JP2013241518A - Rubber compounding oil and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably manufacture a rubber compounding oil in which benzo[a]pyrene and other polycyclic aromatic hydrocarbons (PAH) are decreased in an extent in which regulation in Europe is filled for a long period of time.SOLUTION: Rubber compounding oil is manufactured using a method including a hydrodesulfurization step in which at least a part of ethylene bottom oil obtained by thermal cracking of a naphtha-containing raw material is hydrodesulfurized as a raw material, thereby obtaining desulfurized oil; and a hydrogenation step in which an aromatic ring of the desulfurized oil is aromatic hydrogenated. As a result, the rubber compounding oil can be stably manufactured for a long period of time by controlling time activity decrease of a catalyst.

Description

  The present invention relates to a rubber compounding oil (also referred to as a process oil for rubber or a plasticizer for rubber) that is used by mixing with rubber when manufacturing a rubber product such as a tire, a manufacturing method thereof, and a rubber composition for a tire. The present invention relates to a method for manufacturing a product.

Rubber blended oil is blended into rubber when manufacturing rubber products such as tires, and penetrates into the polymer structure of the rubber, facilitating the manufacture and processing of rubber products such as kneading, extruding, molding, etc. It improves the physical properties of the product. Such a rubber compounding oil needs to have good compatibility with rubber.
Rubber includes natural rubber and synthetic rubber, and there are various types of synthetic rubber. Of these, natural rubber and styrene-butadiene rubber are particularly frequently used as tire rubber. And as a rubber compounding oil mix | blended with these rubber | gum, what contains a large amount of aromatic hydrocarbons and has high affinity to rubber is generally used.

  For such a rubber compounding oil, so-called “extract” is used. Extracts can be obtained by removing the oil fraction obtained by vacuum distillation of crude oil and the oil obtained by dewaxing and hydrorefining as necessary after removing the vacuum residue. It is obtained by an extraction treatment with a solvent having an affinity for, and contains a relatively large amount of heavy aromatic compounds.

On the other hand, in Europe, “PAH (polycyclic aromatic hydrocarbon) content in oil used for tires is benzo [a] pyrene content of 1 wtppm or less, and the total PAH content of 8 target substances is Strict environment-related regulations such as “It must be 10wtppm or less” came into effect in 2010.
As described above, it is desired to reduce the concentration of aromatic hydrocarbons including polycyclic aromatic hydrocarbons for oils used as rubber compounding oils.

In addition, the above-mentioned target 8 substances are referred to as “PAH8 substances” and refer to the following 8 substances among PAHs that are subject to regulation in Europe. Hereinafter, these may be simply referred to as PAH8.
(1) Benzo [a] anthracene (benzoanthracene)
(2) Chrysene
(3) Benzo [b] fluoranthene (benzo [b] fluoranthene)
(4) Benzo [j] fluoranthene (benzo [j] fluoranthene)
(5) Benzo [k] fluoranthene (benzo [k] fluoranthene)
(6) Benzo [e] pyrene (benzo [e] pyrene)
(7) Benzo [a] pyrene (benzo [a] pyrene)
(8) Dibenzo [a, h] anthracene (dibenzo [a, h] anthracene

For example, Patent Document 1 discloses a process in which the content of a polycyclic aromatic compound is reduced by performing an extraction step with furfural, etc., on a lubricating oil fraction having a boiling point of 260 to 650 ° C. after distillation under reduced pressure. Oil is disclosed.
Patent Document 2 discloses that a specific carcinogenic polycyclic aromatic compound has a high viscosity, a high flash point, and a high aromaticity by using a specific extract and a specific lubricating base oil. A rubber compounding oil with a reduced content is disclosed.
Further, Patent Document 3 discloses a rubber plasticizer produced by mixing a naphthenic base oil subjected to high-pressure and high-temperature hydrorefining and naphthenic asphalt at a specified ratio.

Japanese Patent No. 3658155 JP 2010-229314 A Japanese Patent No. 3473842

However, these conventional techniques described in Patent Documents 1 to 3 have a problem that a process for obtaining a target object is complicated and a manufacturing cost is high.
The present invention is an alternative to such a conventional technique, and a rubber compounding oil in which benzo [a] pyrene and other polycyclic aromatic hydrocarbons are reduced to the extent that the above-mentioned regulations in Europe are satisfied. It is an object of the present invention to provide a production method that can be stably produced for a long period of time.

