JP2014173025A - Hydrogenation purification method for vacuum gas oil - Google Patents

Abstract

Disclosed is a hydrorefining method for vacuum gas oil that exhibits high desulfurization activity and denitrification activity.
SOLUTION: After titanium alkoxide dissolved in an organic solvent in a refractory inorganic oxide containing alumina is used as a raw material, titanium is supported in an amount of 0.5 to 15% by mass with respect to the refractory inorganic oxide by titania conversion. The sulfur and nitrogen contained in a vacuum gas oil under a hydrogen gas stream using a catalyst obtained by supporting an active metal composed of molybdenum, cobalt and nickel on a carrier prepared through a drying and / or calcination step, followed by calcination A method for hydrorefining vacuum gas oil, characterized by removing water.
[Selection figure] None

Description

  The present invention relates to a hydrorefining method that highly removes sulfur and nitrogen in vacuum gas oil in the presence of hydrogen.

In recent years, liquid fuels have been required to further reduce the sulfur content. In response to this demand, domestic oil companies have already considered various clean fuel production methods. In particular, gasoline has a sulfur content of 10 ppm or less, so oil companies have taken measures such as improving the catalyst and adding equipment.
In general, the main base material of gasoline is cracked gasoline produced by a fluid catalytic cracker (FCC). Therefore, in order to reduce the sulfur content in gasoline, it is important to reduce the sulfur content in cracked gasoline.
It is known that the sulfur content in cracked gasoline depends on the sulfur content in the vacuum gas oil that is the raw material of FCC, and the sulfur content in the cracked gasoline increases as the sulfur content in the vacuum gas oil increases. Therefore, in order to produce clean gasoline having a low sulfur content, it is necessary to highly remove in advance the sulfur content in the vacuum gas oil that is the raw material of FCC.
Normally, hydrorefining equipment (FCC pretreatment) for desulfurizing vacuum gas oil is used in a fixed-bed reaction tower packed with a hydrotreating catalyst in a hydrogen stream under high-temperature and high-pressure reaction conditions. A hydrorefining treatment is performed. As hydrorefining catalysts, catalysts in which an active metal such as molybdenum or cobalt is supported on a carrier such as alumina are widely used.
It is known that the desulfurization activity in hydrorefining of vacuum gas oil is affected by the type of carrier and the type and amount of active metal. For example, Non-Patent Document 1 discloses the influence of a support (alumina or silica) and an active metal (molybten or a mixture of molybten and cobalt). Non-Patent Document 2 discloses desulfurization activity of a catalyst using zirconia or titania as a support and nickel or tungsten as an active metal. Further, Patent Document 1 discloses that catalytic activity (desulfurization and denitrogenation) is improved by using a support obtained by adding silica or boria to alumina.

JP 2010-222458 A

Applied Catalysis A: Applied Catalysis A: General, Elsevier, 345, 2008, p. 80-88 Applied Catalysis A: Applied Catalysis A: General, published by Elsevier, 257, 2004, p. 157-164

  By the way, in addition to high desulfurization activity, high denitrogenation activity is required for the catalyst for hydrorefining of vacuum gas oil. This is because the catalyst used in FCC is poisoned by a compound containing nitrogen, and the yield of cracked gasoline is lowered. However, despite many years of research and improvement, the actual situation is that a catalyst for hydrorefining not only having high desulfurization activity but also high denitrogenation activity is still unknown.

  The object of the present invention is to produce a catalyst for hydrorefining of vacuum gas oil that is excellent in both desulfurization activity and denitrogenation activity, and to use it for hydrorefining of vacuum gas oil that can highly remove sulfur and nitrogen It is to provide a method.

  As a result of intensive studies, the present inventors have obtained a carrier supporting titanium by a sol-gel method using a specific titanium compound as a raw material for a refractory inorganic oxide containing alumina, and a catalyst supporting a specific active metal on the carrier. By using it, it discovered that the above-mentioned subject could be solved and came to complete this invention.

  That is, in the present invention, titanium alkoxide dissolved in an organic solvent in a refractory inorganic oxide containing alumina is used as a raw material, and titanium is supported in an amount of 0.5 to 15% by mass with respect to the refractory inorganic oxide by titania conversion. After that, sulfur in vacuum gas oil under a hydrogen stream is supported under a hydrogen stream using a catalyst obtained by supporting active metal composed of molybdenum, cobalt and nickel on a carrier prepared through drying and / or calcination processes. And a method for hydrorefining vacuum gas oil, characterized by removing nitrogen.

