JPH11349961A - Hydrotreating method for heavy hydrocarbon oil - Google Patents

Abstract

(57) [Summary] [PROBLEMS] A high-quality, high-value-added gasoline fraction obtained by efficiently catalytically hydrotreating low-quality heavy hydrocarbon oils.
To provide a method for producing a kerosene oil fraction, a lubricating oil base material, and the like in a high yield. SOLUTION: (A) a step of bringing a heavy hydrocarbon oil into contact with an amorphous hydrotreating catalyst to perform hydrodesulfurization and denitrification treatment, and (B) a hydrocarbon oil treated in the above (A) step. Is contacted with a zeolite-based hydrocracking catalyst to perform hydrocracking, and (C) the hydrocarbon oil treated in the above step (B) is contacted with an amorphous-based hydrotreating catalyst to hydrodesulfurize it. The heavy hydrocarbon oil is lightened by sequentially performing the treatment steps.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrotreating heavy hydrocarbon oils, and more particularly, to catalytic hydrogenation of low-quality heavy hydrocarbon oils efficiently to obtain high-quality added value. The present invention relates to a method for producing a high-yield gasoline fraction, kerosene-oil fraction, lubricating oil base material and the like in high yield.

[0002]

2. Description of the Related Art In recent years, in the field of petroleum refining, crude oil to be treated tends to be heavier, and the demand for lighter oils such as kerosene oil fractions and lubricating oil base materials has been increasing.
Therefore, in order to balance these supply and demand, the conversion of heavy hydrocarbon oils into light fractions has been attempted. It has been known that a high-quality light oil can be obtained by subjecting a heavy hydrocarbon oil to hydrogenation treatment by bringing it into contact with a catalyst under high-temperature and high-pressure conditions in the presence of hydrogen. Research on catalytic hydrogenation of hydrogen oil has been actively conducted, and many methods have been proposed. For example, JP-A-62-8979
No. 3 discloses a technique comprising a demetallization step and a hydrodesulfurization step. However, this method is mainly intended for desulfurization of heavy hydrocarbon oils, and has a drawback that the yield of a fraction of 343 ° C. or lower is low. Also, Japanese Patent Application Laid-Open No. 2-2
No. 89419 discloses that a metal of Group 6 and Groups 8 to 10 of the periodic table is supported on a carrier comprising an iron-containing aluminosilicate and an inorganic oxide used for hydrocracking of heavy hydrocarbon oil. Techniques relating to catalysts are disclosed. When this catalyst is used, a high decomposition rate can be obtained, but it has a disadvantage that the sulfur content and the nitrogen content of the fraction at 343 ° C. or higher are high and the quality is inferior. Further, JP-A 1-27
Japanese Patent No. 5693 discloses a technique for hydrotreating a heavy hydrocarbon oil in the order of a metal removal step, a hydrodesulfurization step, and a hydrocracking step. However, this method is mainly for heavy distillate systems containing light catalytic circulation oil,
Cracking oil is mainly composed of gas (C ₁ -C ₄ ) and heavy and light naphtha, and is not intended for general heavy hydrocarbon oils.

[0003] In general, in order to catalytically hydrotreat heavy hydrocarbon oils, conventionally, hydrogenation mainly involving demetallization in a fixed bed, a moving bed or a fluidized bed is carried out, followed by a fixed bed or a fluidized bed. Had been hydrodesulfurized or hydrotreated. Further, conventionally, in the operation mainly based on desulfurization, there was a disadvantage that the decomposition rate was extremely low throughout the operation because the reaction temperature was raised together with the deterioration of the catalyst. On the other hand, in the operation mainly for cracking, although a certain cracking rate can be obtained, there is a quality problem that the sulfur content in the residual oil fraction increases with the deterioration of the catalyst. In addition, operation management was complicated, and the desulfurization reaction and decomposition reaction could not be controlled independently.

[0004]

SUMMARY OF THE INVENTION The present invention provides a high-quality, high-value-added gasoline fraction by efficiently catalytically hydrotreating a low-quality heavy hydrocarbon oil under such circumstances. It is an object of the present invention to provide a method for hydrotreating heavy hydrocarbon oil, which can produce a kerosene oil fraction, a lubricating oil base material, and the like in a high yield, and can operate stably. Another object of the present invention is to provide a method for efficiently producing light oil having particularly low sulfur content from heavy hydrocarbon oil.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a specific heavy hydrocarbon oil can be treated with hydrogen using an amorphous hydrotreating catalyst. The objective was achieved by sequentially performing a hydrodesulfurization and denitrification process, a hydrocracking process using a zeolite-based hydrocracking catalyst, and a hydrodesulfurization process using an amorphous hydrocracking catalyst. I found out. The present invention has been completed based on such findings. That is, the present invention relates to hydrotreating at least one heavy hydrocarbon oil selected from heavy gas oil, cracked gas oil, reduced pressure gas oil, coker gas oil, visbreaker gas oil, and solvent deasphalted oil. (A) a step of bringing the heavy hydrocarbon oil into contact with an amorphous hydrotreating catalyst to perform hydrodesulfurization and denitrification, and (B) a step of: treating the hydrocarbon oil treated in the step (A). Contacting with a zeolite-based hydrocracking catalyst and hydrocracking; and (C) contacting the hydrocarbon oil treated in step (B) with an amorphous hydrocracking catalyst;
The present invention provides a method for hydrotreating heavy hydrocarbon oil, comprising sequentially performing a hydrodesulfurization process.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, the heavy hydrocarbon oil is selected from heavy gas oil, cracked gas oil, vacuum gas oil, coker gas oil, bisbreaker gas oil and solvent deasphalted oil. Things are used. Here, heavy gas oil is heavy gas oil obtained by atmospheric distillation of crude oil, and cracked gas oil is gas oil obtained by fluid catalytic cracking of heavy gas oil, vacuum gas oil, or residue oil of normal pressure distillation. That is, the vacuum gas oil is a gas oil obtained by vacuum distillation of atmospheric distillation residue. Also, coker gas oil is
The gas oil fraction obtained from the coker, and the gas breaker gas oil is the gas oil fraction obtained from the bis breaker. Furthermore, the solvent deasphalted oil is a fraction extracted from a vacuum distillation residue with a solvent such as propane.
In the present invention, one of these heavy hydrocarbon oils may be used, or two or more thereof may be used in combination. The method for hydrotreating heavy hydrocarbon oil according to the present invention comprises (A) a hydrodesulfurization and denitrification treatment step using an amorphous hydrotreating catalyst, and (B) a zeolite hydrocracking catalyst. It comprises a hydrocracking step and (C) a hydrodesulfurization step using an amorphous hydrotreating catalyst. Hereinafter, the catalyst used in each step will be described.