As a result of intensive studies on the above problems, the present inventors have focused on ethylene bottom oil obtained from a petrochemical plant, and using this as a raw material, by carrying out a specific two-stage hydrogenation, In this way, we succeeded in stably producing a rubber compounding oil with reduced benzo [a] pyrene and other polycyclic aromatic hydrocarbons for a long period of time, thereby completing the present invention. It was.
That is, the present invention relates to the following [1] to [17].
[1] Hydrodesulfurization step of hydrodesulfurizing at least part of ethylene bottom oil obtained by thermal decomposition of naphtha-containing raw material to obtain desulfurized oil, and hydrogenation for nuclear hydrogenation of the aromatic ring of the desulfurized oil A process for producing a rubber compounding oil, comprising the steps of:
[2] In the hydrodesulfurization step, at least one element selected from molybdenum and tungsten as a main catalyst element on a support mainly composed of any of alumina, silica, titania, zirconia, silica alumina and zeolite. And a hydrodesulfurization catalyst in which at least one element selected from cobalt and nickel is supported as a co-catalyst element, and the raw material is reacted with hydrogen gas at 250 to 400 ° C. [1] Oil production method.
[3] The method for producing a rubber compounding oil according to [1] or [2], wherein in the hydrodesulfurization step, the raw material is reacted with hydrogen gas at a pressure of 1.0 to 20.0 MPaG.
[4] In the hydrogenation step, a hydrogenation catalyst in which at least one element selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum is supported on a support made of an inorganic compound. The method for producing a rubber compounding oil according to any one of [1] to [3], wherein the desulfurized oil is used and reacted with hydrogen gas at 100 to 300 ° C.
[5] The method for producing a rubber compounding oil according to any one of [1] to [4], wherein in the hydrogenation step, the desulfurized oil is reacted with hydrogen gas at a pressure of 1.0 to 20.0 MPaG.
[6] When the hydrogenation step is performed in a continuous reaction system using a hydrogenation catalyst, the cumulative amount of sulfur in the desulfurized oil supplied to the hydrogenation step over one year is 0 per ton of the hydrogenation catalyst. The manufacturing method of the rubber compounding oil in any one of [1]-[5] which is 0.01 ton or less.
[7] In the hydrodesulfurization step, the raw material is reacted with hydrogen gas to convert the sulfur compound in the raw material into hydrogen sulfide, and the reaction liquid obtained in the reaction step is gas-liquid separated. A gas-liquid separation step of removing hydrogen sulfide as a gas from the reaction solution to obtain the desulfurized oil. In the gas-liquid separation step, the reaction solution is decompressed to remove the hydrogen sulfide [1]. -The manufacturing method of the rubber compounding oil in any one of [6].
[8] Production of a rubber compounding oil according to any one of [1] to [7], wherein the raw material is a component (C _v ) having a kinematic viscosity at 100 ° C. of 10 mm ² / s or more in the ethylene bottom oil. Method.
[9] The method for producing a rubber compounding oil according to [8], wherein the component (C _v ) is a distillation residue liquid of the ethylene bottom oil.
[10] The rubber blended oil according to any one of [1] to [9], wherein the naphtha-containing raw material contains 1 to 99% by mass of one or more selected from the group consisting of kerosene, light oil, and natural gas liquid. Production method.
[11] In the hydrodesulfurization step, the raw material diluted with one or more solvents selected from the group consisting of saturated hydrocarbons, saturated ethers, and the rubber compounding oil is reacted with hydrogen gas. [1] A method for producing a rubber compounding oil according to any one of [10].
[12] The method for producing a rubber compounding oil according to any one of [1] to [11], wherein a reaction is performed using a trickle bed reactor in the hydrodesulfurization step and the hydrogenation step.
[13] A rubber compounding oil obtained by the production method according to any one of [1] to [12].
[14] The rubber compounding oil according to [13], wherein the total content of PAH8 substances is 0 wtppm or more and 10 wtppm or less, and the content of benzo [a] pyrene is 0 wtppm or more and 1 wtppm or less.
[15] The rubber compounding oil according to [13] or [14], wherein the aromatic carbon content is 5 to 50%.
[16] The rubber compounding oil according to any one of [13] to [15], which has a kinematic viscosity at 100 ° C. of 10 to 100 mm ² / s.
[17] The rubber compounding oil according to any one of [13] to [16] and at least one rubber selected from the group consisting of natural rubber, styrene butadiene rubber, polybutadiene rubber, butyl rubber, isoprene rubber, and nitrile rubber; A method for producing a rubber composition for tires, comprising mixing the above.

  According to the present invention, since the decrease in the activity of the hydrogenation catalyst is small, the rubber compounded oil in which benzo [a] pyrene and other polycyclic aromatic hydrocarbons are reduced to such an extent that the above-mentioned regulations in Europe are satisfied. Can be manufactured stably over a period. In addition, according to this method, it is possible to effectively use ethylene bottom oil, which has conventionally been limited in use.

2 is a graph in which the total sulfur concentration and total PAH8 content of the rubber compounding oil obtained in Example 1 are plotted against the reaction time. 3 is a graph in which the total PAH content of the rubber compounding oil obtained in Comparative Example 1 is plotted against the reaction time.

Hereinafter, the present invention will be described in detail with reference to embodiments.
The method for producing a rubber compounding oil of the present invention comprises at least a part of an ethylene bottom oil obtained by thermal decomposition of a naphtha-containing raw material, that is, a part of the ethylene bottom oil (for example, a part of components separated by distillation). Alternatively, a hydrodesulfurization process is performed by hydrodesulfurizing all of this as a raw material to obtain desulfurized oil, and a hydrogenation process of nuclear hydrogenating the aromatic ring of the obtained desulfurized oil. Thus, by using a part or all of the ethylene bottom oil as a raw material and hydrogenating it in two stages, benzo [a A rubber compounding oil with reduced pyrene and other polycyclic aromatic hydrocarbons can be stably produced for a long period of time.

