the demand for gasoline, light oil, and jet fuel oil, which are fuel oils for transportation, is expected to grow quite rapidly. In addition, in recent years, as crude oil prices have risen, crude oil has become heavier, and demand for light hydrocarbons has increased, residual oil consisting of heavy hydrocarbon oils is cracked and processed, and naphtha fractions and light oil are used as transportation fuels. It is desired to develop a technique capable of efficiently producing a fraction. And in particular, the flexibility of production, which can change the product composition depending on the season and the place, is an important factor for responding to changes in demand. For this,
Various processes have already been proposed. For example, first
A method has been proposed in which a normal pressure residual oil is treated in combination with a direct desulfurization treatment step and a residual oil fluidized bed catalytic cracking treatment step (R-FCC). However, in this method, since the decomposition in the direct desulfurization process step is small, the R-F having a large processing capacity is used.
It has the drawback of requiring a CC. Further, there is a disadvantage that catalytic cracking gas oil of low value, that is, catalytic cracking gas oil that has a low cetane index and does not serve as direct transportation gas oil (for example, diesel engine fuel) is produced in large quantities. Further, after the atmospheric residual oil is distilled under reduced pressure and fractionated, the resulting reduced pressure gas oil is hydrotreated with the reduced pressure residual oil to be hydrodesulfurized together with the reduced pressure gas oil, and this processed oil is subjected to R-FCC treatment. Methods have also been proposed. This method can process relatively heavy feedstocks, but the main product is FCC.
It becomes gasoline, and at the same time, low-value catalytically cracked gas oil and catalytically cracked residual oil are co-produced. And, there is a drawback that it is not possible to produce a high-quality gas oil fraction other than FCC gasoline. Furthermore, a method has also been proposed in which the same vacuum distillation residue oil as described above is desulfurized in a fixed bed and then subjected to R-FCC. In this method, there is a problem in operating the desulfurization treatment in a fixed bed for a long period of time, and since it is a cracked product oil using vacuum distillation residue oil as a raw material, R-FC
It is feared that the reactivity in the C treatment will be significantly reduced.
In addition to FCC gasoline, a large amount of low-quality catalytically cracked gas oil and catalytically cracked residual oil are also produced. As described above, the fact that there is no satisfactory technology capable of efficiently producing a naphtha fraction or a light oil fraction as a fuel for transportation by decomposing residual oil, and the development of the technique Is strongly desired.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

Next, the effluent oil that has been hydrodemetallized is sent to the hydrocracking process. The hydrocracking process is carried out by an apparatus composed of one to a plurality of reaction towers. Then, in the case of a fixed bed, each reaction tower is divided into a plurality of catalyst beds, and a fluid is introduced into each catalyst bed in order to cool the reactants. The catalyst used in this hydrocracking treatment is alumina, silica, alumina boria, zeolite or the like as a carrier, and one or more metals of Group VIA and Group VIII of the Periodic Table are supported in an oxide state. It is a thing. Also, Japanese Patent Publication No. 60-49131 and Japanese Patent Publication No. 61
No. 24433 gazette, Japanese Patent Publication No. 3-21484 gazette, etc., and a carrier composed of 20 to 80% by weight of an iron-containing zeolite and 80 to 20% by weight of an inorganic oxide, and a periodic table It is also possible to use one or a plurality of Group VIA and Group VIII metals supported in an oxide state. Furthermore, a carrier composed of 10 to 90% by weight of an iron-containing zeolite and 90 to 10% by weight of an inorganic oxide prepared by the technique disclosed in Japanese Patent Application Laid-Open No. 2-289419, is added to Group VIA and the same group of the periodic table. It is also possible to use one or more Group VIII metals supported in an oxide state. Particularly, this Japanese Patent Laid-Open No. 2-289419
The use of an iron-containing aluminosilicate obtained by treating steamed steaming zeolite with an aqueous solution of an iron salt disclosed in Japanese Patent Publication increases the decomposition rate from a fraction at 343 ° C or higher to a fraction at 343 ° C or lower. Very effective in terms. Here, as a metal of Group VIA of the periodic table,
Mo and W are preferable. Further, Ni and Co are preferable as the Group VIII metal. The processing conditions for this hydrocracking treatment are as follows: reaction temperature 300 to 450 ° C., hydrogen partial pressure 30 to 200 kg / cm ² G, hydrogen / oil ratio 300 to 2.0.
00 Nm ^{3 /} kl, LHSV = 0.1 to 2.0 hr ⁻¹ , preferably reaction temperature 380 to 420 ° C., hydrogen partial pressure 100 to 180 kg
/ Cm ² G, hydrogen / oil ratio 500 to 1,000 Nm ³ / kl, LHS
V = 0.2 to 1.0 hr ⁻¹ . As a result of this hydrocracking treatment, a high-quality naphtha fraction and kerosene gas oil fraction can be obtained at a high rate by cracking from a fraction at 343 ° C or higher to a fraction at 343 ° C or lower.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