  By the hydrorefining method of the present invention, sulfur and nitrogen in the vacuum gas oil can be highly removed.

  The present invention is described in detail below.

  The catalyst used in the hydrorefining method of vacuum gas oil of the present invention is a refractory inorganic oxide containing alumina, supported on titanium by a sol-gel method using titanium alkoxide dissolved in an organic solvent as a raw material, and then dried and / or This is a catalyst obtained by carrying an active metal composed of molybdenum, cobalt and nickel on a carrier prepared through a calcining step and calcining it.

  The refractory inorganic oxide containing alumina is not particularly limited as long as it is a refractory inorganic oxide mainly containing alumina as a main component, and examples thereof include alumina and silica / alumina. In particular, it is preferable to use a silica-alumina composite oxide containing 3 to 20% by mass, preferably 5 to 15% by mass of silica, because the effect of the present invention is great. If the silica content is less than 3% by mass or more than 20% by mass, the desulfurization performance of the finally obtained catalyst tends to deteriorate, which is not preferable.

The catalyst carrier is prepared through a drying and / or firing step after supporting titanium by a sol-gel method using a titanium alkoxide dissolved in an organic solvent as a raw material in a refractory inorganic oxide containing alumina.
In other words, the titanium loading in the present invention must be performed as follows, unlike the conventional impregnation method or coprecipitation method using a titanium-containing aqueous solution.

The titanium raw material for supporting titanium is limited to titanium alkoxide dissolved in an organic solvent. The titanium alkoxide is a compound represented by the general formula Ti (OR) ₄ (where R represents an alkyl group), and is not particularly limited, but a titanium alkoxide having an alkyl group having 1 to 8 carbon atoms is preferred. When the number of carbon atoms exceeds 8, the time required to support a predetermined amount of titanium becomes longer, and the production efficiency tends to be lowered. Examples of R include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, and an isobutyl group.

  The organic solvent for dissolving the titanium alkoxide is not particularly limited. Specifically, alcohols such as ethanol, propanol, isopropanol and butanol, ethers such as dimethyl ether and diethyl ether, and hydrocarbons such as hexane and toluene. Can be mentioned. Among these, ethanol and hexane are preferable from the viewpoint of cost or the reactivity control of titanium alkoxide.

Titanium alkoxide dissolved in an organic solvent is supported on a refractory inorganic oxide containing alumina by a sol-gel method.
Specifically, a refractory inorganic oxide containing alumina is placed so that the whole is immersed in a non-aqueous solution in which titanium alkoxide is dissolved, and left for about 0.5 to 24 hours. At this time, it is possible to shorten the standing time required to carry a predetermined amount of titanium by performing ultrasonic irradiation.
In addition, if the refractory inorganic oxide used at this time is a molded object, the shape and length can be used without restriction. However, the average pore diameter of the refractory inorganic oxide (molded body) containing alumina is preferably 60 to 180 mm. If it is less than 60%, the sulfur compound in the vacuum gas oil hardly enters the pores of the catalyst, and if it exceeds 180%, the surface area becomes small and the active metal tends to aggregate, and as a result, the desulfurization performance tends to decrease.
In addition, the average pore diameter of the refractory inorganic oxide is measured by a mercury intrusion method, and is a value calculated using a mercury surface tension of 480 dyne / cm and a contact angle of 150 °.

After standing for a predetermined time, the solution is decanted or filtered to remove most of the organic solvent and the like. Thereafter, the support is usually dried at 30 to 150 ° C., preferably 50 to 130 ° C. for about 0.5 to 10 hours to completely remove the organic solvent and the like. If it is less than 30 degreeC, solvent removal is inadequate, and even if it exceeds 150 degreeC, since the solvent removal effect is small, it is unpreferable, respectively.
After drying, it is usually 300 to 550 ° C., preferably 350 to 500 ° C., and high desulfurization activity can be obtained by baking in air compared with the case of only drying. If it is less than 300 ° C. or exceeds 550 ° C., the desulfurization activity tends to decrease, which is not preferable.

The carrier in the present invention is obtained as described above. The titanium content in the carrier is preferably 0.5 to 15% by mass in terms of its oxide (TiO ₂ ). If it is less than 0.5% by mass, it tends to be difficult to obtain high desulfurization activity and denitrification activity, which is not preferable. On the other hand, if it exceeds 15% by mass, the desulfurization activity tends to decrease and the catalyst price becomes expensive.

  In the present invention, it is necessary to support three kinds of metals, molybdenum, cobalt, and nickel, on the support obtained by the above method. The method for supporting these active metals is not particularly limited as long as it is a commonly used method, and examples thereof include an impregnation method. The supported amounts of metal components are as follows.

