JP2001107060A - Preparation method for gas oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an effective preparation method for gas oil in which a sulfur content and a nitrogen content contained in a hydrocarbon oil hardly poisons a catalyst, a removing activity of an aromatic hydrocarbon and a sulfur content is high, and gas oil having a little contents of a sulfur content and an aromatic hydrocarbon is obtained by using a hydrogenation refining catalyst with a low ratio of hydrogenation decomposition. SOLUTION: A preparation of gas oil comprises three steps, the first comprising contacting a hydrocarbon oil containing at least 80 wt.% of a fraction having ranges of boiling point of 170-390 deg.C and containing a sulfur content and an aromatic hydrocarbon with hydrogen in the presence of a hydrogenation catalyst to decrease the contents of a sulfur content to not more than 0.05 wt.%, the second step comprising removing gas components from the resulting hydrogenation refined oil obtained in the first step 1, and the third step comprising contacting the refined oil obtained in the second step with hydrogen in the presence of a hydrogenation refining catalyst in which at least one noble metal selected among noble metals of the periodic table group VIII is carried on a substantially amorphous metallic oxide carrier containing silicon and magnesium as principal components to decrease the aromatic hydrocarbon and a sulfur content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing light oil having a low content of sulfur and aromatic hydrocarbons from hydrocarbon oil.

[0002]

2. Description of the Related Art Diesel engines are excellent in fuel efficiency, and light oil is expected to continue to grow in demand as a transportation fuel, but environmental regulations on light oil are becoming more stringent. Last year, the European Union announced sulfur regulations for gas oil since 2000, according to which the sulfur content of gas oil is currently 0.05% by weight, by 2000 it was 0.035% by weight, and in 2005 it was Was reduced to 0.005% by weight. In Japan as well, the Environment Agency has stated that it is necessary to further reduce the sulfur content of diesel oil.
It is believed that it can be reduced to 005 to 0.01% by weight. Aromatic hydrocarbons are also expected to be regulated. Since it is recognized that aromatic hydrocarbons are involved in the generation of black smoke in diesel exhaust gas, reduction of such hydrocarbons is strongly demanded.

[0003] These environmental regulations are very strict for petroleum refining manufacturers, and there is an urgent need to develop catalysts and process technologies relating to ultra-deep desulfurization and aromatic hydrogenation to meet the new regulations. As a method for reducing the sulfur content and aromatic hydrocarbons in gas oil, a two-stage hydrorefining method for simultaneously performing hydrodesulfurization and hydrogenation of aromatic hydrocarbons has been proposed.

For example, Japanese Patent Application Laid-Open No. Hei 5-237391 discloses that hydrocarbon oil is subjected to deep desulfurization to reduce the sulfur content to 0.05%.
Weight percent or less, a second step of removing gaseous components from the refined oil of the first step, and a process wherein the refined oil of the second step has a unit cell length of less than 24.65 angstroms, silica / Contacting a Y-type zeolite having an alumina ratio of greater than 5 and an alkali metal or alkaline earth metal content of less than 0.3% by weight with an aqueous solution of an alkali metal or alkaline earth metal to form an alkali metal or alkaline earth metal In the presence of a catalyst carrying a Group VIII noble metal of the periodic table on a zeolite that has been treated to increase the content of 1.5 times or more than that before the treatment, it is contacted with hydrogen to produce an aromatic hydrocarbon and a sulfur component. And a third step for reducing hydrogenation.

Japanese Patent Application Laid-Open No. 8-283747 discloses that
In a similar two-stage hydrorefining method, a catalyst in which at least one kind of Group VIII metal of the periodic table is supported on a carrier containing a crystalline clay mineral containing silicon and magnesium as main components is used in the third step. There has been proposed a hydrorefining method characterized in that it is used for hydrotreating. However, in these methods, the catalyst used in the third step is significantly poisoned by sulfur and nitrogen contained in the feedstock,
There is a problem that the purpose of reducing aromatic hydrocarbons and sulfur content is not sufficiently achieved.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst which is less susceptible to catalyst poisoning by sulfur and nitrogen contained in hydrocarbon oil, has a high activity for removing aromatic hydrocarbons and sulfur, and An object of the present invention is to provide a method for efficiently producing gas oil having a low sulfur content and a low aromatic hydrocarbon content by using a hydrorefining catalyst having a low hydrocracking ratio.

