JP5371327B2 - Method for producing hydrocarbon oil - Google Patents

Description

  The present invention relates to a method for producing a hydrocarbon oil suitable for efficiently hydrotreating and catalytically reforming a hydrocarbon containing pyrolysis oil.

Benzene, toluene, and xylene (BTX) are very important petrochemical feedstocks for polymers and other petrochemical syntheses. Global demand for BTX is constantly growing. BTX can typically be produced by catalytic reforming of a naphtha fraction.
Naphtha fractions contained in pyrolysis oil produced by pyrolyzing heavy petroleum fractions can be produced more economically than other naphtha fractions, but naphtha fractions contained in pyrolysis oil Has a large amount of unsaturated component, sulfur component and nitrogen component, it cannot be suitably used as a catalytic reforming raw material.

  In general, when unsaturated components are contained in the catalytic reforming raw material, coke tends to be deposited on the catalytic reforming catalyst, so that the activity of the reforming catalyst is reduced and the regeneration temperature and regeneration frequency of catalyst regeneration are reduced. In addition, it is known that when a sulfur content or a nitrogen content is contained, the noble metal and acid sites of the catalytic reforming catalyst are poisoned to reduce the activity. For this reason, when using pyrolysis oil as a catalytic reforming raw material, it is possible to remove unsaturation, sulfur and nitrogen contained in the pyrolysis oil to a level that can be accepted as a catalytic reforming raw material by a method such as hydrodesulfurization. There is a need to.

Multi-stage hydrodesulfurization is known as a general processing method for pyrolysis oil (Patent Documents 1 to 3). However, hydrogenation of the unsaturated component reduces the octane number. In order to prevent the loss of unsaturated components and reduce the loss of octane number, when the reaction is carried out at a low pressure, the sulfur content and the nitrogen content are not sufficiently reduced, and the level is not acceptable as a catalytic reforming raw material.
Increasing the severity of hydrodesulfurization conditions can easily cause carbon precipitation due to polymerization reaction of unsaturated components contained in pyrolysis oil, causing clogging of reactor and heat exchanger (fouling), rapid catalyst There was a problem of causing deterioration.
Special Table 2003-52842 JP-T-2005-516078 JP-T-2006-508196

  This invention solves the said subject, and when processing pyrolysis oil, it makes it a subject to provide a catalytic reforming raw material economically, preventing carbon precipitation in a hydrotreating process.

  As a result of diligent research on the treatment of pyrolysis oil, the present inventors mixed pyrolysis oil with other heavy raw materials at a specific ratio, and performed two-stage hydrotreatment under specific hydrogenation conditions. The inventors have found that a suitable catalytic reforming raw material can be obtained without causing fouling or the like, and have arrived at the present invention.

  That is, the method for producing a hydrocarbon oil of the present invention includes a first step of hydrotreating a first hydrocarbon oil containing 1 to 25% by volume of pyrolysis oil to obtain a first hydrotreated oil; A second step of obtaining a second hydrocarbon oil having a 5% distillation temperature of 30 ° C or higher and a 95% distillation temperature of 180 ° C or lower from the first hydrotreated oil obtained in the first step; The third hydrocarbon oil obtained in the second step is further hydrotreated to obtain a second hydrotreated oil, and 5% from the second hydrotreated oil obtained in the third step. This is a method for producing a hydrocarbon oil comprising a fourth step of obtaining a third hydrocarbon oil having a distillation temperature of 80 ° C. or higher and a 95% distillation temperature of 180 ° C. or lower.

In the hydrogenation treatment in the first step, the reaction pressure is preferably 5.0 MPaG or more, and in the hydrogenation treatment in the third step, the hydrogen oil ratio is preferably 10 to 50 NL / L.
Furthermore, it is preferable that the reaction temperature in the hydrogenation treatment in the first step is 40 ° C. or higher than the reaction temperature in the hydrogenation treatment in the third step.