The supported amount of molybdenum is preferably 10 to 25% by mass and more preferably 16 to 23% by mass in terms of oxide (MoO ₃ ) with respect to the catalyst. If it is less than 10% by mass, the active sites are insufficient, and if it exceeds 25% by mass, molybdenum tends to aggregate, and as a result, desulfurization activity and denitrogenation activity tend to decrease.
The amount of cobalt supported is preferably 0.5 to 6.0% by mass, more preferably 1.5 to 5.0% by mass in terms of oxide (CoO) with respect to the catalyst. When it is less than 0.5% by mass or exceeds 6.0% by mass, the desulfurization activity and the denitrification activity tend to decrease.
The supported amount of nickel is preferably 0.2 to 4.0% by mass, more preferably 0.5 to 2.5% by mass in terms of oxide (NiO) with respect to the catalyst. If it is less than 0.2% by mass, the denitrification activity is remarkably reduced, and if it exceeds 4.0% by mass, the desulfurization activity tends to be reduced.

  Molybdenum, cobalt and nickel can be supported simultaneously or separately, but no significant difference in desulfurization performance is observed, but it is preferable to support them simultaneously from the viewpoint of reducing catalyst production costs.

In addition, it is preferable to support phosphorus together with the active metal because desulfurization performance can be improved. The amount of phosphorus supported is preferably 0.05 to 0.50 mol / mol, more preferably 0.10 to 0.40 mol / mol with respect to molybdenum. If it is less than 0.05 mol / mol or more than 0.50 mol / mol, the desulfurization activity and the denitrification activity tend to decrease, which is not preferable.
The method for supporting phosphorus is not particularly limited. For example, a method of adding a phosphorus compound to a solution impregnated with an active metal and supporting it with the active metal is preferably employed.

  After supporting the active metal, the supported metal component is converted into an oxide by firing in air at 420 to 650 ° C., preferably 450 to 600 ° C., usually for 1 to 3 hours. When the temperature is lower than 420 ° C. or exceeds 650 ° C., the desulfurization activity and the denitrification activity tend to decrease, which is not preferable.

  The present invention can highly remove sulfur and nitrogen in vacuum gas oil by hydrorefining vacuum gas oil under a hydrogen stream using the catalyst produced as described above.

  In the present invention, the vacuum gas oil is a fraction containing 70% by volume or more of a fraction having a boiling point of 360 to 550 ° C., and is a distillate from a vacuum distillation apparatus in petroleum refining or a bottom fraction produced by an FCC apparatus. (CLO fraction). In addition, oil derived from synthetic oil derived from oil sand, coal liquefied oil, bitumen reformed oil, and the like can also be mentioned.

  The hydrorefining of vacuum gas oil in the present invention is not particularly limited as long as it is a commonly used method. For example, a fixed bed reactor is charged with a catalyst and further subjected to preliminary sulfidation, and then heated under a hydrogen atmosphere at a high temperature. Examples include a method performed under high pressure conditions.

  The preliminary sulfidation treatment can be performed by a conventional method that has been conventionally practiced in refinery. That is, the catalyst charged in the reactor is converted from an oxide to a sulfide using a compound containing sulfur such as hydrogen sulfide gas, dimethyl disulfide or straight-run gas oil in a hydrogen stream in the range of 200 to 350 ° C. Convert to.

  The reaction temperature in hydrorefining of vacuum gas oil is usually 300 to 420 ° C. If it is less than 300 ° C., the desulfurization activity and the denitrification activity tend to be remarkably lowered, which is not practical. Moreover, when it exceeds 420 degreeC, since catalyst deterioration will become remarkable and it will approach the heat-resistant temperature (usually about 425 degreeC) of a reaction apparatus, it is unpreferable.

  The reaction pressure (hydrogen partial pressure) in hydrorefining of vacuum gas oil is preferably 3 to 15 MPa, more preferably 5 to 10 MPa. If it is less than 3 MPa, desulfurization activity and denitrogenation activity tend to decrease remarkably, and if it exceeds 15 MPa, hydrogen consumption increases and the operating cost increases, which is not preferable.

Liquid hourly space velocity in the hydrogenation refining of vacuum gas oil is not particularly restricted, it is preferably 0.2～4.0H ^-1, more preferably 0.5~3.5h ^-1. If it is less than 0.2h- ¹ , the throughput is low, so the productivity is low and it is not practical. On the other hand, if it exceeds 4.0 h ⁻¹ , the reaction temperature becomes high and the catalyst deterioration is accelerated.