[0007]

In order to achieve the above object, the present invention provides a method for producing gas oil, comprising at least 80% by weight of a fraction having a boiling point in the range of 170 to 390 ° C. and containing sulfur and aromatic hydrocarbons. A hydrocarbon oil containing hydrogen and hydrogen in the presence of a hydrorefining catalyst to reduce the sulfur content to 0.05% by weight or less, and the hydrogenation obtained in the first step. A second step of removing a gas component from the refined oil, and applying the refined oil obtained in the second step to a substantially amorphous metal oxide carrier containing silicon and magnesium as a main component;
A third step of contacting with hydrogen in the presence of a hydrotreating catalyst carrying at least one noble metal selected from Group II noble metals to reduce aromatic hydrocarbons and sulfur content. It is a feature.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the first step of the present invention, hydrodesulfurization of hydrocarbon oil is mainly performed, and in the next second step, hydrogen sulfide generated in the first step, removal of a gas component containing ammonia is performed,
Further, in the third step, hydrodesulfurization is mainly performed simultaneously with the hydrogenation of the aromatic hydrocarbon. In the first step, it is necessary to perform refining at a high temperature in order to reduce the sulfur concentration of light oil to 0.05% by weight or less. In the second step, it is necessary to remove gas components such as hydrogen sulfide and ammonia to minimize the active poisoning of the catalyst in the third step. And in the third step,
A catalyst that is less susceptible to catalyst poisoning by sulfur and nitrogen is required. General noble metal catalyst, for example, Pd-Pt / Al ₂ O
_{When 3} is used as a catalyst in the third step, Pd and Pt are significantly poisoned by the sulfur and nitrogen components contained in the refined oil in the second step, so that the hydrogenation of aromatic hydrocarbons almost proceeds. Did not. However, the present inventors, in the third step, a substantially amorphous metal oxide carrier containing silicon and magnesium as main components, at least one noble metal selected from Group VIII noble metals of the periodic table. It has been found that the use of a catalyst loaded with, suppresses catalyst poisoning due to sulfur content and facilitates the hydrogenation reaction of aromatic hydrocarbons, thereby completing the present invention.

First, the starting oil used in the present invention has a boiling point of 17
It contains 80% by weight or more, preferably 90% by weight or more of a fraction at 0 ° C. or more and 390 ° C. or less, and contains a sulfur content and an aromatic hydrocarbon. Here, the hydrocarbon oil preferably has a sulfur content of 0.5 to 2.0% by weight and an aromatic hydrocarbon content of 80% by weight or less. Examples of the hydrocarbon oil include a distillate obtained by atmospheric or reduced pressure distillation of crude oil, a distillate obtained by fluid catalytic cracking (FCC), a distillate obtained by thermal cracking, and the like. Among them, a distillate obtained by atmospheric distillation of crude oil, a distillate obtained by fluid catalytic cracking (FCC), and a mixture thereof are preferably used.