  The nuclear hydrogenation is a reaction in which a hydrogen atom is added to an aromatic carbon-carbon double bond in a raw material, and is also referred to as nuclear hydrogenation.

<Method for producing rubber compounding oil>
[Ethylene bottom oil]
In the petrochemical industry, naphtha is generally pyrolyzed at high temperature, and the resulting pyrolyzate is distilled to obtain ethylene, propylene, other olefins, aromatic compounds such as benzene, toluene, xylene, cracked kerosene, cracked gasoline. The product is separated into each fraction such as Among these fractions, the heavy fraction having the highest boiling point is called “ethylene bottom oil”, and is used as a raw material and fuel such as carbon black. Since the naphtha pyrolysis plant is often called an ethylene plant, the aforementioned heavy fraction is called ethylene bottom oil. Also, naphtha pyrolysis plants are sometimes called naphtha crackers.

In this embodiment, as an ethylene bottom oil, a raw material further containing at least one of kerosene, light oil, and natural gas liquid in addition to naphtha in addition to ethylene bottom oil obtained by thermal decomposition of naphtha is pyrolyzed. The ethylene bottom oil obtained in this way can also be used.
Natural gas liquid (NGL) is a high-boiling liquid component at the time of natural gas collection, and is a generic term for liquid hydrocarbons separated and recovered from natural gas produced from underground through wells (oil / natural gas). Glossary of terms). In the present specification, a raw material that contains at least naphtha and further includes at least one of kerosene, light oil, and natural gas liquid is referred to as a naphtha-containing raw material.

When a raw material further containing at least one of kerosene, light oil, and natural gas liquid is used as the naphtha-containing raw material, the total content of kerosene, light oil, and natural gas liquid is 100% by mass of the naphtha-containing raw material. In the inside, it can be 1-99 mass%. Since the naphtha-containing raw material with a high content contains a lot of kerosene, light oil, and natural gas liquid, which is cheaper than naphtha, it is more economical as a naphtha cracker than a naphtha-containing raw material with a low content. On the other hand, from the naphtha-containing raw material having a high content, a lot of ethylene bottom oil, which is a heavy oil and its use is limited, is sometimes used. On the other hand, since the production method of the present embodiment effectively uses ethylene bottom oil, even if it is a naphtha-containing raw material with a high total content of kerosene, light oil and natural gas liquid, Can be used as a raw material without problems.
The total ratio of kerosene, light oil and natural gas liquid in the naphtha-containing raw material is sometimes referred to as a raw material diversification rate.

The properties of ethylene bottom oil obtained by thermal decomposition of naphtha-containing raw materials depend on the type of naphtha-containing raw materials, thermal decomposition conditions, operating conditions of the purification distillation tower, etc., but as general properties, the total PAH8 content is 1000 to 3000 wtppm, the content of benzo [a] pyrene is 50 to 200 wtppm, the kinematic viscosity at 100 ° C. is less than 10 mm ² / s, and the aromatic carbon content is 50% or more.

In this specification, the value of kinematic viscosity is a value measured according to JIS K2283.
Further, quantification of PAH8 including benzo [a] pyrene can be performed using GC-MS (gas chromatograph mass spectrometer) or the like.
Further, in the present specification, the aromatic carbon ^content, the area of the peak of 110~150ppm for (equivalent. The total number of carbon atoms) 13 C-NMR in (nuclear magnetic resonance spectrum) measurement, the total peak area integrated value It is the ratio (percentage) of the integrated value (corresponding to the number of aromatic carbons). Ethylene bottom oil and rubber compounded oil obtained from the ethylene bottom oil by the production method of this embodiment include many compounds having aromatic rings and condensed rings thereof as aromatic compounds. It is difficult to identify and quantify one by one. Therefore, when judging the amount of the aromatic compound contained in these objects, generally, the aromatic carbon content (Ca%) measured by ASTM D2140 is often used as an index. However, recently, it has become possible to directly determine the amount of an aromatic compound by measurement using NMR. Therefore, in the present specification, the aromatic carbon content ratio is defined as the ratio of aromatic carbon obtained as described above by ¹³ C-NMR.

[Component ( _Cv )]
In the hydrodesulfurization step of the present embodiment, a part or all of the ethylene bottom oil obtained by thermal decomposition of the naphtha-containing raw material is used as a raw material, and this is hydrodesulfurized. Preferably, among the ethylene bottom oil, A component (C _v ) having a kinematic viscosity at 100 ° C. of 10 mm ² / s or more is used as a raw material, and this is hydrodesulfurized. By hydrodesulfurizing a component (C _ν ) having a kinematic viscosity at 100 ° C. of 10 mm ² / s or more, the viscosity of the resulting rubber compounded oil does not become too low. Problems such as the generation of steam become violent and the rubber compounded oil tends to bleed out from the vulcanized product of the rubber composition containing the rubber compounded oil are less likely to occur.
The 100 ° C. kinematic viscosity of the component (C _ν ) is preferably 20 mm ² / s or more. Moreover, the preferable upper limit of 100 degreeC kinematic viscosity of a component (C ( _nu )) is 10000 mm < ² > / s from a viewpoint on the handling in a manufacturing process.