Amorphous hydrotreating catalyst This amorphous hydrotreating catalyst is used for the hydrodesulfurization and denitrification treatment in the above-mentioned step (A) and for the hydrodesulfurization treatment in the step (C). That is usually
A material in which at least one metal selected from metals belonging to Groups 6, 8, 9 and 10 of the periodic table is supported on an amorphous carrier is used. Examples of the amorphous carrier include alumina, silica, silica-alumina,
Examples include sepiolite or those obtained by adding at least one compound selected from boron, silicon and phosphorus to these. As the metal belonging to Group 6 of the periodic table supported on such an amorphous carrier, tungsten and molybdenum are preferable. Nickel and cobalt are preferable as the metals belonging to Groups 8 to 10 of the periodic table. Note that the Group 6 metal and the Group 8 to 10 metals may be used alone or in combination of a plurality of types of metals. In particular, the hydrogenation activity is high and the deterioration is small. , Ni-Mo, Co-Mo, Ni-W, N
Combinations such as i-Co-Mo are preferred.

[0008] The amount of the metal carried is not particularly limited and may be appropriately selected according to various conditions.
Usually 1 to 35 as metal oxide based on the total weight of the catalyst
% By weight. If the supported amount is less than 1% by weight,
If the effect of the hydrotreating catalyst is not sufficiently exhibited, and if it exceeds 35% by weight, the improvement of the hydrogenation activity is not remarkable for the supported amount, and it is economically disadvantageous. Especially,
The range of 5 to 30% by weight is preferred from the viewpoint of hydrogenation activity and economy. The loading method is not particularly limited, and any known method such as an impregnation method, a coprecipitation method, and a kneading method can be employed. Further, after a desired metal is supported on the carrier at a predetermined ratio, drying is performed, if necessary, followed by baking treatment. The sintering temperature and time are appropriately selected according to the type of the metal supported, and the like. The average pore diameter of the catalyst thus obtained is preferably in the range of 50 to 150 °, and if the average pore diameter is less than 50 °, heavy molecules cannot be sufficiently diffused into the pores. , The reaction becomes insufficient,
On the other hand, if it exceeds 150 °, the surface area becomes small and the reaction does not proceed sufficiently.

In the case where a catalyst obtained by adding at least one compound selected from boron, silicon and phosphorus to alumina is used as the carrier, the catalyst may be a boron compound, a silicon compound or a phosphorus compound based on the total weight of the carrier. Is preferably contained at a ratio of 0.5 to 20% by weight. When the content is less than the lower limit, the effect of improving the hydrogenation activity is small, and when the content exceeds the upper limit,
Although the effect of improving the hydrogenation activity is hardly seen for the amount thereof, it is not economical, and the desulfurization activity and the denitrification activity may decrease, which is not preferable. In particular, each is preferably in the range of 1 to 18% by weight from the viewpoint of the effect of improving the hydrogenation activity. The carrier is prepared by adding a boron compound, a silicon compound or a phosphorus compound at a predetermined ratio to alumina or an alumina precursor having a water content of 65% by weight or more, for example, at a temperature of about 60 to 100 ° C., preferably for 1 hour or more. More preferably 1.5
After heating and kneading for at least a period of time, molding, drying and baking can be performed by a known method to produce the compound. If the heating and kneading is less than 1 hour, kneading may be insufficient and the dispersion state of boron atoms and the like may be insufficient,
If the kneading temperature is outside the above range, boron or the like may not be highly dispersed, which is not preferable. The addition of boron, silicon, phosphorus or a compound thereof may be carried out in a solution by heating and dissolving in water, if necessary.

Here, the alumina precursor is not particularly limited as long as it produces alumina by firing, and examples thereof include aluminum hydroxide, pseudoboehmite, boehmite, bayerite, alumina hydrate such as gibbsite, etc. Can be mentioned. The above-mentioned alumina or alumina precursor is desirably used with a water content of 65% by weight or more. If the water content is less than 65% by weight, the added compounds such as phosphorus may not be sufficiently dispersed. . As the boron compound, in addition to boron oxide, various boron compounds which can be converted to boron oxide by firing can be used. For example, boric acid, ammonium borate, sodium borate, sodium perborate, Examples include orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium perborate, calcium borate, diborane, magnesium borate, methyl borate, butyl borate, tricyclohexyl borate, and the like. The phosphorus compound used in the carrier obtained by adding a phosphorus compound to alumina among the above carriers may include simple phosphorus. Specific examples of the phosphorus simple substance include yellow phosphorus and red phosphorus.

Examples of the phosphorus compound include inorganic phosphoric acids having a low oxidation number such as orthophosphoric acid, hypophosphoric acid, phosphorous acid, and hypophosphorous acid, or alkali metal salts or ammonium salts thereof, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, and tetraphosphoric acid. Polyphosphoric acid such as polyphosphoric acid or alkali metal salts or ammonium salts thereof, metaphosphoric acid such as trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid or alkali metal or ammonium salts thereof, phosphorus chalcogenide, organic phosphoric acid, organic phosphate And the like. Among these, alkali metal salts or ammonium salts of inorganic phosphoric acid or condensed phosphoric acid having a low oxidation number are particularly preferred from the viewpoints of activity, water resistance, heat resistance and durability. As the silicon compound, besides silicon oxide, various silicon compounds which can be converted to silicon oxide by firing can be used. For example, silicic acid, metasilicic acid, hexafluorosilicic acid or alkali metal salts thereof, silicon fluoride , Silicon chloride, silicon sulfide, silicon acetate, siloxane, siloxene and their halogen-substituted, alkyl-substituted and allyl-substituted products. Among these, alkali metal salts of silicic acid are preferred from the viewpoints of activity, water and heat resistance, durability and the like.

Zeolite-based hydrocracking catalyst This zeolite-based hydrocracking catalyst is used in the hydrocracking treatment in the step (B), and is usually a carrier containing alumina and boron oxide and / or a Y-type zeolite. A carrier containing at least one metal selected from metals belonging to Groups 6, 8, 9 and 10 of the periodic table is preferably used. In the carrier containing alumina and boron oxide, the content ratio of alumina and boron oxide is preferably from 95/5 to 70/30 by weight, particularly preferably from 90/10 to 80/20. Preferred examples of the Y-type zeolite include faujasite-type aluminosilicate, iron-containing steaming aluminosilicate by a nitric acid method, and iron-containing steaming aluminosilicate by a sulfuric acid method. One of these is contained in a carrier. Or a combination of two or more kinds may be contained in the carrier. As the carrier used for this catalyst, the above-mentioned Y-type zeolites 5 to 6
Those comprising 0% by weight and 95 to 40% by weight of an inorganic oxide are preferred. If the content of the Y-type zeolite in the carrier is less than 5% by weight, the effect as a hydrocracking catalyst is not sufficiently exhibited, and if it exceeds 60% by weight, overcracking proceeds and the gas yield increases. The yield of the intermediate product decreases, which is uneconomical.