The hydrorefining temperature in the first step of the present invention is preferably
Preferably 280 to 450 ° C, more preferably 320 to
420 ° C, most preferably in the range of 340-400 ° C.
You. If the reaction temperature is too low, less than 280 ° C, the sulfur concentration will be insufficient.
Min, while the reaction temperature is 45
If the temperature exceeds 0 ° C, the material of the reactor is limited and the life of the catalyst is shortened.
It is disadvantageous in that the running cost is low. What
The hydrorefining temperature in the first step is the average temperature of the reaction tower
(WABT). In addition, the first step hydrorefining
The pressure is preferably 1 to 20 MPa, more preferably 2
~ 15MPa, most preferably in the range of 3 ~ 10MPa
is there. If the refining pressure is lower than 1 MPa, the sulfur content
It is difficult to reduce it sufficiently, while exceeding 20 MPa
If the pressure is increased, the capital investment will be enormous. The first step
The hydrorefining pressure referred to in the above is a hydrogen partial pressure. Further
To the supply of petroleum distillate in the first step (liquid hourly space velocity, LHS
V) is 1-10h ^-1Is preferred, and particularly preferably 2 to
6h^-1Range. Hydrogen / hydrocarbon of the first step
The flow rate of the oil is preferably 30 to 600 Nl / l, and particularly preferably 6 to 600 Nl / l.
0 to 500 Nl / l is a preferred range.

As the hydrorefining catalyst used in the first step, a catalyst usually used for hydrorefining petroleum distillate can be used. For example, a catalyst in which an active metal is supported on a porous inorganic oxide such as alumina, titania, boria, silica, silica-alumina, alumina-titania, alumina-boria, silica-magnesia, and alumina-magnesia is used. As the active metal to be supported, at least one metal selected from Group V, Group VI, and Group VIII iron group metals of the periodic table is used, and examples thereof include vanadium, chromium, molybdenum, tungsten,
Cobalt, nickel and the like can be mentioned. These active metals can be present on the support in the form of metals, oxides, sulfides or mixtures thereof. In particular, in the first step of the present invention,
It is preferable to use a catalyst in which at least one of cobalt and nickel and at least one of molybdenum and tungsten are supported on an alumina carrier, and more preferably, a catalyst in which cobalt and molybdenum are supported as active metals on an alumina carrier. That is. The loading amount of the active metal is preferably in the range of 3 to 20% by weight as an oxide.

The shape of the hydrorefining catalyst is granular, tablet-like, column-like (including those having a cross-section of three leaves or four leaves).
Any of these may be used. The hydrorefining catalyst in the first step may be preliminarily sulfurized by a known method before being used in hydrorefining. The type of the hydrorefining reaction tower used in the first step of the present invention may be any of a fixed bed, a fluidized bed and an expanded bed, but a fixed bed flow reactor is particularly preferred. In the first step, the contact between hydrogen, petroleum distillate and the catalyst may be any of parallel upward flow, parallel downward flow, and countercurrent.

In the present invention, the content of sulfur in the hydrocarbon oil must be reduced to 0.05% by weight or less by the hydrorefining in the first step, and the content is preferably 0.03% by weight.
Or less, more preferably 0.02% by weight or less, and most preferably 0.015% by weight or less. In the present invention, the reason why the sulfur content in the hydrocarbon oil is set to 0.05% by weight or less by the hydrorefining in the first step is that the sulfur content in the hydrocarbon oil exceeds 0.05% by weight. If included, the third
This is because aromatic hydrocarbons are not sufficiently reduced in the hydrorefining process.

Next, after hydrorefining in the first step,
In the second step, gas components including the hydrogen sulfide, ammonia gas and the like generated in the first step are separated from the obtained hydrorefined oil. For this separation, a commonly used gas separator or the like can be used.

The temperature among the separation conditions in the second step is as follows:
Preferably 200-450 ° C, more preferably 220
To 400 ° C, most preferably 240 to 370 ° C, and the pressure is preferably equal to the reaction pressure of the first step, specifically 1 to 20 MPa, preferably 2 to 15 M
Pa, most preferably in the range of 3 to 10 MPa. Then, two or more gas component separators in the second step are preferably provided in series. When two or more units are provided in series, it is preferable that the temperature of the subsequent separator be lower than the temperature of the preceding separator. The separated gas obtained from the second step can be reused together with hydrogen for makeup after removing hydrogen sulfide and ammonia by a usual washing method such as water washing and amine washing.