When the 100 ° C. kinematic viscosity of the ethylene bottom oil obtained by thermal decomposition of the naphtha-containing raw material is 10 mm ² / s or more, the ethylene bottom oil can be used as it is in the hydrodesulfurization step as a component (C _ν ). it can. On the other hand, when the 100 ° C. kinematic viscosity of the ethylene bottom oil is less than 10 mm ² / s, it may be used as it is in the hydrodesulfurization process, but the low boiling point component contained in the ethylene bottom oil is removed by the distillation process. The distillation residue liquid (residual oil) after removal is adjusted so that its 100 ° C. kinematic viscosity is 10 mm ² / s or more, and the distillation residue liquid is used as a component (C _ν ) for the hydrodesulfurization step. More preferred. The distillation step may be any of atmospheric distillation, vacuum distillation (vacuum distillation), a combination of atmospheric distillation and vacuum distillation, and is appropriately selected.

The component (C _ν ) used for the hydrodesulfurization step preferably has an aromatic carbon content of 55% or more and 100% or less. When the aromatic carbon content is less than 55%, the aromatic carbon content of the finally obtained rubber compounded oil tends to be lower than a desired value. The content of aromatic carbon in the component (C _v ) is more preferably 60 to 95%, further preferably 70 to 90%.

In addition, the component (C _ν ) preferably has a total content of PAH8 of 0 wtppm or more and 3000 wtppm or less. If it exceeds 3000 wtppm, it may be difficult to sufficiently reduce the total PAH8 content of the finally obtained rubber compounding oil.
The total sulfur concentration of the component (C _ν ) is preferably 0% by mass or more and 1% by mass or less, and the concentration of asphaltenes contained is preferably 0% or more and 3% or less. If the total sulfur concentration exceeds 1% by mass, it may be difficult to sufficiently reduce the total PAH8 content of the finally obtained rubber compounding oil.

[Hydrodesulphurization process]
Hereinafter, as a preferred example, the hydrodesulfurization step will be described with reference to the case where the hydrodesulfurization step is performed using the above-described component (C _v ) as a raw material.
Hydrodesulfurization process is a component (C _[nu) is reacted with hydrogen gas, a reaction step of converting sulfur compounds present in component (C _[nu) to hydrogen sulfide (H 2 _S), obtained in the reaction step Gas-liquid separation of the obtained reaction liquid to remove hydrogen sulfide as a gas from the reaction liquid, thereby obtaining a desulfurized oil. Note that the reaction step and the gas-liquid separation step may be performed in the same step. By performing such a hydrodesulfurization process and reducing sulfur compounds in the raw material, it is possible to suppress a decrease in catalytic activity due to the deposition of sulfur on the hydrogenation catalyst in the hydrogenation process described later, It becomes possible to manufacture stably for a long time.
Here, as described above, if the ethylene bottom oil obtained by thermal decomposition of the naphtha-containing raw material is 100 ° C. and a kinematic viscosity of 10 mm ² / s or more, the ethylene bottom oil can be used as it is as a component (C _ν ). On the other hand, if the 100 ° C. kinematic viscosity is less than 10 mm ² / s, the ethylene bottom oil is subjected to a distillation step to remove low boiling components, and the resulting 100 ° C. kinematic viscosity is 10 mm ² / s or more. using distillation residue solution as component (C _[nu).

In the hydrodesulfurization process, the reaction process is performed in the presence of a solid catalyst in a continuous reaction system or a batch reaction system. From the viewpoint of productivity, the continuous reaction method is preferable.
A gas-liquid reaction is preferable as a reaction form, and a trickle bed using a trickle bed reactor in which a component (C _ν ) is caused to flow downward in a packed bed of a solid catalyst and hydrogen gas to be brought into contact therewith is also caused to flow downward. The method is preferred. When the reaction form is a gas phase reaction, the energy required for evaporating the component (C _v ) and the solvent becomes large, which is economically disadvantageous. On the other hand, when the reaction form is a liquid phase reaction, there is a limit to the amount of hydrogen dissolved in the component (C _v ) or the solvent, so that a desired hydrogenation process becomes difficult.

If a continuous reaction process performing reaction step, the ratio of hydrogen gas to be supplied is such that the range of the supply amount 1ton per 100 to 1000 nm ³ components (C _[nu), it is preferable to adjust the flow rate of hydrogen gas. When the hydrogen gas flow rate is less than 100 Nm ³ , hydrodesulfurization may be insufficient, and when the hydrogen gas flow rate exceeds 1000 Nm ³ , it is economically disadvantageous.