The inorganic oxide used for the Y-type zeolite-containing carrier includes, for example, alumina such as boehmite gel and alumina sol, silica such as silica sol, and porous materials such as silica-alumina, with alumina being particularly preferred. Used. The faujasite-type aluminosilicate in the Y-type zeolite can be produced by a known method, for example, a method described in JP-B-8-18819. The iron-containing steaming aluminosilicate by the nitric acid method and the iron-containing steaming aluminosilicate by the sulfuric acid method can be produced by a known method, for example, a method described in Japanese Patent Publication No. 6-74135. On the other hand, a carrier containing alumina and boron oxide can be produced by various methods.However, usually, boric acid is added to an alumina slurry to obtain an alumina-boric acid slurry, which is formed into pellets and the like, and dried. Manufactured by firing at a high temperature. As the carrier of the catalyst in the step (B) of the present invention, a carrier containing Y-type zeolite, particularly a carrier containing Y-type zeolite and alumina and boron oxide (boria) are preferable. When Y-type zeolite and alumina boria are contained, it is preferable to select the range of Y-type zeolite: alumina-boria = 5: 95 to 40:60 (weight ratio). As the metal belonging to Group 6 of the periodic table to be supported on such a carrier containing Y-type zeolite or a carrier containing alumina and boron oxide, tungsten and molybdenum are preferable, and metals belonging to Groups 8 to 10 of the periodic table are used. Preferably, nickel and cobalt are used. The Group 6 metal and the Group 8 to 10 metals may be used alone or in combination of two or more metals. However, they have particularly high hydrocracking activity and little deterioration. Therefore, a combination of Ni-Mo and Co-Mo is preferable.

The amount of the metal supported is not particularly limited and may be appropriately selected according to various circumstances. Usually, the metal of Group 6 is used as a metal oxide in an amount of 0.5 to 24 parts of the entire catalyst.
% By weight, preferably 8 to 20% by weight.
The metal of the group is 0.5 to 20% by weight, preferably 1.5 to 8% by weight of the whole catalyst as a metal oxide. The loading method is not particularly limited, and any known method such as an impregnation method, a coprecipitation method, and a kneading method can be employed. Further, after a desired metal is supported on the carrier at a predetermined ratio, drying is performed, if necessary, followed by baking treatment. The sintering temperature and time are appropriately selected according to the type of the metal supported, and the like. The hydrocracking catalyst thus obtained preferably has an average pore size of 50 to 200 °, more preferably 50 to 150 °. This average pore diameter is 5
If it is less than 0 °, the reaction does not proceed sufficiently because the heavy molecules do not sufficiently diffuse into the pores. On the other hand, if it exceeds 200 °, the surface area becomes small and the progress of the reaction is insufficient. Next, a preferred embodiment of each step will be described.

Step (A) This step is a step of bringing the heavy hydrocarbon oil into contact with the amorphous hydrotreating catalyst and subjecting it to hydrodesulfurization and denitrification. The following conditions are used as the reaction conditions in this step. First, the reaction temperature is 300 to 450
C. is preferred. When the reaction temperature is lower than 300 ° C., the progress of the reaction is extremely slow. When the reaction temperature is higher than 450 ° C., solid carbon (coke) is generated on the catalyst, and the life of the catalyst is significantly reduced. For the same reason as above, the reaction temperature is 36
The range of 0 to 420 ° C is more preferable. Also, the reaction pressure,
That is, the hydrogen partial pressure is preferably in the range of 30 to ²⁰⁰ kg / cm ² . If the pressure is less than 30 kg / cm ² , solid carbon is precipitated, the catalyst life is significantly reduced, and
Pressures exceeding g / cm ² are uneconomical in equipment design. For the same reason as above, the hydrogen partial pressure is 100 to 180 kg /
More preferably, it is in the range of cm ² . In addition, hydrogen /
Oil ratio is preferably in the range of 300~2000Nm ³ / kl. If the above ratio is less than 300 Nm ³ / kl, hydrodesulfurization and denitrification will not proceed sufficiently, and if it exceeds 2000 Nm ³ / kl,
It is uneconomical in equipment design. For the same reason as above, the ratio is more preferably in the range of 500 to 1000 Nm ³ / kl. Liquid hourly space velocity (LHSV)
The range of 0.1 to 10 h ^-1 is preferred. LHSV is 0.1h ^-1
If it is less than 10 h ^-1 , there is a disadvantage that the reaction time is insufficient and hydrodesulfurization and denitrification of the feedstock are not completed.
For the same reason as above, the LHSV is more preferably in the range of 0.3 to 5.0 h ^-1 . A part or the whole of the hydrodesulfurized and denitrified hydrocarbon oil is supplied to the next hydrocracking step (B). If necessary, the treated hydrocarbon oil is gas-liquid separated into a gas component and a liquid component.
(B) It may be supplied to the step.

Step (B) This step is a step of bringing the hydrocarbon oil treated in the above step (A) into contact with the zeolite-based hydrocracking catalyst and subjecting it to a hydrocracking treatment. The following conditions are used as reaction conditions in this step. First, the reaction temperature is 30
The range of 0-450 degreeC is preferable. The reaction temperature is 300
If the temperature is lower than 450 ° C., the progress of the reaction becomes extremely slow.
If the ratio exceeds the above, over-decomposition proceeds and the yield of intermediate products decreases due to an increase in gas yield, which is uneconomical. For the same reason as above, the reaction temperature is more preferably in the range of 380 to 420 ° C. The reaction pressure, that is, the hydrogen partial pressure is 30.
The range is preferably from 200 to 200 kg / cm ² . The above pressure is 3
If it is less than 0 kg / cm ² , the properties of the generated middle distillate, for example, hue and smoke point, will deteriorate, and a pressure exceeding 200 kg / cm ² is uneconomical in terms of equipment design. For the same reason as above, the hydrogen partial pressure is more preferably in the range of 100 to 180 kg / cm ² . Furthermore, the hydrogen / oil ratio is 300-
Preferably it is in the range of 2000 Nm ³ / kl. If the ratio is less than 300 Nm ³ / kl, the reaction does not proceed sufficiently, if and product properties of the cracked oil is deteriorated, and in excess of 2000 Nm ³ / kl is an uneconomical on the device design. For the same reasons as above,
More preferably, the ratio is in the range of 500-1000 Nm ³ / kl. LHSV is 0.1-3.0h
It is preferably in the range of ^-1 . When the LHSV is less than 0.1 h ^-1 , a sufficient processing speed cannot be obtained from an economic viewpoint, and when the LHSV exceeds 3.0 h ^-1 , the reaction time is insufficient and the yield of cracked oil is sufficiently obtained. I can't. For the same reason as above, LHSV is 0.2 to 2.0 h ^-1 , and furthermore, 0.2 to 1.0 h.
It is preferably in the range of ^-1 . A part or the whole of the hydrocracked hydrocarbon oil is supplied to the next hydrodesulfurization step (C). If necessary, the treated hydrocarbon oil may be gas-liquid separated into a gas component and a liquid component, and then only the liquid component may be supplied to the step (C).