Subsequently, after the gas components are separated by the gas separator of the second step, in the third step, the refined oil obtained in the second step is mixed with pure hydrogen or a hydrogen-containing gas in the presence of a hydrotreating catalyst. Perform hydrorefining. At this time, when a hydrogen-containing gas is used, the hydrogen content is preferably at least 60% by volume, more preferably at least 80% by volume. This hydrogen-containing gas is, for example, a mixed gas of a product gas from a reaction tower and unreacted hydrogen, and includes hydrogen, a hydrocarbon gas, an inert gas, and a small amount of hydrogen sulfide.

When hydrogen is used in the third step, pure hydrogen is preferable, but when a hydrogen-containing gas is used, the concentration of hydrogen sulfide must be 0.2% by volume or less.
0 volume ppm or less is preferable, and 300 volume ppm
The following are more preferred.

Further, the catalyst carrier used in the third step of the present invention must be composed of a substantially amorphous metal oxide containing silicon and magnesium as main components. Here, a substantially amorphous metal oxide containing silicon and magnesium as main components excludes oxygen that is always the largest among the elements constituting the metal oxide, and hydrogen that is largely present as water or a hydroxyl group. In addition, it means a substantially amorphous metal oxide in which the two most significant elements based on the number of atoms are silicon and magnesium. Silicon and magnesium, which are the main components of the catalyst carrier, may contain a large amount of silicon and a small amount of magnesium, or conversely, a small amount of silicon and a large amount of magnesium. The atomic ratio of Mg / Si is 0.45 to 1. It is preferable to set the range to 5. The reason is that the atomic ratio of Mg / Si is less than 0.45 or 1.
If it exceeds 5, the aromatic hydrogenation activity decreases.

The amorphous metal oxide may contain a small amount of components other than silicon and magnesium, such as transition metals and typical metals. In addition, there are "crystalline" and "amorphous" metal oxides containing silicon and magnesium as main components, and "crystalline" metal oxides are included in the scope of the present invention. Absent. Examples of crystalline metal oxides containing silicon and magnesium as main components include stevensite, hectorite, saponite, chlorite, talc, vermiculite, serpentine, antigolite, sepiolite, attapulgite, palygorskite, enstatite, and phorite. Stellite, protoenstatite, etc., but these metal oxides are "crystalline"
Therefore, it is out of the scope of the present invention.

The reason that the catalyst carrier used in the third step of the present invention is limited to an amorphous metal oxide is that the amorphous metal oxide has a solid acid property required for hydrorefining. That's why. The catalyst used in the third step of the present invention is not an essential component, but a binder may be used if necessary for molding. The binder is not particularly limited, and examples thereof include alumina, silica, silica-alumina, and other metal oxides. When the binder is used, the total amount of SiO ₂ and MgO in the carrier is 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. The molding method can be performed by any method commonly used, and examples include extrusion molding and tablet molding. The shape of the catalyst used in the third step is granular, tablet-like, column-like (the cross-section is three-lobed,
And the like, and the molded support is preferably calcined. The firing temperature at this time is preferably from 300 ° C. to 800 ° C., and 400 ° C.
The temperature is more preferably 700 ° C. or lower.

As the noble metal of Group VIII of the periodic table used as an active metal for the catalyst carrier in the third step of the present invention, Ru, Rh, Pd, and Pt are preferable, and Pd and Pt are more preferable. These precious metals may be used alone or in combination of two or more.
In particular, it is preferable to use a mixture of Pt and Pd. The loading amount of these noble metals is preferably 0.05% by weight or more and 5% by weight or less. These metals can be supported by any method generally used, and specific examples include an ion exchange method, an impregnation method, and a gas phase supporting method. Preferred raw materials vary depending on the supporting method, but in the case of the ion exchange method and the impregnation method, for example, chloride, nitrate, acetate, chloroammine complex and the like are used.In the gas phase supporting method, a carbonyl compound having a vapor pressure is preferably used. Can be The supporting of the metal may be carried out before or after the molding of the carrier, but is preferably carried out usually after the molding.