  As described above, the present invention causes fouling and the like by mixing pyrolysis oil with other heavy fractions at a specific ratio and performing a two-stage hydrotreatment under specific hydrogenation conditions. A suitable catalytic reforming raw material can be obtained. As a result, there is an advantage that the catalytic reforming raw material can be provided more economically than straight-run naphtha.

  The method for producing a hydrocarbon oil of the present invention includes a first step of obtaining a first hydrotreated oil by hydrotreating a first hydrocarbon oil containing 1 to 25% by volume of pyrolysis oil, A second step of obtaining a second hydrocarbon oil having a 5% distillation temperature of 30 ° C. or higher and a 95% distillation temperature of 180 ° C. or lower from the first hydrogenated product oil obtained in the step; The third hydrocarbon oil obtained in step 3 is further hydrotreated to obtain a second hydrotreated oil, and 5% is distilled from the second hydrotreated oil obtained in the third step. This is a method for producing a hydrocarbon oil comprising a fourth step of obtaining a third hydrocarbon oil having a temperature of 80 ° C. or higher and a 95% distillation temperature of 180 ° C. or lower.

[Pyrolysis oil]
The process for obtaining the pyrolysis oil used in the present invention is not particularly limited to the pyrolysis apparatus, the raw oil, and the operating conditions, and any known production process can be employed. The thermal cracking device is a device that decomposes heavy hydrocarbons obtained from atmospheric residue oil, vacuum residue oil, catalytic cracking residue oil, and the like without using a catalyst at a high temperature to obtain light hydrocarbons. For example, a visbreaking process, a flexi coking process, a delayed coking process, a yurika process, an HSC process, etc., which are described in the Petroleum Society edition of “Oil Refinery Process” Kodansha Scientific, 1998) are well known.

As the pyrolysis oil, oil having the following properties can be preferably used. 5% distillation temperature of 40 to 90 ° C., preferably 50 to 80 ° C., 95% distillation temperature of 120 to 190 ° C., preferably from 130 to 180 ° C., bromine number is 15~100gBr ₂ / 100g, preferably 20~90gBr ₂ / 100g, more preferably 25~80gBr ₂ / 100g, sulfur content, 50 to 15,000 mass ppm, preferably from 100 to 13,000 mass ppm, more preferably from 300 to 10,000 mass ppm, nitrogen content Is 1 to 100 ppm by mass, preferably 3 to 90 ppm by mass, more preferably 5 to 70 ppm by mass, and the density (15 ° C.) is 0.680 to 0.770 g / cm ³ , preferably 0.690. ˜0.760 g / cm ³ , more preferably 0.700 to 0.750 g / cm ³ .

[First Step Raw Material Oil (First Hydrocarbon Oil)]
In the present invention, the pyrolysis oil is not treated alone, but is mixed with a heavy fraction and hydrotreated in the first step. Examples of the heavy fraction mixed with the pyrolysis oil include straight-run gas oil, vacuum gas oil, and pyrolysis gas oil.
As the heavy fraction, those having the following properties can be suitably used. 5% distillation temperature is 200 to 350 ° C, preferably 240 to 320 ° C, 95% distillation temperature is 500 to 600 ° C, preferably 530 to 560 ° C, and bromine number is 1 to ₂₀ gBr 2/100 g, preferably 1~12gBr a _2/100 g, sulfur content, 1.0 to 5.0 wt%, preferably from 1.5 to 3.0 wt%, nitrogen content is 400 to 2,000 mass ppm, preferably 550 to It is 1500 mass ppm, and the density (15 ° C.) is 0.850 to 0.960 g / cm ³ , preferably 0.860 to 0.950 g / cm ³ .