Step (C) This step is a step of bringing the hydrocarbon oil treated in the above step (B) into contact with the above-mentioned amorphous hydrotreating catalyst and subjecting it to hydrodesulfurization treatment. As the reaction conditions in this step, the same conditions as in the step (A) can be adopted. However, the LHSV is advantageously in the range of 0.5 to 20 h ^-1 , preferably 5 to 10 h ^-1 . A part of the hydrodesulfurized hydrocarbon oil can be recycled to the above-mentioned step (A) and / or step (B), if desired. If necessary, after the treated hydrocarbon oil is gas-liquid separated into a gas component and a liquid component, only the liquid component may be recycled to the step (A) and / or the step (B). In the present invention, after the treatment in each step,
The gas component that has been gas-liquid separated as required,
The hydrorefining treatment can be performed together.

In this hydrorefining treatment step, the following conditions are used as the reaction conditions. First, the reaction temperature is 3
The range of 00-450 degreeC is preferable. The reaction temperature is 30
If the temperature is lower than 0 ° C., the progress of the reaction is remarkably slowed down.
If the temperature exceeds ℃, over-decomposition proceeds, and the yield of intermediate products decreases due to an increase in gas yield, which is uneconomical. For the same reason as above, the reaction temperature is more preferably in the range of 360 to 420 ° C. The reaction pressure, that is, the hydrogen partial pressure is 3
0-200 kg / cm ² , further 100-180 kg / c
A range of m ² is preferred. Although the above pressure is sufficient at about 30 kg / cm ² , it is economical to supply the gas component in the high-pressure gas-liquid separation tank to the reactor as it is, so the pressure of this process is determined by the conditions of each step in the preceding stage. Is done. Furthermore, the hydrogen / oil ratio 300～2000Nm ³ / kiloliter, is preferably in the range of more 500 to 1000 nm ³ / kl. Although the above ratio of about 300 Nm ³ / kl is sufficient, it is economical to supply the gas component of the high-pressure gas-liquid separation tank to the reactor as it is. Is determined by the following conditions. LHSV is preferably in the range of 0.5 to 10 h ^-1 . If the LHSV is less than 0.5 h ^-1 , a sufficient processing speed cannot be obtained from an economical viewpoint, and 10 h
If it exceeds ^-1 , the reaction time is insufficient and the treatment of cracked oil is not performed sufficiently. For the same reason as above, LHSV is 1.
More preferably, it is in the range of ⁰ to 5.0 h ^-1 .

As the hydrorefining catalyst used in the above hydrorefining treatment, alumina, a compound obtained by adding a compound of boron, silicon or phosphorus to alumina, or a catalyst containing iron-containing aluminosilicate is used as a carrier. A catalyst supporting at least one selected from metals belonging to Groups 6, 8, 9, and 10 is preferably used. As such a thing, the thing similar to what was used in the above-mentioned (A), (C) step or (B) step can be used. Such a hydrorefining catalyst preferably has an average pore diameter of 20 to 100 °. If the average pore diameter is less than 20 °, the diffusion resistance in the catalyst will increase and the reaction will not proceed sufficiently. On the other hand, if it exceeds 100 °, the surface area becomes small, and a sufficient reaction rate cannot be obtained. For the same reason as above, the average pore diameter is more preferably 20 to 60 °. After hydrotreating the heavy hydrocarbon oil in this way, the treated oil is introduced into a separation step according to a conventional method, and is separated into a gas portion and a liquid portion by treating in a plurality of separation tanks. Among them, the gas portion is subjected to a treatment such as an increase in hydrogen purity after removing hydrogen sulfide, ammonium and the like, and is recirculated to the reaction step together with the newly supplied hydrogen gas.

On the other hand, the liquid portion separated in the separation step
It is introduced into a distillation step and fractionated (separated) into each fraction according to a conventional method. Conditions for this separation include, for example,
Under normal pressure, that is, in normal pressure 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 gas oil fraction is 343 to 3
By using 80 ° C. and 380 ° C. or higher as residual oil, naphtha fraction, kerosene fraction, light oil fraction and residual oil fraction can be separated. In addition, you may perform this distillation fractionation by vacuum distillation. The residual oil fraction is further subjected to vacuum distillation to obtain a desired fraction. In this manner, a high-quality, high-quality, high-value-added gasoline fraction, kerosene-oil fraction, lubricating oil base, etc. can be produced from a low-quality heavy hydrocarbon oil in high yield.

[0021]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Preparation Example 1 Preparation of Alumina A 50 wt% aqueous solution of gluconic acid 280 was added to 80 kg of an aqueous sodium aluminate solution having a concentration of 5.0 wt% in terms of Al ₂ O ₃
After adding g, 94 kg of an aluminum sulfate aqueous solution having a concentration of 2.5% by weight in terms of Al ₂ O ₃ was added to obtain an alumina slurry having a pH of 7.0. This alumina slurry was collected by filtration with a table filter and washed with 0.2% by weight of aqueous ammonia to prepare an alumina hydrate containing pseudoboehmite. Next, a small amount of aqueous ammonia was added to the alumina hydrate to adjust the slurry pH of the alumina hydrate to 10.6.
After adjusting to 0 and further adjusting the alumina concentration to 8.8% by weight, the mixture was refluxed and stirred at 95 ° C. for 20 hours to grow the crystallite diameter of pseudo-boehmite to 65 °. This alumina hydrate was heated and concentrated with a kneader to obtain a kneaded product (X). The kneaded product (X) was formed into granules having a diameter of 0.9 mm by an extruder, dried in air at 110 ° C. for 16 hours, and fired at 550 ° C. for 3 hours. The average diameter of pores of 600 ° or less of the obtained alumina obtained by nitrogen adsorption method is 134 °, and pores having a diameter in the range of 100 to 150 ° are 60 °.
84.0% of the pores at 0 ° or less, and 1.2% of the pores at 60 ° or less were 600% or less. The average diameter of pores in the range of 62 to 600 ° determined by the mercury intrusion method is 1
28 °, and 62 pores having a diameter of 128 ° ± 10 °
90.4% of the pores in the range of -600 ° and 138% or more of the pores were 5.4% of the pores in the range of 62-600 °.