Preferably a hydrogen / oil ratio in hydrotreating of vacuum gas oil is 150 to 600 nm ³ / kL, and more preferably from 200 to 400 nm ³ / kL. A hydrogen / oil ratio of less than 150 Nm ³ / kL is not preferable because desulfurization activity is reduced. Further, if it exceeds 600 Nm ³ / kL, there is no significant change in desulfurization activity and denitrification activity, which is not preferable because it only increases the operating cost.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

[Preparation of catalyst a]
(In terms of Al ₂ O ₃ 3 kg) basic aluminum salt solution and the alumina hydrate slurry obtained by neutralizing an acidic aluminum salt aqueous solution was washed with a by-product salts were removed, the obtained alumina hydrate The product was adjusted to pH 10.5 and aged at 95 ° C. for 10 hours. The slurry after completion of aging was dehydrated and concentrated and kneaded with a kneader to a predetermined moisture content to obtain an alumina kneaded product. 190 g of nitric acid was added to the obtained alumina kneaded product, and after concentration and kneading again to a predetermined moisture content, it was molded into a 1.8 mm cylindrical shape and dried at 110 ° C. The dried molded product was fired at a temperature of 550 ° C. for 3 hours to obtain alumina.
The average pore diameter of alumina was measured to be 100 mm. The average pore diameter in the present invention is measured by a mercury intrusion method, and is a value calculated using a surface tension of 480 dyne / cm and a contact angle of 150 °.

1 kg of the alumina and 2 L of ethanol were placed in a 5 L container and irradiated with ultrasonic waves for 10 minutes. Thereafter, 1.3 L of an ethanol solution containing 300 g of Ti (OiPr) ₄ was added, followed by ultrasonic irradiation for 1 minute, and then allowed to stand for 3 hours. After standing, the solvent was removed by decantation and the ethanol was washed. The obtained solid was dried in air at 120 ° C. for 3 hours, and further calcined at 480 ° C. for 2 hours, whereby a carrier containing titania (titania- Alumina support) was obtained. The titania content in this carrier was 4% by weight.

  Next, 258 g of molybdenum trioxide, 54 g of basic cobalt carbonate, and 12 g of basic nickel carbonate are suspended in ion-exchanged water, and 85 g of malic acid is added to the suspension to dissolve it. Impregnated. The impregnated product was dried and then calcined at 480 ° C. for 1 hour to obtain the desired catalyst a. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst b]
A titania-alumina carrier was obtained in the same manner as catalyst a except that 800 g of Ti (OiPr) ₄ was used. The titania content in this carrier was 10.5% by weight.
The catalyst was prepared in the same manner as catalyst a to obtain catalyst b. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst c]
The same titania-alumina carrier as catalyst a was used as the carrier, and the catalyst was prepared in the same manner as catalyst a except that 228 g of molybdenum trioxide, 54 g of basic cobalt carbonate, 24 g of basic nickel carbonate, and 95 g of malic acid were used. And catalyst c was obtained. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 18% by weight, 2.5% by weight and 1.0% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst d]
The same titania-alumina carrier as that of catalyst a was used as the carrier, and the catalyst was prepared in the same manner as catalyst a except that 65 g of phosphoric acid was used instead of malic acid to obtain catalyst d. The supported amounts of molybdenum oxide, cobalt oxide, nickel oxide and phosphorus pentoxide in this catalyst were 20% by weight, 2.5% by weight, 0.5% by weight and 3.0% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst e]
In the alumina preparation of catalyst a, the same operation was performed except that nitric acid was not added to the alumina hydrate, and 1.5 kg of commercially available silica sol S-20L (manufactured by JGC Catalysts and Chemicals) was added. 10% by weight of silica-alumina was obtained. A titania-silica-alumina carrier was obtained in the same manner as in catalyst a except that this silica-alumina was used instead of alumina. The titania content in the titania-silica-alumina support was 4% by weight.
A catalyst e was obtained in the same manner as in the catalyst a except that the titania-silica-alumina carrier was used as the carrier. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst f]
A titania-alumina support was obtained in the same manner as in the catalyst a except that 650 g of Ti (OnBu) ₄ was used instead of Ti (OiPr) _{4 and} the standing time was changed from 3 hours to 6 hours. The titania content in this carrier was 8.2% by weight.
The catalyst was prepared in the same manner as catalyst c to obtain catalyst f. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 18% by weight, 2.5% by weight and 1.0% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst g]
A catalyst g was obtained in the same manner as in the catalyst a except that alumina before supporting titania was used instead of the titania-alumina carrier as the carrier. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst h]
In the carrier preparation, the same preparation as that of the catalyst a was performed except that a solution obtained by adding a titanyl sulfate aqueous solution (4% by mass in terms of titania) to an acidic aluminum salt aqueous solution as an acid solution for neutralizing the basic aluminum salt aqueous solution was used. A titania-alumina support was obtained. The titania content in the carrier was 4% by weight.
The catalyst was prepared in the same manner as catalyst a to obtain catalyst h. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst i]
In the carrier preparation, a titania-alumina carrier was obtained in the same manner as catalyst a except that commercially available titania powder TA-300 (Fuji Titanium Co., Ltd.) was added to the alumina kneaded product. The titania content in the carrier was 4% by weight.
The catalyst was prepared in the same manner as catalyst a to obtain catalyst i. The supported amounts of molybdenum oxide, cobalt oxide and nickel oxide in this catalyst were 20% by weight, 2.5% by weight and 0.5% by weight, respectively, with respect to the catalyst.