The pyrolysis oil is mixed with the heavy fraction and used for the hydrotreatment in the first step. The content of pyrolysis oil in the raw oil is 1 to 25% by volume, preferably 3 to 20% by volume. Preferably, it is 5 to 15% by volume. If the pyrolysis oil exceeds 25% by volume, carbon deposition is likely to occur due to the polymerization reaction of the unsaturated component contained in the pyrolysis oil, and the reactor and heat exchanger are clogged (fouling), and sudden catalyst Since deterioration occurs, it is not preferable, and if it is less than 1% by volume, it is not preferable because the pyrolysis oil cannot be processed substantially and the processing efficiency of the pyrolysis oil decreases.
As for the method for mixing the pyrolysis oil and the heavy fraction, it is only necessary to provide the hydrotreating apparatus in a sufficiently mixed state, and the mixing method is not particularly limited, and an existing method can be used.

The feed oil (first hydrocarbon oil) in the first step in the present invention preferably has a 5% distillation temperature of 130 to 180 ° C, more preferably 140 to 170 ° C, and a 95% distillation temperature of 450-600 degreeC is preferable, More preferably, it is 500-550 degreeC.
Bromine number is preferably at most 40gBr ₂ / 100g, more preferably not more than 30gBr ₂ / 100g. When bromine number exceeds 40gBr 2 _/ 100g, a polymer produced by such unsaturation of the polymerization reaction, is likely to occur fouling, the risk of reactor and heat exchanger clogging, rapid catalyst deterioration Since it increases, it is not preferable.
The sulfur content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and the nitrogen content is preferably 2.0% by mass or less, more preferably 1.5% by mass or less. If the sulfur content exceeds 5.0% by mass or the nitrogen content exceeds 1.5% by mass, it will not be sufficiently desulfurized and denitrified by the hydrogenation treatment in the first step and the third step, and can be accepted as a catalytic cracking raw material. Since it does not reach the level, it is not preferable.

[First step]
The hydrotreatment of the 1st process of this invention can be implemented from a normal hydrodesulfurization apparatus. There are no particular restrictions on the reaction system such as batch type, flow type, fixed bed type, fluidized bed type, etc., but hydrogen and feedstock are continuously added to the hydrotreating catalyst packed in the fixed bed flow type reactor. The type of supplying and contacting is preferable.
The reaction temperature is preferably 300 to 500 ° C, more preferably 340 to 450 ° C. If the reaction temperature is less than 300 ° C., the hydrogenation reaction does not proceed sufficiently, and the effects of desulfurization, denitrogenation, and hydrogenation of unsaturated components are low, such being undesirable. Moreover, since reaction activity will fall rapidly when reaction temperature exceeds 500 degreeC, it is unpreferable.
The reaction pressure is preferably 5.0 MPaG or more, more preferably 5.6 to 25 MPaG, and even more preferably 7.0 to 15 MPaG. When the reaction pressure is less than 5.6 MPaG, the hydrogenation reaction does not proceed sufficiently, and the effects of desulfurization, denitrogenation, and unsaturated hydrogenation are low, which is not preferable. On the other hand, if it exceeds 15 MPaG, the equipment construction cost and the hydrogen cost in operation increase, and the economic efficiency decreases, which is not preferable.
The purity of hydrogen used in the reaction is preferably 60 vol% or more, more preferably 65 to 90 vol%, and still more preferably 70 to 85 vol%. When the hydrogen purity is less than 60 vol%, the hydrogenation reaction does not proceed sufficiently and the effects of desulfurization, denitrogenation and unsaturated hydrogenation are low, which is not preferable. Moreover, when it exceeds 90 vol%, the apparatus construction cost and the hydrogen cost in operation increase, and the economic efficiency is lowered, which is not preferable.