Preparation Example 2 Preparation of Amorphous Hydrotreating Catalyst A
Ltd. Water 1.33 l boric acid 534g was added to a solution prepared by dissolving warming, it was kneaded in a kneader by mixing the kneaded product (X) 5 kg in Preparation Example 1, 1/16-inch cylindrical pellets extruded The product was dried at 110 ° C. for 16 hours in the air, and calcined at 550 ° C. for 3 hours to obtain a catalyst carrier containing 15% by weight of boron oxide. To 1 kg of the carrier, 650 ml of an aqueous solution containing 170 g of molybdenum oxide and 75 g of cobalt carbonate was added and impregnated.
The resultant was dried while gradually raising the temperature to 550 ° C., and then calcined at 550 ° C. for 1 hour to obtain an amorphous hydrogenation catalyst A. The supported amounts of molybdenum and cobalt in this catalyst were 14.0% by weight and 3.7% by weight, respectively, as metal oxides.

Preparation Example 3Preparation of alumina slurry Stainless steel with 200 liter steam jacket
Sodium aluminate solution (Al_TwoO_ThreeExchange
Glucon of 80kg and 50% by weight
240 g of the acid solution was added and heated to 60 ° C. Then sulfuric acid
Aluminum solution (Al_TwoO_Three(Converted concentration: 2.5% by weight) 8
Prepare 8kg in a separate container and it will reach pH 7.2 in 15 minutes
Add the diluted aluminum sulfate solution
An aluminum slurry (prepared slurry I) was obtained. Then,
100 kg of the prepared slurry I
1m internal volume^ThreeAnd keep it at 60 ° C.
10m through the external circulation line ^Three/ Hr at a flow rate of 0.
It was circulated for 5 hours to obtain an alumina seed. Then Al
Sodium mate aqueous solution (Al_TwoO_ThreeConverted concentration 5.0 weight
%) At a flow rate of 150 kg / hr with aluminum sulfate aqueous solution.
Solution (Al_TwoO_Three(Converted concentration 2.5% by weight)
Alumina seed through external circulation line at hr flow rate
10m^Three/ Hr at the same time while circulating at a flow rate of
Was. This operation was continuously performed for 3 hours. Also during this time
1m^ThreeAdjust the pH of the slurry in the tank to aqueous aluminum sulfate
PH 7.0 to 7.5 by controlling the amount of liquid added
Retention mix slurry II was obtained. The prepared slurry II was changed to Al_Two
O_ThreeTransfer 3.0 kg in conversion to a flat plate filter and dehydrate
300 liters of 0.3% by weight ammonium water (60 ° C)
And washed. 15% by weight of deionized water
Ammonia water at pH 10.5_TwoO_ThreeConverted concentration
A slurry of 19% by weight, then at 95 ° C. for 30 hours,
The mixture was baked with stirring to obtain an alumina slurry.

PREPARATION EXAMPLE 4 Crystalline aluminosi containing iron sulfate method
Preparation of silicate (Fe-SHY) Synthetic Na-Y zeolite (Na ₂ O content: 13.3% by weight,
The SiO ₂ / Al ₂ O ₃ molar ratio was 5.0 exchanged with ammonium, and NH ₄ —Y zeolite (Na ₂ O content 1.3% by weight) was used.
I got This was steamed at 580 ° C. to obtain a steamed zeolite. After suspending 10 kg of steaming zeolite in 115 liters of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Next, 63.7 kg of a 10% by weight sulfuric acid solution was added to this suspension over 35 minutes.
Further, a ferric sulfate solution having a concentration of 0.57 mol / liter 11.5
kg was added over 10 minutes, and after the addition, the mixture was further stirred for 30 minutes, followed by filtration and washing to obtain an iron-containing crystalline aluminosilicate (Fe-SHY) slurry I having a solid content of 30.5% by weight.

<Various physical properties of iron-containing crystalline aluminosilicate> (a) TPR measurement (heat-up program reduction measurement) The iron-containing crystalline aluminosilicate obtained above was dried and sized to form a 100 mg quartz glass tube. Filling,
It was calcined at 377 ° C. for 2 hours under a flow of dry air. After cooling to room temperature, it was kept in a hydrogen-argon mixed gas stream for several hours. Thereafter, the temperature was raised to 1077 ° C. at a rate of 10 ° C./min, and the mass balance of hydrogen was measured during this time. In addition,
The amount of hydrogen was determined with a thermal conductivity detector (TCD). The obtained [Fe] dep and the temperature of the high-
It is shown in the table. (B) Measurement of lattice constant [UD] The dried iron-containing crystalline aluminosilicate obtained above and a silicon internal standard powder were mixed well, pulverized, and filled in a sample holder for X-ray powder diffraction. This is C
A u-tube, an applied voltage of 40 kV, and an applied current of 40 mA were measured by a step scan, and the lattice constant [UD] of the iron-containing crystalline aluminosilicate was calculated from the obtained peak angle. The results are shown in Table 1.

(C) Measurement of Terminal SiOH Group / Bronsted Acid Ratio A dried powder sample (30 mg) formed into a wafer having a diameter of 20 mm was subjected to a pressure of not more than 1.0 × 10 ⁻⁴ mmHg. After heat treatment at 450 ° C. for 1 hour to remove the physically adsorbed water, the mixture is cooled to room temperature, and the spectrum is measured by a transmission method using an infrared spectrophotometer. From then obtained IR spectrum, 3740 absorbance D and 3560 ± absorbance C, 3630 ± 10 cm ^-1 of ± 10 cm ^-1 1
The absorbance E at 0 cm ^-1 is measured and divided by the actual wafer weight to standardize. The standardized absorbance is C '
Assuming that D'E ', the terminal SiOH group / Bronsted acid ratio is a value obtained from the formula of C' / (D '+ E').
The results are shown in Table 1.

[0027]

[Table 1]

Preparation Example 5 Zeolite-based hydrocracking catalyst B
Preparation of B-1 and B-2 The alumina slurry obtained in Preparation Example 3 and the iron-containing crystalline aluminosilicate (Fe-SHY) slurry I (30.5% by weight concentration) obtained in Preparation Example 4 were weighed in terms of solid content. The ratio is 90 /
The resulting mixture was mixed and concentrated in a kneader to obtain a kneaded material having a plasticity of 10. The kneaded material was extruded with an extruder at 1 /
After forming into a 16-inch size cylindrical pellet and drying at 110 ° C. for 16 hours,
It was calcined at 0 ° C. for 3 hours to obtain a carrier 1. Next, Carrier 2 was obtained in the same manner as in Carrier 1, except that the calcination conditions were calcination at 650 ° C. for 3 hours in an atmosphere containing steam. In addition, the lattice constants of the carriers 2 and 1 when the calcination conditions were 650 ° C. for 3 hours in the presence of steam were 24.30 and 24.29 °, respectively, which were the same as those of the iron-containing crystalline aluminosilicate. Next, a suspension of molybdenum trioxide and nickel carbonate in pure water was heated at 90 ° C.
And then malic acid was added to dissolve it. This solution is impregnated into the supports 1 and 2 so as to have a MoO ₃ content of 15.0% by weight and a NiO content of 4.25% by weight with respect to the entire catalyst, and then molybdenum trioxide and nickel carbonate are dried and calcined. And zeolite-based hydrocracking catalyst B-
1, B-2 was obtained. The surface area, pore volume, and average pore diameter of the catalyst were measured, and the results are shown in Table 2.