The catalyst used in the third step of the present invention is usually subjected to a calcination treatment. The firing temperature at this time is preferably from 300 ° C to 700 ° C, more preferably from 400 ° C to 600 ° C. Although not an essential condition, it is preferable to perform hydrogen reduction in a hydrogen stream as a pretreatment, and the reduction temperature at this time is preferably 200 ° C or higher and 500 ° C or lower, more preferably 250 ° C or higher and 450 ° C or lower.
The temperature is preferably from 80 ° C to 400 ° C.

The hydrorefining temperature in the third step of the present invention is preferably 150 to 400 ° C., more preferably 20 to 400 ° C.
It is in the range of 0-370C, most preferably 240-350C. When the reaction temperature is lower than 150 ° C., the hydrogenation reaction of the aromatic hydrocarbon does not sufficiently proceed. On the other hand, when the reaction temperature is higher than 400 ° C., the life of the catalyst is shortened, and a cracking reaction occurs and gas oil The yield decreases. The hydrorefining temperature in the third step is the temperature of the highest temperature section of the reaction tower (generally, near the outlet of the reaction tower).

The type of the hydrorefining reaction tower in the third step may be any of a fixed bed, a fluidized bed and an expanded bed, but a fixed bed flow reactor is particularly preferred. In the third step, the contact between the hydrogen, the petroleum distillate and the catalyst used in the first step may be any of parallel upward flow, parallel downward flow, and countercurrent. Furthermore, the hydrorefining pressure in the third step is preferably 1 to 20 MPa, more preferably 2 to 15 MPa,
Most preferably, it is in the range of 3 to 10 MPa. As described above, the pressure in the third step is preferably equal to or similar to the pressure in the first step. The reason is that the purification pressure is 1
If the pressure is lower than MPa, the hydrogenation reaction of the aromatic hydrocarbon in the third step does not proceed sufficiently, while if the pressure is higher than 20 MPa, equipment investment becomes large. The third
The hydrorefining pressure of the process is the hydrogen partial pressure.

The feed amount (liquid hourly space velocity, LHSV) of the petroleum distillate in the third step is preferably 0.1 to 10 h ^-1 , more preferably 0.5 to 5 h ^-1 , and particularly preferably ¹ to 5 h ^-1. Ｈ4h ⁻¹ . Further, the flow ratio of hydrogen / hydrocarbon oil in the third step is preferably 100 to 2000 Nl / l, more preferably 200 to 1500 Nl / l.
And 300 to 1000 Nl / l is a particularly preferred range.

The method for hydrogenating aromatic hydrocarbons in a hydrocarbon oil in the third step of the present invention is a method for hydrogenating aromatic hydrocarbons while suppressing hydrocracking. Is a hydrogenation method in which the yield of a product having a boiling point lower than the initial boiling point of the refined oil in the second step is 5% by weight or less. The yield of the product having a boiling point lower than the initial boiling point of the feedstock is preferably 6% by weight.
Or less, more preferably 4% by weight or less, particularly preferably 2% by weight or less. Thus, in the third step of the present invention, the aromatic hydrocarbon is reduced to preferably 10% by weight or less, more preferably 5% by weight or less.

[0027]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the scope of the examples. Example 1 A third step hydrotreating catalyst was prepared as follows. To 2266 g of No. 3 water glass, 564 g of sodium hydroxide (granular, purity: 95%) was added, and ion-exchanged water was added to make a total volume of 6 liters. %) 1932 g
Was added to ion-exchanged water to make the total amount 6 liters. Then, 8 liters of ion-exchanged water maintained at 60 ° C. is placed in a 30 liter container, and the hydrate is added thereto at a constant rate (100 ml / min) while adding the α liquid and the β liquid under strong stirring. A precipitate formed.
Next, the precipitate is sufficiently washed with water and then extruded.
After drying at 10 ° C for 12 hours, it was calcined at 600 ° C for 3 hours to prepare a silica-magnesia carrier a. The resulting carrier a had a chemical composition of 64% by weight of silica and 36% by weight of magnesia.