The liquid hourly space velocity (LHSV) is preferably from 0.5~4.0h ^-1, more preferably 1.0~3.0h ^-1. When the LHSV is less than 0.5 h ^−1, it is not preferable because economic efficiency cannot be secured. On the other hand, if the LHSV is more than 4.0 h ⁻¹ , the hydrogenation reaction does not proceed sufficiently, and the effects of desulfurization, denitrogenation, and unsaturated hydrogenation are low.
The hydrogen / oil ratio is preferably 100 to 1000 NL / L, more preferably 200 to 500 NL / L. A hydrogen / oil ratio of less than 100 NL / L is not preferable because the hydrogenation reaction does not proceed sufficiently and the effects of desulfurization, denitrogenation, and unsaturated hydrogenation are low. On the other hand, if the hydrogen / oil ratio exceeds 1000 NL / L, it is not preferable because economic efficiency is remarkably lowered.

  The hydrotreating catalyst is composed of at least one type of catalyst including a NiMo catalyst. Here, the NiMo catalyst is a catalyst containing nickel and molybdenum as active metal elements, and the nickel and molybdenum contents are preferably 1 to 10% by mass of nickel and 2 to 30% by mass of molybdenum. The method for producing the hydrogenation catalyst is not particularly limited, but it is preferable to produce the hydrogenation catalyst by including the above-mentioned active metal element in a porous inorganic oxide carrier that is an oxide such as alumina, silica, or silica-alumina. Further, it may contain an element such as phosphorus, boron or fluorine. Further, hydrogenation containing a chelating organic compound such as ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediamine-N, N, N ′, N′-tetraacetic acid, nitrilotriacetic acid, citric acid, etc. A treatment catalyst may be used.

[Second step]
The second step of the present invention is a second hydrocarbon oil having a 5% distillation temperature of 30 ° C. or higher and a 95% distillation temperature of 180 ° C. or lower from the first hydrotreated oil obtained in the first step. It is the process of obtaining. Fractionation can be carried out by commonly used distillation, so that the 5% distillation temperature is 30 ° C or higher, preferably 40 ° C or higher, and the 95% distillation temperature is 180 ° C or lower, preferably 160 ° C or lower. Do so. When the 5% distillation temperature is lower than 30 ° C., a large amount of lower hydrocarbons are contained, and the lower hydrocarbons are gasified in the hydrotreatment of the third step, and the hydrogen purity in the reaction tower is lowered. Absent. If the 95% distillation temperature exceeds 180 ° C., the sulfur content and nitrogen content increase, and the hydrotreatment of the third step cannot be sufficiently desulfurized and denitrified, and can be accepted as a raw material for catalytic reforming. Since it does not reach the level, it is not preferable.

The naphtha fraction (second hydrocarbon oil) obtained in the second step preferably has a sulfur content of 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass. % or less, the nitrogen content is preferably from 5 mass ppm, more preferably 3 ppm by mass or less, more preferably 1 mass ppm, a bromine number is preferably from 10gBr ₂ / 100g, more preferably 5gBr ₂ / 100g, more preferably not more than 3gBr ₂ / 100g.
The fraction other than the second hydrocarbon oil obtained in the second step is not particularly limited, but the light fraction is a gas fraction such as LPG, and the heavy fraction is, for example, kerosene raw material, catalytic cracking It can be used as a raw material.

[Third step]
The third step of the present invention is a step of further hydrotreating the second hydrocarbon oil obtained in the second step. The feed oil in the third step is mixed with an oil having a boiling point range, sulfur content, nitrogen content, and unsaturated content similar to the second hydrocarbon oil obtained in the second step, such as straight-run naphtha. Can also be used.
The hydrogenation treatment in the third step can also be performed with a normal hydrodesulfurization apparatus. There are no particular restrictions on the reaction system such as batch type, flow type, fixed bed type, fluidized bed type, etc., but hydrogen and feedstock are continuously added to the hydrotreating catalyst packed in the fixed bed flow type reactor. The type of supplying and contacting is preferable.