As the solid catalyst to be used, one that can act as a catalyst for hydrodesulfurization reaction can be used. For example, alumina, silica, titania, zirconia, boria, magnesia, zeolite (Z type zeolite such as Y type zeolite, X type zeolite, L type zeolite, beta type zeolite, ZSM-5, MFI type zeolite, chabasite, mordenite, Erio (Night), or a composite oxide or mixed oxide composed of two or more of them as a carrier, and the carrier is a member of Groups 6, 8, 9, and 10 of the periodic table. A catalyst supporting at least one metal among the elements can be used. Examples of the periodic table group 6 metal include Cr, Mo, and W. Examples of Group 8, Group 9, and Group 10 metals in the periodic table include Co, Ni, Rh, Ru, Pd, and Pt.
When using 2 or more types of metal to carry | support, Preferably, combinations, such as Ni-Mo, Co-Mo, Ni-W, are mentioned. Further, when a composite oxide or mixed oxide is used as the carrier, for example, one formed by using zeolite, alumina, silica alumina or the like as a matrix is preferably used. When using zeolite, Y-type zeolite is preferable.

  Among these, from the viewpoint of high sulfur resistance and desulfurization capacity, Mo and W as main catalyst elements are supported on a carrier mainly composed of any of alumina, silica, titania, zirconia, silica alumina and zeolite. It is preferable to use a hydrodesulfurization catalyst in which at least one element selected from the above and at least one element selected from Co and Ni are supported as promoter elements.

Liquid hourly space velocity in the actual plant (LHSV) is a component (C _[nu) standards, usually 0.1 to 10 ^-1, preferably may be appropriately adjusted in the range of 0.3~8hr ^-1. If the LHSV is less than 0.1 hr ⁻¹ , the amount of the solid catalyst is too large, which is not advantageous in terms of economy. On the other hand, if the LHSV exceeds 10 hr ⁻¹ , hydrodesulfurization may be insufficient.

The temperature in the reaction step is usually from 100 to 450 ° C, preferably from 250 to 400 ° C, more preferably from 270 to 350 ° C. If the reaction temperature is less than the lower limit of the above range, hydrodesulfurization may be insufficient, and if the reaction temperature exceeds the upper limit of the above range, the raw material intensity may deteriorate due to hydrocracking of the component (C _ν ). There is sex.
The pressure is usually in the range of 1.0 to 20.0 MPaG, preferably 2.0 to 5.0 MPaG. If the pressure is less than the above range, the desired hydrodesulfurization may not proceed sufficiently.

Moreover, in the hydrodesulfurization process, in order to remove the generated reaction heat, a component (C _v ) diluted with a solvent may be reacted with hydrogen gas. In the reaction step of the hydrodesulfurization step, the nuclear hydrogenation of the aromatic ring may proceed simultaneously with the hydrodesulfurization, and in this case, the reaction heat tends to become remarkable. In addition, for example, in order to control the polarity of the resulting rubber compounding oil, the nuclear hydrogenation of the aromatic ring may be actively promoted. In that case, the reaction heat is large, and the reaction heat must be removed. Control of the reaction temperature may be difficult. Also, from the viewpoint of preventing fouling of the catalyst, it is an effective means to dilute the component (C _v ) as a substrate with a solvent.
The solvent used for the dilution is inactive in the reaction step of the hydrodesulfurization step of the present embodiment; sufficiently dissolves the component (C _ν ); and later easily separated from the rubber compounding oil by distillation or the like. It is required that the boiling point be lower than that of the obtained rubber compounding oil. The solvent satisfying such conditions can be appropriately selected from saturated hydrocarbons, saturated ethers, and the like, and preferred examples include decahydronaphthalene, tetralin, tetrahydrofuran, 1,4-dioxane and the like.
Moreover, as a solvent, the rubber compounding oil manufactured in the example of this embodiment can also be used. When rubber compounded oil is selected as the solvent, the solvent and product (rubber compounded oil) are the same, so there is no need to separate them, and a part of the mixture of solvent and product is circulated as the solvent. Reuse it. Therefore, it can be an economically effective process.

In the case of a batch reaction system, an autoclave or the like is used as a reactor. At that time, the reaction time is preferably 1 to 5 hours. Various conditions such as the solid catalyst to be used, the ratio of the component ( _Cv ) and hydrogen gas, the hydrodesulfurization temperature and pressure are the same as in the case of the continuous reaction system. In the case of the batch reaction method, the reaction may be carried out by diluting the component (C _v ) with a solvent.

After completion of the reaction step in the hydrodesulfurization step, a gas-liquid separation step is performed in which the reaction solution obtained in the reaction step is gas-liquid separated, hydrogen sulfide is removed from the reaction solution as a gas, and purged out of the system. By this degassing, a liquid component containing a residual oil (desulfurized oil) with a reduced sulfur concentration and a solvent when a solvent for dilution is used is obtained. This liquid component is supplied to the next hydrogenation step.
When purging hydrogen sulfide out of the system in this way, unreacted hydrogen gas is accompanied by hydrogen sulfide. If the amount of hydrogen gas is large and there is a large negative economic impact, amines, caustic soda, etc. After selectively removing hydrogen sulfide using the absorption liquid, hydrogen gas can be circulated to the reactor in the hydrodesulfurization process or sent to the reactor in the subsequent hydrogenation process. preferable.
Further, the removal of hydrogen sulfide by gas-liquid separation proceeds more effectively as the operating pressure during gas-liquid separation is lower. Accordingly, it is preferable to remove hydrogen sulfide by reducing the pressure of the reaction solution obtained in the reaction step. However, if the operating pressure is too low, degassing proceeds efficiently, but it may affect the subsequent absorption operation using an absorbing liquid such as amine or caustic soda. In addition, the power cost for hydrogen gas circulation also increases. Therefore, the operation pressure at the time of gas-liquid separation is appropriately set in view of the process optimum value.