The carrier a was impregnated with a mixed aqueous solution of tetraammineplatinum chloride and tetraamminepalladium chloride, dried at 110 ° C. for 12 hours, and calcined at 500 ° C. for 3 hours to prepare a catalyst A. Note that P in the catalyst A
The loadings of t and Pd were 0.3% by weight and 0.7% by weight, respectively.

The feedstock has a sulfur content of 1.5
8% by weight, and the fraction from 176 ° C. to 385 ° C.
The first step hydrorefining was carried out under the reaction conditions shown in Table 1 below by a pressurized fixed-bed flow reactor using a straight run containing 0% by weight.

As the hydrorefining catalyst in the first step, a catalyst having 5 wt% CoO and 18 wt% MoO ₃ supported on an alumina carrier was used. The catalyst was presulfurized in a known manner.
Next, the purified oil obtained by separating the gas component from the refined oil obtained in the first step by a high-pressure gas separator in the second step and recovering the same in the third step using the catalyst A under the conditions shown in Table 2 below Hydrorefining was performed. Prior to the reaction, add 3 parts of catalyst A
Hydrogen reduction was performed at 20 ° C. for 3 hours. The amounts of the aromatic hydrocarbons in the feed oil, the refined oil of the second step and the refined oil of the third step are as follows:
Analysis was performed using HPLC (backflush method). The distillation properties of the raw material oil, the refined oil of the second step, and the refined oil of the third step were measured by gas chromatography of the distilled gas. The properties of the resulting refined oil in the third step are shown in Table 3 below.

Comparative Example 1 In the preparation of the hydrorefining catalyst in the third step, γ was used instead of the silica-magnesia carrier a.
Catalyst B was prepared in the same manner as in Example 1 except that a negative-type alumina extruded product was used as a carrier. Hydrorefining was carried out in the same manner as in Example 1, except that the obtained catalyst B was used as a catalyst in the third step instead of the catalyst A. The properties of the refined oil obtained as a result are also shown in Table 3 below.

[Comparative Example 2] In preparing the hydrorefining catalyst in the third step, instead of the silica-magnesia carrier a, Mizukalife P-1 (trade name: one kind of layered clay mineral) was used.
An extruded powder of Mizusawa Chemical Industry Co., Ltd.) was used as a carrier. An extruded product of Mizuka Life P-1 was prepared as follows. Mizukalife P-1 powder was placed in an aqueous solution of ammonium acetate (2 mol / l), heated at 80 ° C. for 2 hours with sufficient stirring, ion-exchanged, filtered, and dried at 110 ° C. for 12 hours. When Na in Mizukalife P-1 powder after drying was analyzed,
The content was 0.01% by weight based on the baked product at 00 ° C. Next, the dried Mizuka life P-1 was kneaded with alumina hydrate peptized with diluted nitric acid (Condea), extruded, dried at 110 ° C. for 12 hours, and further baked at 500 ° C. for 3 hours. Thus, a carrier was prepared. The amount of Mizukalife P-1 in the carrier was 80% by weight.

This carrier is impregnated with a mixed aqueous solution of tetraammineplatinum chloride and tetraacinepalladium chloride,
After drying at 110 ° C. for 12 hours, the mixture was calcined at 500 ° C. for 3 hours to prepare Catalyst C. Note that Pt in the catalyst C,
The supported amounts of Pd were 0.3% by weight and 0.7% by weight.
Hydrorefining was carried out in the same manner as in Example 1, except that the obtained catalyst C was used as the catalyst in the third step instead of the catalyst A. The properties of the refined oil obtained as a result are also shown in Table 3 below.