The reaction temperature is preferably 250 to 350 ° C, more preferably 280 to 320 ° C. When the reaction temperature is less than 250 ° C., the hydrogenation reaction does not proceed sufficiently, and the sulfur content, nitrogen content, and unsaturated content cannot be reduced to a predetermined amount. Moreover, since reaction activity will fall remarkably when reaction temperature exceeds 320 degreeC, it is unpreferable.
The reaction temperature in each of the hydrogenation treatments in the first step and the third step is preferably at least 40 ° C. higher than the third step, more preferably 50 ° C. or higher. If the reaction temperature in the first step is not 40 ° C. or higher than that in the third step, the unsaturated portion is not sufficiently hydrogenated in the first step, and fouling and recombination reactions occur in the third step. .

The reaction pressure is preferably 0.5 to 10 MPaG, more preferably 1 to 4 MPaG. When the reaction pressure is less than 0.5 MPaG, the hydrogenation reaction does not proceed sufficiently, and the effects of desulfurization, denitrogenation, and unsaturated hydrogenation are low, which is not preferable. On the other hand, if it exceeds 10 MPaG, the equipment construction cost and the hydrogen cost in operation increase, which is not preferable because the economy is lowered.
The purity of hydrogen used in the reaction is preferably 50 vol% or more, more preferably 55 to 75 vol%. When the hydrogen purity is less than 50 vol%, the hydrogenation reaction does not proceed sufficiently, and the effects of desulfurization, denitrogenation and unsaturated hydrogenation are low, which is not preferable. On the other hand, if it exceeds 75 vol%, the equipment construction cost and the hydrogen cost in operation increase, which is not preferable because the economy is lowered.

LHSV is preferably 3.0~8.0h ^-1, more preferably 3.5~5.0h ^-1. If the LHSV is less than 3.0 h ⁻¹ , the economical efficiency cannot be secured, which is not preferable. Further, when the LHSV exceeds 8.0 h ⁻¹ , the hydrogenation reaction does not proceed sufficiently, and desulfurization, denitrogenation to a mixed oil containing pyrolysis oil containing a large amount of sulfur, nitrogen and unsaturated components, Since the effect of hydrogenation of unsaturated components is low, it is not preferable.
The LHSV of the hydrogenation treatment in the third step is preferably at least 1.5 times or more , particularly preferably 2 or more times that of the LHSV in the first step. If the LHSV of the hydrogenation process in the third step is not more than 1.5 times greater than that in the hydrogenation process in the first step, the unsaturated component will not be sufficiently hydrogenated in the first step and fouling and rehydration will occur in the third step. This is not preferable because a combination reaction occurs.

The hydrogen / oil ratio is preferably 10 to 50 NL / L, more preferably 30 to 45 NL / L. When the hydrogen / oil ratio is less than 10 NL / L, the hydrogenation reaction does not proceed sufficiently, and desulfurization, denitrogenation to a mixed oil containing pyrolysis oil containing a large amount of sulfur, nitrogen and unsaturated components, Since the effect of hydrogenation of unsaturated components is low, it is not preferable. On the other hand, when the hydrogen / oil ratio exceeds 50 NL / L, the economy is remarkably lowered.
When the hydrogen / oil ratio of the hydrotreating is compared between the first step and the third step, the hydrogen / oil ratio of the first step is preferably at least twice as large as that of the third step, and preferably three times or more. If the hydrogen / oil ratio of the hydrotreating process in the first step is not more than twice as large as that in the third step, the unsaturated component is not sufficiently hydrogenated in the first step and fouling and recombination reactions occur in the third step. This is not preferable.
As the hydrotreating catalyst, at least one kind of catalyst containing the same NiMo catalyst as that used in the first step can be used.

[Fourth step]
The fourth step of the present invention is a third hydrocarbon oil having a 5% distillation temperature of 80 ° C. or higher and a 95% distillation temperature of 180 ° C. or lower from the second hydrotreated oil obtained in the third step. Is obtained by fractional distillation. The fractional distillation can be carried out by a commonly used distillation, and the 5% distillation temperature is 80 ° C. or higher, preferably 85 ° C. or higher, more preferably 90 ° C. or higher, and the 95% distillation temperature is 180 ° C. or lower. Preferably, the temperature is 160 ° C. or lower, more preferably 150 ° C. or lower. When the 5% distillation temperature is less than 80 ° C., a large amount of naphtha having 5 or less carbon atoms is contained, and the catalytic reforming cannot be efficiently performed in the catalytic reforming apparatus. If the 95% distillation temperature exceeds 180 ° C., both the sulfur content and the nitrogen content are remarkably increased, so that it does not reach a level acceptable as a raw material for catalytic reforming.