[Hydrogenation process]
In the hydrogenation step, the aromatic ring of the desulfurized oil obtained by the hydrodesulfurization step is nuclear hydrogenated. As a result, the PAH8 substance contained in the desulfurized oil is removed, and the concentration of the aromatic compound contained is controlled, and benzo [a] pyrene and other polycyclic aromatic carbonizations are satisfied to the extent that the above-mentioned European regulations are satisfied. A rubber compounding oil with reduced hydrogen can be produced.

The hydrogenation step is carried out in the presence of a solid catalyst in a continuous reaction system or a batch reaction system. From the viewpoint of productivity, the continuous reaction method is preferable.
A gas-liquid reaction is preferable as a reaction form, and a trickle bed system using a trickle bed reactor in which desulfurized oil is allowed to flow downward in a packed bed of a solid catalyst and hydrogen gas to be brought into contact therewith is also preferable to flow downward is preferable. . When the reaction form is a gas phase reaction, the energy required for evaporating the desulfurized oil and the solvent becomes large, which is economically disadvantageous. On the other hand, when the reaction form is a liquid phase reaction, there is a limit to the amount of hydrogen dissolved in the desulfurized oil or the solvent, so that the desired nuclear hydrogenation process becomes difficult.
Moreover, in order to remove the reaction heat by nuclear hydrogenation, you may dilute with a solvent similarly to the hydrodesulfurization process. As the preferred solvent, those described in the description of the hydrodesulfurization step can be used.
In addition, when a solvent for dilution is used in the preceding hydrodesulfurization step, the desulfurized oil is supplied as a raw material to the hydrogenation step in a state of being mixed with the solvent. Thereby, also in a hydrogenation process, nuclear hydrogenation advances in the state diluted with the solvent, and can remove reaction heat.

When performing hydrogenation by a continuous reaction system, it is preferable to adjust a hydrogen gas flow rate so that the ratio of the hydrogen gas supplied may be in the range of 100 to 1000 Nm ³ per 1 ton of desulfurized oil supply. When the hydrogen gas flow rate is less than 100 Nm ³ , nuclear hydrogenation may be insufficient, and when the hydrogen gas flow rate exceeds 1000 Nm ³ , it is economically disadvantageous.

As the solid catalyst used in the hydrogenation step, a catalyst that can act as a catalyst for the hydrogenation reaction can be used. For example, the same catalyst as that used in the hydrodesulfurization step can be used. However, since the purpose of the hydrogenation step is nuclear hydrogenation of desulfurized oil, it is preferable to use a catalyst having high nuclear hydrogenation ability even if the sulfur resistance is low.
Examples of such a catalyst include one of alumina, silica, titania, zirconia, boria, magnesia, and zeolite, or a composite oxide or mixed oxide composed of two or more of these, and activated carbon. It is preferable to use a catalyst in which one or more inorganic compounds are used as a carrier and at least one of the metals in Groups 8 to 10 of the periodic table is supported on the carrier. Specifically, at least one selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum as a catalytic element is supported on a carrier made of an inorganic compound such as alumina, silica, zeolite, or activated carbon. The hydrogenation catalyst made is mentioned. Among these catalytic elements, at least one of nickel, palladium, and platinum is more preferable.

Liquid hourly space velocity in the actual plant (LHSV) is a desulfurized oil basis, usually 0.1 to 10 ^-1, preferably may be appropriately adjusted in the range of 0.3~8hr ^-1. If the LHSV is less than 0.1 hr ⁻¹ , the amount of the solid catalyst is too large, which is not advantageous in terms of economy. On the other hand, if it exceeds 10 hr ⁻¹ , hydrogenation may be insufficient.

  Moreover, when performing a hydrogenation process by a continuous reaction system, it is preferable that the accumulation sulfur amount contained in the desulfurization oil supplied to a hydrogenation process for one year is 0.01 ton or less per 1 ton of hydrogenation catalysts. This is due to the following reason. That is, sulfur contained in the desulfurized oil is gradually deposited on the hydrogenation catalyst used in the hydrogenation step, and the activity of the catalyst is reduced. In particular, the hydrogenation catalyst used in the hydrogenation step is prioritized to have high nuclear hydrogenation ability, and therefore the hydrogenation catalyst may be inferior in sulfur resistance. Such a decrease in the activity of the catalyst can be a factor that hinders stable operation of the plant. Therefore, from the viewpoint of operation management, the amount of sulfur in the desulfurized oil is preferably controlled to be low. Specifically, it is preferable to manage the cumulative amount of sulfur contained in the desulfurized oil supplied to the hydrogenation process in consideration of the life required for the catalyst. From this point of view, as described above, in the operation of an actual plant for one year (8760 hours), the cumulative amount of sulfur contained in the desulfurized oil supplied to the reactor in the hydrogenation process is 1 ton of hydrogenation catalyst (carrier). Is preferably 0.01 ton or less. More preferably, it is 0.005 ton or less per 1 ton of catalyst, and further preferably 0.001 ton or less per 1 ton of catalyst.