Comparative Example 3 In preparing the hydrorefining catalyst in the third step, a carrier was prepared as follows. Acid type Y zeolite powder (manufactured by Tosoh Corporation, HSZ-330H)
UA: trade name) was steamed at 800 ° C. for 6 hours, then placed in 0.5N diluted nitric acid, stirred at 80 ° C. for 1 hour, filtered, washed and dried. The obtained Y-type zeolite had a unit cell length of 24.25 angstroms, a silica / alumina ratio of 41.0, and a Na content of 0.1% by weight. Catalyst D was prepared in the same manner as in Example 1 except that this zeolite was used as a raw material instead of ion-exchanged stevensite (Comparative Example 2). Hydrorefining was carried out in the same manner as in Example 1, except that the obtained catalyst D was used as a catalyst in the third step instead of the catalyst A. The properties of the refined oil obtained as a result are also shown in Table 3 below.

[0035]

Table 1 Reaction conditions of the first step Reaction pressure (MPa) 5 Hydrogen / hydrocarbon oil ratio (Nl / l) 200 LHSV (h ^-1 ) 2 Reaction temperature (° C) 350

[0036]

Table 2 Reaction conditions for the third step Reaction pressure (MPa) 5 Hydrogen / hydrocarbon oil ratio (Nl / l) 400 LHSV (h ^-1 ) 2 Reaction temperature (° C) 320

[0037]

[Table 3] Properties of obtained refined oil * 1: A hydrocarbon having one or more aromatic rings. * 2: Indicates the amount of the fraction having a boiling point lower than the initial boiling point of the refined oil of the second step, which is generated in the third step.

As can be seen from Table 3, according to the embodiment of the present invention, in the third step, a method using a catalyst using a γ-type alumina carrier (Comparative Example 1), a catalyst using a layered clay mineral carrier was used. Compared with the method used (Comparative Example 2) and the method using a catalyst using a Y-type zeolite carrier (Comparative Example 3), the content of aromatic hydrocarbons in the refined oil could be significantly reduced. . Further, in the examples of the present invention, the generation of cracked light fractions generated by hydrocracking was less than in the method using a catalyst using a Y-type zeolite carrier in the third step (Comparative Example 3). Thus, it has been found that the method according to the present invention is an excellent method for producing light oil having a low sulfur content and a low aromatic hydrocarbon content.

[0039]

As described above, according to the present invention, the hydrogenation activity for converting an aromatic hydrocarbon into a saturated hydrocarbon is high,
In addition, the rate of hydrocracking can be suppressed to a low level, and gas oil having a low sulfur content and a low aromatic hydrocarbon content can be efficiently produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10G 45/52 C10G 45/52 67/00 67/00 C10L 1/08 C10L 1/08 (72) Inventor Eiji Yokozuka 3-18-5 China, Ichikawa City, Chiba Prefecture Sumitomo Metal Mining Co., Ltd. F-term in Central Research Laboratory (reference) BC72B BC75A BC75B CC02 DA06 EA02Y EC26 FA01 FB05 FB09 FB14 FB67 4H029 CA00 DA00 DA01 DA09 DA10

Claims (1)

[Claims] 1. A fraction having a boiling point of 170 to 390 ° C.
A hydrocarbon oil containing at least 0% by weight and containing sulfur and an aromatic hydrocarbon is brought into contact with hydrogen in the presence of a hydrorefining catalyst to reduce the sulfur content to 0.05% by weight or less. One step, a second step of removing a gas component from the hydrorefined oil obtained in the first step, and the purified oil obtained in the second step is substantially composed of silicon and magnesium as main components. Aromatic hydrocarbons and sulfur in contact with hydrogen in the presence of a hydrorefining catalyst in which at least one noble metal selected from Group VIII noble metals of the periodic table is supported on an amorphous metal oxide support And a third step of reducing the amount of light oil.