[0029]

[Table 2]

[Note] Measurement method Surface area: BET method Pore volume: Nitrogen adsorption method Average pore diameter: Mercury intrusion method Preparation Example 6 Iron nitrate crystalline aluminosilicate (F
Preparation of e-SHY) Synthetic Na-Y zeolite (Na ₂ O content 13.3% by weight,
The SiO ₂ / Al ₂ O ₃ molar ratio was 5.0 exchanged with ammonium, and NH ₄ —Y zeolite (Na ₂ O content 1.3% by weight) was used.
I got This is steamed at 580 ° C and USY
-1 was obtained. After suspending 10 kg of USY-1 in 2000 liters of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Then, a 10% by weight nitric acid solution 8 was added to the suspension.
1.9 kg was added in 40 minutes, and 21.9 liters of a 0.57 mol / liter ferric nitrate solution was added in 10 minutes. After the addition, the mixture was further stirred for 30 minutes, filtered and washed.
An iron-containing crystalline aluminosilicate (Fe-SHY) slurry II having a solid content of 30.5% by weight was obtained.

<Various physical properties of iron-containing crystalline aluminosilicate> (a) TPR measurement (heat-reduction program reduction measurement) 100 mg of the Fe-SHY obtained above was filled in a quartz glass tube, and was placed at 377 ° C. under flowing dry air. For 2 hours. After cooling to room temperature, it was kept in a hydrogen-argon mixed gas stream for several hours. Thereafter, the temperature was raised to 1077 ° C. at a rate of 10 ° C./min, and the mass balance of hydrogen was measured during this time. The amount of hydrogen was determined with a thermal conductivity detector (TCD). Table 3 shows the obtained [Fe] dep and the temperature of the high-temperature side reduction peak. (B) Measurement of lattice constant [UD] The Fe-SHY obtained above and the silicon internal standard powder were mixed well, pulverized, and filled in a sample holder for X-ray powder diffraction. This was measured by a step scan using a Cu bulb, an applied voltage of 40 kV, and an applied current of 40 mA, and the lattice constant [UD] of the crystalline aluminosilicate containing iron was calculated from the obtained peak angle. The results are shown in Table 3.

[0032]

[Table 3]

Preparation Example 7 Zeolite-based hydrocracking catalyst B
Preparation of -3, B-4 Alumina slurry obtained in Preparation Example 3 and iron-containing crystalline aluminosilicate (Fe-SHY) slurry obtained in Preparation Example 6
II (30.5% by weight) in terms of solids, weight ratio 90/1
The mixture was mixed and concentrated in a kneader so as to be 0 to obtain a plastic kneaded material. This kneaded material was extruded 1/1 by an extruder.
Molded into a 6-inch cylindrical pellet,
After drying at 110 ° C. for 16 hours, 550 ° C. in a dry air flow
For 3 hours to obtain a carrier 3. Next, Carrier 4 was obtained in the same manner as Carrier 3, except that the calcination conditions were calcination at 650 ° C. for 3 hours in an atmosphere containing steam. The carrier 4 and 3 were sintered at 650 ° C. for 3 hours in an atmosphere containing water vapor, and had lattice constants of 24.32 and 24.33 °, respectively, which were the same as those of the iron-containing crystalline aluminosilicate. Next, a suspension of molybdenum trioxide and nickel carbonate in pure water was added to 90
℃, then malic acid was added and dissolved. This solution is applied to the supports 3 and 4 with MoO ₃
And then dried and calcined to obtain zeolite-based hydrocracking catalysts B-3 and B-4. The surface area, pore volume and average pore diameter of the catalyst were measured.
It is shown in the table.

[0034]

[Table 4]

[Note] Measurement method Surface area: BET method Pore volume: Nitrogen adsorption method Average pore diameter: Mercury intrusion method Preparation Example 8 Preparation of faujasite type aluminosilicate
Ltd. Na ₂ O content of 0.8 _{wt%, SiO 2 / Al 2 O} 3 molar ratio
5.0 g of Y-type zeolite is charged into a rotary kiln, and subjected to a self-steaming treatment at 700 ° C. for 3 hours to form a steaming zeolite Y (hereinafter referred to as STM).
It is called zeolite Y. ) Got. Table 5 shows the physical properties of the STM zeolite Y. 500 g of STM zeolite Y obtained above was suspended in 6250 ml of pure water,
The temperature was raised to 75 ° C. with stirring, and 467 of 10% by weight nitric acid aqueous solution was used.
7 g were added over 30 minutes. 30 minutes after the end of addition,
After maintaining at 75 ° C., the mixture was filtered, and the obtained solid content was adjusted to 20%.
The resultant was washed with twice the amount of warm water and then dried to obtain a desired faujasite-type aluminosilicate (hereinafter, referred to as aluminosilicate Y). Table 5 shows the physical properties of this aluminosilicate Y.

[0036]

[Table 5]

Preparation 9Zeolite-based hydrocracking catalyst B
Preparation of -5 11 g of the aluminosilicate Y obtained in Preparation Example 8 and boehmite
Add 485 g of Togel to 50 ml of deionized water
And kneaded the mixture to a water content suitable for wet extrusion molding.
Conditioning, molding pressure 30kg / cm^Two1mm in diameter and 3 in length
mm. Dry this molded product at 120 ° C for 3 hours
After that, calcination is performed at 500 ° C. for 3 hours in the air, and the
Aluminosilicate containing 10% by weight of silicate Y
-An alumina carrier was obtained. Next, 75 g of this carrier was
(NO_Three)_Two・ 6H_Two13.6 g of O and (NH_Four) ₆Mo₇
O_{twenty four}・ 4H_Two45 ml of aqueous solution containing 74.8 g of O
And then impregnated in vacuum and dried at 90 ° C for 3 hours
And then calcined at 500 ° C. for 5 hours to obtain pelletized
Olite-based hydrocracking catalyst B-5 was obtained. In addition, this touch
The cobalt content in the medium is 4 wt.
%, Molybdenum content is MoO_ThreeConverted to 10 weight
%Met. Surface area, pore volume and average pore diameter of this catalyst
The diameter is shown in Table 6.