The temperature of the hydrogenation step is usually 50 to 400 ° C, and preferably 100 to 300 ° C. If the reaction temperature is less than the above range, the reduction of the PAH8 substance may be insufficient, and if it exceeds the above range, the raw material basic unit may deteriorate due to hydrocracking of the desulfurized oil.
The pressure in the hydrogenation step is usually 1.0 to 20.0 MPaG, preferably 2.0 to 5.0 MPaG. If the pressure is less than the above range, the desired nuclear hydrogenation does not proceed sufficiently, and the total content of PAH8 in the finally obtained rubber compounded oil exceeds 10 wtppm, or the aromatic carbon content ratio of the rubber compounded oil can be controlled. It may be difficult.

  In the case of a batch reaction system, an autoclave or the like is used as a reactor. At that time, the reaction time is preferably 1 to 5 hours. Various conditions such as the solid catalyst used, the ratio of desulfurized oil and hydrogen gas, the temperature and pressure of nuclear hydrogenation are the same as in the case of the continuous reaction system.

After completion of such a hydrogenation step, the reaction solution is gas-liquid separated into a liquid component (aggregate) and a gas component (unreacted hydrogen gas, etc.) by a known method. And the target rubber compounding oil can be obtained by removing a solvent by distillation etc. as needed with respect to a liquid component, or refine | purifying.
Since such a hydrogenation step is performed after the hydrodesulfurization step is performed in advance, the amount of sulfur deposited on the hydrogenation catalyst used in the hydrogenation step is small, and a decrease in the activity of the catalyst is suppressed. Therefore, stable operation for a long time is possible.

<Rubber compounding oil>
According to the production method described above, a rubber compounding oil in which benzo [a] pyrene and other polycyclic aromatic hydrocarbons are reduced can be stably produced for a long period of time using an ethylene bottom oil whose use is limited. The rubber compounded oil thus obtained has the above-mentioned European regulations, that is, the total PAH8 content is 0 wtppm or more and 10 wtppm or less, and the benzo [a] pyrene content is 0 wtppm or more and 1 wtppm or less. Satisfy the condition.

Further, the rubber compounding oil is preferably a kinematic viscosity at 100 ° C. is in the range of 10 to 100 mm ² / s, more preferably in the range of 20 to 40 mm ² / s. If the kinematic viscosity is too low, the normal properties of the vulcanized product of the rubber composition containing the rubber compounding oil may be insufficient, or the heat aging property may be inferior due to oil evaporation during heat aging. On the other hand, when the kinematic viscosity is too high, the fluidity is low and the handleability tends to be lowered.

Moreover, it is preferable that the aromatic carbon content rate of the manufactured rubber compounding oil is 5 to 50%, and it is more preferable that it is 10 to 40%. If it is less than 5%, the compatibility with the rubber is lowered, bleed is generated in the vulcanizate of the rubber composition containing the rubber compounding oil, and further, the rubber composition containing the rubber compounding oil is added. The normal physical properties and heat aging physical properties of the sulfate may be inferior. On the other hand, if it exceeds 50%, the total PAH8 content tends to easily exceed 10 wtppm. In addition, as described above, the aromatic carbon content ratio is a value obtained using ¹³ C-NMR.

  In addition, the rubber compounding oil is a rubber composition for tires prepared by blending the rubber compounding oil, from the viewpoint of affinity with rubber, softening property, high flash point, safety, handling property, and the rubber compounding oil. When a tire is manufactured, it is preferable that the tire has the following properties from the viewpoint of improving the fuel efficiency, gripping property and heat aging resistance of the tire.

Density at 15 ° C .: Usually 0.90 to 1.10 g / cm ³ , preferably 0.95 to 1.05 g / cm ³ .
Flash point: usually 200 ° C. or higher, preferably 250 ° C. or higher.
Kinematic viscosity at 40 ° C.: Normal 20~2000mm ² / s, preferably from 100 to 1000 mm ² / s.
Aniline point: Usually 20 ° C to 110 ° C, preferably 30 ° C to 80 ° C.
Pour point: Usually −40 to + 30 ° C., preferably −30 to + 20 ° C.
Glass transition point (Tg): Usually −60 to −10 ° C., preferably −55 to −30 ° C. Here, the glass transition point (Tg) is calculated from the calorific value change peak in the glass transition region, which is observed when the temperature is increased at a constant temperature increase rate (10 ° C./min) with a DSC (differential scanning calorimeter). Temperature.