Example 1 1) Hydrotreating Hydrodemetallizing catalyst γ-alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Hydrogenolysis catalyst Iron-containing aluminosilicate carrier (special Kosho 61-2443
No. 3, gazette of the preparation method described in Example 1), cobalt oxide 4% by weight, molybdenum oxide 10% by weight, hydrodesulfurization and hydrodenitrogenation catalyst γ-alumina carrier, molybdenum oxide 11% by weight, cobalt oxide 1% by weight. %, Nickel oxide 1% by weight Hydrotreating conditions Treatment temperature 390 to 410 ° C. Hydrogen partial pressure 130 kg / cm ² G Hydrogen / oil ratio 1,200 Nm ³ / kl LHSV 0.20 hr ^{−1 The} above hydrogenation and demetalization catalyst 20 % By volume, 60% by volume of hydrocracking catalyst and 20 by hydrodesulfurization and hydrodenitrogenation catalyst
The volume% was loaded in this order into a fixed bed 1 liter reactor. Then, the arabian heavy atmospheric distillation residual oil was treated under the above treatment conditions. The Arabian heavy atmospheric distillation residue oil was passed downward at 200 cc / hr. The spilled oil was treated according to a conventional method, and then the liquid portion was subjected to atmospheric distillation according to a conventional method to separate each fraction. The results of the distillation separation are shown in Table 1.

[Procedure amendment 4]

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[Table 1]

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[Table 2]

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[Table 3]

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Example 2 As a heavy hydrocarbon oil as a raw material oil, the following Arabian heavy atmospheric distillation residual oil was used. Properties Specific gravity 0.9798 Kinetic viscosity (50 ℃) 1,098cSt Sulfur content 4.13% by weight Nitrogen content 2,500ppm Vanadium content 85ppm Nickel content 26ppm Residual carbon 15% by weight 1) Hydrotreatment Hydrodemetalization catalyst γ Alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Hydrogenolysis catalyst Iron-containing aluminosilicate carrier (JP-A-2-28941)
9 prepared in Example 1), cobalt oxide 4% by weight,
Molybdenum oxide 10% by weight Hydrodesulfurization and hydrodenitrogenation catalyst γ-alumina carrier, molybdenum oxide 11% by weight, cobalt oxide 1% by weight, nickel oxide 1% by weight Hydrogenation treatment condition Treatment temperature 390-410 ° C Hydrogen partial pressure 160 kg / cm ² G Hydrogen / oil ratio 800 Nm ³ / kl LHSV 0.20 hr ^-1 21% by volume of the above hydrodemetallizing catalyst, 36% by volume of hydrocracking catalyst and 43% by volume of hydrodesulfurization and hydrodenitrogenation catalyst 43
The volume% was loaded in this order into a fixed bed 1 liter reactor. Then, the arabian heavy atmospheric distillation residual oil was treated under the above treatment conditions. The Arabian heavy atmospheric distillation residue oil was passed downward at 200 cc / hr. The spilled oil was treated according to a conventional method, and then the liquid portion was subjected to atmospheric distillation according to a conventional method to separate each fraction. The results of the distillation separation are shown in Table 4.

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[Table 4]

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[Table 5]

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[Table 6]

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Comparative Example The feed oil used in Example 1 was treated under the hydrotreating conditions using the following hydrodemetallizing catalyst and hydrodesulfurizing and hydrodenitrogenating catalyst, and then distilled under atmospheric pressure according to a conventional method. ..
The results of the distillation separation are shown in Table 7. Hydrodemetalization catalyst γ-alumina carrier, molybdenum oxide 1.5% by weight, nickel oxide 3% by weight, vanadium oxide 3% by weight Hydrodesulfurization and hydrodenitrogenation catalyst γ-alumina carrier, molybdenum oxide 11% by weight, cobalt oxide 1 % By weight, nickel oxide 1% by weight Hydrogenation condition Treatment temperature 390-410 ° C Reaction partial pressure 130 kg / cm ² G LHSV 0.2 hr ^-1 Reactor fixed bed 1 liter (hydrodemetallization catalyst 20% by volume, hydrogenation Desulfurization and hydrodenitrogenation catalyst 80% by volume)

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[Table 7]

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[Table 8]

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Table 9 shows the overall yield obtained by the two-stage treatment of hydrodemetalization, hydrodesulfurization and hydrodenitrogenation followed by fluid catalytic cracking.

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[Table 9]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiichiro Kanda 1280, Kamizumi, Sodegaura, Chiba Idemitsu Kosan Co., Ltd.

Claims (2)

[Claims] 1. A heavy hydrocarbon oil is hydrotreated in the presence of a catalyst in the order of hydrodemetallization treatment, hydrocracking treatment, hydrodesulfurization and hydrodenitrogenation treatment, and then the resulting hydrogen. A method for treating a heavy hydrocarbon oil, which comprises subjecting a residual oil to a fluidized bed catalytic cracking treatment after a chemical treatment oil is separated by distillation. 2. A catalyst used in the hydrocracking treatment comprises a carrier composed of 10 to 90% by weight of an iron-containing aluminosilicate and 90 to 10% by weight of an inorganic oxide on a group VIA and VIII of the periodic table. The method for treating heavy hydrocarbon oil according to claim 1, wherein the metal or the metal compound is supported.