[0038]

[Table 6]

[Note] Measurement method Surface area: BET method Pore volume: Nitrogen adsorption method Average pore diameter: Mercury intrusion method Example 1 Amorphous hydrotreating catalyst prepared in Preparation Example 2 in a high-pressure fixed-bed reactor A 50 ml, the zeolite-based hydrocracking catalyst B-1 prepared in Preparation Example 5, 40 ml, and the hydrotreating catalyst A 10 ml were charged in this order. Next, the heavy gas oil shown in Table 7 was added to this reactor with L
HSV: 1.0 hr ^-1 , hydrogen partial pressure: 110 kg / cm ² ,
The oil was passed under the condition of a hydrogen / oil ratio: 1000 Nm ³ / kl, and a hydrogenation treatment was carried out so that the decomposition rate of the 360 ⁺ ° C fraction was 65% by weight. Table 8 shows the reaction temperature, the yield of the middle distillate (135-360 ° C fraction) and the specific gravity and viscosity index of the 360 ⁺ ° C fraction in the product oil at the 400th hour of operation.
Here, the 360 ⁺ ° C fraction refers to a fraction whose boiling point exceeds 360 ° C. The hydrotreated oil was separated into a kerosene fraction having a boiling point of 125 to 235 ° C and a gas oil fraction having a boiling point of 235 to 360 ° C, and analyzed.
Has a specific gravity of 0.786, a smoke point of 24 mm, and 235 to
The 360 ° C fraction (light oil) had a specific gravity of 0.826, a sulfur content of 15 ppm, a monocyclic aromatic of 13.6% by volume, and a polycyclic aromatic of 1.7% by volume. Example 2 In Example 1, the zeolite-based hydrocracking catalyst B-1 was used.
Was carried out in the same manner as in Example 1, except that the zeolite-based hydrocracking catalyst B-2 prepared in Preparation Example 5 was used instead. Table 8 shows the results.

[0040]

[Table 7]

[0041]

[Table 8]

Example 3 In a high-pressure fixed-bed reactor, 50 ml of the amorphous hydrotreating catalyst A prepared in Preparation Example 2 and 40 ml of the zeolite-based hydrocracking catalyst B-3 prepared in Preparation Example 7 were mixed with the above hydrogenation. 10 ml of treated catalyst A were charged in this order. Next, the same heavy gas oil as used in Example 1 was charged into this reactor with LHSV: 1.0 hr ^-1 , hydrogen partial pressure: 110
kg / cm ^2, a hydrogen / oil ratio: by passing the oil under the condition of 1000 Nm ³ / kl, 360 ⁺ ° C. fraction degradation rate was hydrotreated so that 65 wt%. Reaction temperature at 400 hours of operation, middle distillate (135-360 ° C distillate)
The 360 ⁺ ° C. fraction gravity and viscosity index of the resulting rate and in the product oil are shown in Table 9. Example 4 In Example 3, the zeolite-based hydrocracking catalyst B-3 was used.
Was carried out in the same manner as in Example 3, except that the zeolite-based hydrocracking catalyst B-4 prepared in Preparation Example 7 was used instead. Table 9 shows the results.

[0043]

[Table 9]

Example 5 In a high-pressure fixed bed reactor, 50 ml of the amorphous hydrotreating catalyst A prepared in Preparation Example 2 and 40 ml of the zeolite-based hydrocracking catalyst B-5 prepared in Preparation Example 9 were mixed with the above hydrogenation. 10 ml of treated catalyst A were charged in this order. Next, the same heavy gas oil as used in Example 1 was charged into this reactor with LHSV: 1.0 hr ^-1 , hydrogen partial pressure: 110
kg / cm ^2, a hydrogen / oil ratio: by passing the oil under the condition of 1000 Nm ³ / kl, 360 ⁺ ° C. fraction degradation rate was hydrotreated so that 65 wt%. Reaction temperature at 400 hours of operation, middle distillate (135-360 ° C distillate)
The 360 ⁺ ° C. fraction gravity and viscosity index of the resulting rate and in the product oil are shown in Table 10. The hydrotreated oil has a boiling point of 125 to 23.
A kerosene fraction at 5 ° C and a gas oil fraction with a boiling point of 235 to 360 ° C were separated and analyzed. The 125 to 235 ° C fraction (kerosene) had a specific gravity of 0.791 and a smoke point of 23.5 mm, 2
The 35-360 ° C fraction (light oil) had a specific gravity of 0.826, a sulfur content of 45 ppm, a monocyclic aromatic of 12.5% by volume, and a polycyclic aromatic of 1.7% by volume.

[0045]

[Table 10]

PREPARATION EXAMPLE 10 Crystalline alumino containing iron sulfate method
Preparation of silicate (Fe-SHY) Synthetic Na-Y zeolite (Na ₂ O content: 13.3% by weight,
The SiO ₂ / Al ₂ O ₃ molar ratio was 5.0 exchanged with ammonium, and NH ₄ —Y zeolite (Na ₂ O content 1.3% by weight) was used.
I got This was steamed at 580 ° C. to obtain a steamed zeolite. After suspending 10 kg of steaming zeolite in 115 liters of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Next, 63.7 kg of a 10% by weight sulfuric acid solution was added to this suspension over 35 minutes.
Further, a ferric sulfate solution having a concentration of 0.57 mol / liter 11.5
kg was added in 10 minutes, and after stirring for an additional 30 minutes, the mixture was filtered and washed, and the iron-containing crystalline aluminosilicate (Fe-SHY) slurry having a solid content of 30.5% by weight III
I got

<Various physical properties of iron-containing crystalline aluminosilicate> (a) TPR measurement (heat-up program reduction measurement) The iron-containing crystalline aluminosilicate obtained above was dried and sized, and placed in a 100 mg quartz glass tube. Filling,
It was calcined at 377 ° C. for 2 hours under a flow of dry air. After cooling to room temperature, it was kept in a hydrogen-argon mixed gas stream for several hours. Thereafter, the temperature was raised to 1077 ° C. at a rate of 10 ° C./min, and the mass balance of hydrogen was measured during this time. In addition,
The amount of hydrogen was determined with a thermal conductivity detector (TCD). The obtained [Fe] dep and the temperature of the high-
The results are shown in Table 1. (B) Measurement of lattice constant [UD] The dried iron-containing crystalline aluminosilicate obtained above and a silicon internal standard powder were mixed well, pulverized, and filled in a sample holder for X-ray powder diffraction. This is C
A u-tube, an applied voltage of 40 kV, and an applied current of 40 mA were measured by a step scan, and the lattice constant [UD] of the iron-containing crystalline aluminosilicate was calculated from the obtained peak angle. The results are shown in Table 11.