[Preparation of catalyst j]
The same titania-alumina support as catalyst a was used. Except that basic nickel carbonate was not used, active metal loading was carried out in the same manner as catalyst a to obtain catalyst j. The supported amounts of molybdenum oxide and cobalt oxide on the catalyst were 20% by weight and 2.5% by weight, respectively.

[Example 1]
100 ml of catalyst a was charged into a fixed bed reactor, and presulfided at 320 ° C. for 20 hours under a hydrogen stream containing 3% by volume of H ₂ S to activate the catalyst. Then, vacuum gas oil (density at 15 ° C .: 0.9266 g / ml, sulfur content: 2.3 wt%, nitrogen content: 1000 wt ppm) was passed through, under a hydrogen stream, liquid space velocity 2.0 h ⁻¹ , Hydrogenation purification was performed at a hydrogen partial pressure of 6.5 MPa, a hydrogen oil ratio of 422 Nm ³ / kL, and reaction temperatures of 340 ° C., 360 ° C., and 380 ° C. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Example 2]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst b was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Example 3]
The same presulfidation and hydrorefining as in Example 1 were carried out except that the catalyst c was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Example 4]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst d was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Example 5]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst e was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Example 6]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst f was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Comparative Example 1]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst g was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Comparative Example 2]
Presulfidation and hydrorefining were performed in the same manner as in Example 1 except that the catalyst h was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Comparative Example 3]
Presulfidation and hydrorefining were performed in the same manner as in Example 1 except that the catalyst i was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

[Comparative Example 4]
The same preliminary sulfidation and hydrorefining as in Example 1 were carried out except that the catalyst j was used. The sulfur content of the product oil obtained at each reaction temperature is shown in Table 1, and the nitrogen content is shown in Table 2.

  From the above results, a catalyst in which molybdenum, cobalt, and nickel are supported on a support in which titania is added by a sol-gel method using titanium alkoxide as a raw material has higher desulfurization activity and desulfurization than catalysts in which titania is added by other methods. It can be seen that it has nitrogen activity. Furthermore, it can be seen that the effect is great when the support contains silica or when the metal support liquid contains phosphorus.

Claims (5)

  Using titanium alkoxide dissolved in an organic solvent in a refractory inorganic oxide containing alumina as a raw material, 0.5 to 15% by mass of titanium is supported on the refractory inorganic oxide in terms of titania by a sol-gel method, followed by drying and / or Or removing sulfur and nitrogen in vacuum gas oil under a hydrogen stream using a catalyst prepared by supporting active metal consisting of molybdenum, cobalt and nickel on a carrier prepared through a calcination process. A hydrorefining method of vacuum gas oil characterized by the above.   The method for hydrorefining vacuum gas oil according to claim 1, wherein the refractory inorganic oxide is alumina or silica-alumina containing 3 to 20% by weight of silica.   The method for hydrorefining vacuum gas oil according to claim 1 or 2, wherein the active metal and phosphorus are supported at 0.05 to 0.5 mol / mol with respect to molybdenum.   The method for hydrorefining vacuum gas oil according to any one of claims 1 to 3, wherein the firing temperature in the firing step at the time of carrier preparation is 300 to 550 ° C. The reaction temperature in hydrorefining is 300 to 420 ° C., the hydrogen partial pressure is 3 to 15 MPa, the liquid space velocity is 0.2 to 4.0 h ⁻¹ , and the hydrogen / oil ratio is 150 to 600 Nm ³ / kL. The method for hydrorefining vacuum gas oil according to any one of claims 1 to 4.