[Contact reforming raw material]
In order to use the third hydrocarbon oil produced by the above-mentioned steps suitably as a catalytic reforming raw material, the sulfur content is preferably 2 ppm by mass or less, more preferably 1 ppm by mass or less, particularly preferably 0. .5 mass ppm or less. If the sulfur content exceeds 2 mass ppm, the rate of poisoning of the precious metal contained in the catalytic reforming catalyst due to sulfur increases remarkably, and the activity is impaired.
The nitrogen content is preferably 2 mass ppm or less, more preferably 1 mass ppm or less, and particularly preferably 0.5 mass ppm or less. If the nitrogen content exceeds 2 ppm by mass, the acidity of alumina contained in the catalytic reforming catalyst is neutralized and the activity is impaired, which is not preferable.
Bromine number is preferably at most 5gBr ₂ / 100g, more preferably 3gBr ₂ / 100g or less, particularly preferably not more than 1gBr ₂ / 100g. When bromine number exceeds 5gBr 2 _/ 100g, significantly accumulated carbonaceous on catalytic reforming catalyst, because activity is greatly impaired undesirably.

[Catalytic modification]
The catalytic reforming apparatus for performing catalytic reforming and its operating conditions are not particularly limited, and any known manufacturing apparatus and operating conditions can be adopted. The catalytic reformer uses a platinum-alumina catalyst or a bimetallic alumina catalyst in which a second metal such as rhenium, germanium, tin, or iridium is added to platinum, and is desulfurized and desulfurized in a boiling range of about 80 to 180 ° C. It is an apparatus widely used to process straight-run heavy naphtha to obtain reformate, which is a high octane gasoline base material, and aromatic hydrocarbons such as benzene, toluene and xylene. For example, there are UOP platforming process, reniforming process, ERE power forming process, Magna forming process and the like described in “Oil Refinery Process” edited by Petroleum Society (Kodansha Scientific, 1998).

The reaction temperature is preferably 400 to 600 ° C, more preferably 450 to 550 ° C. The liquid space velocity is preferably 0.5 to 5 h ⁻¹ , more preferably ¹ to 2 h ⁻¹ . The reaction pressure is preferably 0.1 to 2 MPaG, more preferably 0.2 to 1.5 MPaG. The purity of hydrogen used in the reaction is preferably 70 to 90 vol%, more preferably 75 to 85 vol%. The hydrogen / oil ratio is preferably 250 to 500 NL / L, more preferably 350 to 400 NL / L.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.

Example 1
Hydrogenation treatment in the first step by mixing 9% by volume of pyrolysis oil obtained by pyrolyzing heavy oil by the delayed coking method and 91% by volume of heavy fraction obtained by mixing straight-run gas oil, vacuum gas oil, and pyrolysis gas oil A first hydrocarbon oil was prepared as a raw material oil. A fixed bed filled with a commercially available NiMo catalyst using this first hydrocarbon oil under conditions of a reaction temperature of 361 ° C., a reaction pressure of 9.3 MPaG, a hydrogen purity of 76 vol%, a hydrogen / oil ratio of 232 NL / L, and LHSV of 1.7 h ^−1. The hydrogenation process of the 1st process was implemented using the flow-type reaction apparatus.