(C) Measurement of Terminal SiOH Group / Bronsted Acid Ratio A dried powdery sample (30 mg) formed into a wafer having a diameter of 20 mm was pressed at a pressure not larger than 1.0 × 10 ⁻⁴ mmHg. After heat treatment at 450 ° C. for 1 hour to remove the physically adsorbed water, the mixture is cooled to room temperature, and the spectrum is measured by a transmission method using an infrared spectrophotometer. From then obtained IR spectrum, 3740 absorbance D and 3560 ± absorbance C, 3630 ± 10 cm ^-1 of ± 10 cm ^-1 1
The absorbance E at 0 cm ^-1 is measured and divided by the actual wafer weight to standardize. The standardized absorbance is C '
Assuming that D'E ', the terminal SiOH group / Bronsted acid ratio is a value obtained from the formula of C' / (D '+ E').
The results are shown in Table 11.

[0049]

[Table 11]

Preparation Example 11 Preparation of Alumina Slurry 80 kg of a sodium aluminate solution (concentration in terms of Al ₂ O _3: 5.0% by weight) and 240 g of a 50% by weight gluconic acid solution were placed in a 200-liter steam-jacketed stainless steel container. And heated to 60 ° C. Next, an aluminum sulfate solution (2.5% by weight in terms of Al ₂ O ₃ ) 8
8 kg was prepared in a separate container, and the diluted aluminum sulfate solution was added so that the pH became 7.2 in 15 minutes to obtain an aluminum hydroxide slurry (formulated slurry). The prepared slurry was dehydrated with a flat filter and washed with 0.3% by weight aqueous ammonia at 60 ° C. to obtain a washed alumina cake.
To this washed alumina cake, 15% by weight of aqueous ammonia and pure water were added to obtain a slurry having a solid concentration of 12% by weight (as Al ₂ O ₃ ) and a pH of 10.5. This was stirred at 95 ° C. for 8 hours in a stainless steel aging tank equipped with a reflux condenser.
After aging for a period of time, the mixture was concentrated by heating and deammonia and partially removed of water to obtain a 20% by weight alumina slurry (as Al ₂ O ₃ ).

Preparation Example 12 Zeolite-based hydrocracking catalyst
Preparation of B-6 Al ₂ O ₃ / B was added to the alumina slurry obtained in Preparation Example 11.
Boric acid was added so that the weight ratio of ₂ O ₃ was 85/15 to obtain an alumina-boric acid slurry. This alumina
The boric acid slurry and the iron-containing crystalline aluminosilicate (Fe-SHY) slurry III obtained in Preparation Example 10 are introduced into a kneader such that the weight ratio becomes 90/10 in terms of solid content, and the mixture is extruded with heating and stirring. After concentrating to a possible concentration, the mixture was formed into a cylindrical pellet using an extruder with a die having a hole diameter of 1.8 mm. Next, after drying at 110 ° C. for 12 hours, it was calcined at 550 ° C. for 3 hours to obtain a zeolite-based hydrocracking catalyst B-6. Table 12 shows the surface area, pore volume, and average pore diameter of this catalyst.

[0052]

[Table 12]

[Note] Measurement method Surface area: BET method Pore volume: Nitrogen adsorption method Average pore diameter: Mercury intrusion method Example 6 Amorphous hydrotreating catalyst prepared in Preparation Example 2 in a high pressure fixed bed reactor A 50 ml, the zeolite-based hydrocracking catalyst B-6 prepared in Preparation Example 12, 40 ml, and the above-mentioned hydrotreating catalyst A 10 ml were charged in this order. Next, the heavy gas oil shown in Table 13 was introduced into this reactor with LHSV: 1.0 hr ^-1 , hydrogen partial pressure: 110 kg / c.
The oil was passed under the conditions of m ² , hydrogen / oil ratio: 1000 Nm ³ / kl, and hydrogenation treatment was performed so that the distillation rate at 360 ⁺ ° C was 65% by weight. Table 14 shows the reaction temperature, the middle distillate (125-360 ° C. fraction) yield, the specific gravity of the 360 ⁺ ° C. fraction in the product oil, and the viscosity index at the 400th hour of operation. Here, the 360 ⁺ ° C fraction refers to a fraction whose boiling point exceeds 360 ° C. Of this middle distillate, 125 to 23
The 5 ° C fraction (kerosene) has a specific gravity of 0.793 and a smoke point of 25 mm
235-360 ° C fraction (light oil) has a specific gravity of 0.8
33. Sulfur content is 5 ppm, monocyclic aromatic is 11.2% by volume, and polycyclic aromatic is 1% by volume. Therefore, the sulfur content and the polycyclic aromatic content in light oil are low, and it has good properties. Light oil can be obtained, and kerosene having properties similar to those obtained by a normal production method can be obtained.

[0054]

[Table 13]

[0055]

[Table 14]

[0056]

According to the method of the present invention, a low-quality heavy hydrocarbon oil is efficiently subjected to catalytic hydrogenation, and a high-quality, high-value-added gasoline fraction, a kerosene oil fraction, and a lubricating oil base are obtained. The material can be produced at a high yield and stable operation is possible. Further, according to the method of the present invention, highly desulfurized (ie, ultra-low sulfur content) gas oil can be efficiently produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10G 47/16 C10G 47/16 47/18 47/18 47/20 47/20

Claims (6)

[Claims] 1. A method for hydrotreating at least one heavy hydrocarbon oil selected from heavy gas oil, cracked gas oil, vacuum gas oil, coker gas oil, visbreaker gas oil and solvent deasphalted oil. (A) a step of bringing the heavy hydrocarbon oil into contact with an amorphous hydrotreating catalyst to perform hydrodesulfurization and denitrification, and (B) converting the hydrocarbon oil treated in the step (A) into zeolite. Contacting with a hydrocracking catalyst for hydrocracking, and (C) the above (B)
A step of bringing the hydrocarbon oil treated in the step into contact with an amorphous hydrotreating catalyst and subjecting it to a hydrodesulfurization treatment, in order. 2. The hydrotreating method according to claim 1, wherein a part of the hydrocarbon oil treated in the step (C) is recycled to the step (A) and / or the step (B). 3. An amorphous hydrotreating catalyst used in the steps (A) and (C) is applied to an amorphous carrier by using a group 6, 8, 9, or 10 of the periodic table. 2. The hydrotreating method according to claim 1, wherein at least one metal selected from metals belonging to the group III is supported. 4. The zeolite-based hydrocracking catalyst used in the step (B) is added to a support containing Y-type zeolite and / or a support containing alumina and boron oxide to form a group 6, group 8, or group 8 of the periodic table. 2. The hydrotreating method according to claim 1, wherein at least one metal selected from metals belonging to Group 9 and Group 10 is supported. 5. The method according to claim 4, wherein the Y-type zeolite is at least one selected from faujasite-type aluminosilicate, iron-containing steaming aluminosilicate by a nitric acid method, and iron-containing steaming aluminosilicate by a sulfuric acid method. Hydrotreating method. 6. The content of the Y-type zeolite in the carrier is 5 to 5.
The hydrotreating method according to claim 4 or 5, wherein the amount is 60% by weight.