The hydrotreated oil obtained in the first step was subjected to fractional distillation treatment in the second step to obtain a second hydrocarbon oil. 12 volume% of the second hydrocarbon oil obtained in the second step and 88 volume% of straight-run naphtha were mixed to prepare a feed oil for hydroprocessing in the third step. A hydrogenation treatment in the third step was performed using the raw material oil.
The hydrogenation treatment in the third step is performed using a commercially available NiMo catalyst under the conditions of a reaction temperature of 305 ° C., a reaction pressure of 2.5 MPaG, a hydrogen purity of 60 vol%, a hydrogen / oil ratio of 37 NL / L, and LHSV 4.5 h ⁻¹ . This was carried out using a fixed bed flow reactor.

The second hydrotreated oil obtained by the hydrotreating process in the third step was subjected to fractional distillation treatment in the fourth step to obtain a third hydrocarbon oil that is a feedstock oil for catalytic reforming.
The obtained raw material oil for catalytic reforming was subjected to a reaction with a commercially available platinum-alumina catalyst under the conditions of a reaction temperature of 522 ° C., a reaction pressure of 0.35 MPaG, a hydrogen purity of 81 vol%, a hydrogen / oil ratio of 331 NL / L, and LHSV of 1.2 h ^−1. A catalytic reforming treatment was performed. After the gas-liquid separation of the catalytic reforming reaction product, the liquid component was subjected to a stabilizer to adjust the vapor pressure to obtain a catalytic reforming oil.

  In each step from the first step to the fourth step, a pyrolysis oil, a heavy fraction, a first hydrocarbon oil, a second hydrocarbon oil, a straight-run naphtha, used as a raw material oil or obtained as a product, Table 1 shows the properties of the third step (second hydrotreating) feedstock, catalytic reforming feedstock, and catalytic reforming oil.

Claims (2)

A heavy fraction having a 5% distillation temperature of 200 to 350 ° C and a 95% distillation temperature of 500 to 600 ° C has a 5% distillation temperature of 40 to 90 ° C and a 95% distillation temperature of 120 to 190 ° C. As a content in the first hydrocarbon oil, 1 to 25% by volume of pyrolysis oil is mixed , 5% distillation temperature is 130 to 180 ° C, 95% distillation temperature is 450 to 600 ° C, bromine number is 40gBr ₂ / 100g or less, the first hydrocarbon oil sulfur content of 5.0 mass% or less, the reaction temperature 300 to 500 ° C., a reaction pressure 5.6～25MPaG, hydrogen purity 60 vol% or more, liquid hourly space velocity (LHSV ) Hydrotreating with a hydrotreating catalyst containing nickel and molybdenum under conditions of 0.5 to 4.0 h ⁻¹ and a hydrogen / oil ratio of 100 to 1000 NL / L to obtain a first hydrotreated oil 1st step, 5% cut from the first hydrotreated oil obtained in the 1st step Temperature 30 ° C. or more, a second step of 95% distillation temperature to obtain a second hydrocarbon oil is 180 ° C. or less, the second hydrocarbon oil further obtained in the second step, the reaction temperature 250-350 Nickel and molybdenum under the conditions of ℃, reaction pressure of 0.5 to 10 MPaG, hydrogen purity of 50 vol% or more, liquid hourly space velocity (LHSV) of 3.0 to 8.0 h ⁻¹ , and hydrogen / oil ratio of 10 to 50 NL / L. A third step of obtaining a second hydrotreated oil by hydrotreating with the hydrotreating catalyst contained, a 5% distillation temperature of 80 ° C. or higher from the second hydrotreated oil obtained in the third step; 95% distillation temperature of 180 ° C. or less, a sulfur content of 2 ppm by mass or less, a nitrogen content of 2 ppm by mass or less, include a fourth step of bromine number to obtain a third hydrocarbon oil is less 5gBr ₂ / 100g A method for producing a hydrocarbon oil for a catalytic reforming raw material. The method for producing a hydrocarbon oil according to claim 1, wherein the reaction temperature in the hydrotreating process in the first step is 40 ° C or higher than the reaction temperature in the hydrotreating process in the third step.