<Rubber composition>
By kneading the rubber compounding oil described above into rubber such as natural rubber, styrene butadiene rubber, polybutadiene rubber, butyl rubber, isoprene rubber, and nitrile rubber using a known apparatus, a rubber composition for tires, for example, is obtained. Can do. Examples of the rubber kneading apparatus include a kneader, a Banbury mixer (registered trademark), a twin screw extruder, a two roll, a calendar roll. In addition to the rubber compounding oil, the rubber composition is blended with a crosslinking agent, a sulfur compound, a filler, a reinforcing agent such as carbon black, a fiber, an antioxidant and the like as necessary, and then vulcanized (crosslinked). Rubber products. Examples of rubber products include tires.

  As described above, according to the production method of the present embodiment, the rubber compounded oil in which benzo [a] pyrene and other polycyclic aromatic hydrocarbons are reduced using the ethylene bottom oil whose use is limited. Can be manufactured stably for a long period of time.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to an Example.
In each example, various measurements were performed by the following methods.
(1) PAH8 total content and content of benzo [a] pyrene Carried out by GC-MS SIM analysis. The conditions were as follows.
Internal standard: Perylene d-12
Column: HP-5MS 5% Phenyl Methyl Siloxane is used Column length: 30m
Injection: 280 ° C
Initial temperature: 80 ° C
Temperature increase rate: 10 ° C / min
Final temperature: 300 ° C

(2) Aromatic carbon content
^The measurement was performed by ¹³ C-NMR measurement (measurement model: JEOL EX-400 (manufactured by JEOL Ltd.)).
(I) Preparation of NMR sample 0.18-0.20 g of sample and chloroform-D (Wako chloroform-D, (D, 99.8%) + 0.05 v / v% TMS, 536-74263) 0.60 g-0. 65 g is mixed and added to an NMR sample tube (inner diameter φ4.2 mm) so that the height is 4 cm from the tube bottom.
(Ii) Measuring method The waiting time (Pulse Delay) is set to 20 seconds, and measurement is performed at a total number of 2000 using non-NOE mode gated decoupling.
(Iii) Analysis Method The obtained FID signal is subjected to phase correction, baseline correction, and reference peak setting (TMS, CHCl ₃ ) using EXcalibur for Windows (registered trademark) version 4.5 (manufactured by JEOL Ltd.). Perform (normal automatic setting).
From the peak area S _Al between the chemical shift δ 10 ppm to 50 ppm and the peak area S _Ar between the chemical shift δ 110 ppm to 150 ppm, the aromatic carbon content ratio (%): D _Ar = 100 × S _Ar / (S _Ar + S _Al ) calculate.
In ordinary ethylene bottom oil and hydrides thereof, a carbon peak appears only between chemical shifts δ 10 ppm to 50 ppm and 110 ppm to 150 ppm, and no carbon peak appears outside these regions. The same was true for the ethylene bottom oil, component ( _Cv ), rubber compounding oil and the like measured in the following examples.

(3) Total sulfur concentration Using a chlorine-sulfur analyzer (Mitsubishi Kasei Kogyo, model TSX-10 type), the following measurement method was used.
Electrolyte: 25 mg aqueous solution of sodium azide; 50 mL + glacial acetic acid; 0.3 mL + potassium iodide; 0.24 g
Dehydrated liquid: phosphoric acid; 7.5 mL + pure water; 1.5 mL
Counter electrode solution: Special grade potassium nitrate 10% by mass aqueous solution Oxygen introduction pressure: 0.4 MPaG
Argon introduction pressure: 0.4 MPaG
Sample introduction part temperature: 850 to 950 ° C.
Sample: 30 μL is injected with a micro syringe.

(4) Asphaltene concentration It was carried out by the following measuring method using Iatroscan MK-6 (manufactured by Mitsubishi Chemical Medience Corporation).
(I) Sample preparation A sample is dissolved in THF to make a 1 wt% solution. This sample is spotted by about 1 mm at the origin of sintered thin layer rod chroma rod-SIII (manufactured by Mitsubishi Chemical Medience Corporation) for Iatroscan using a spotting guide and a micro dispenser attached to Iatroscan MK-6. This sintered thin layer rod is developed in the order of n-hexane, toluene, dichloromethane / 0.1 vol% methanol mixed solvent using a developing layer DT-150 (developing solvent 70 ml). At the time of switching the developing solvent, the solvent is removed at 120 ° C. using a rod dryer TK-8.
(Ii) Measurement method Measurement is performed using a flame ionization detector at a scan speed of 30 seconds / scan.
(Iii) Analytical method SIC 480II for IATROSCAN (manufactured by System Instruments Co., Ltd.) is used to classify asphaltene, resin, aromatic and saturated components from the peak close to the origin, respectively, and asphaltene peaks relative to the total peak area. The area is defined as the asphaltene concentration (asphaltene ratio) (%).

[Example 1]
The ethylene bottom oil obtained by the thermal decomposition of naphtha was measured at 100 ° C. for a kinematic viscosity of 3.8 mm ² / s. Therefore, the following distillation step was performed on the ethylene bottom oil. The properties of the ethylene bottom oil are shown in Table 1.
(Distillation process)
The ethylene bottom oil was distilled under reduced pressure to remove low-boiling components, and a residual oil (distillation residue liquid) having a kinematic viscosity at 100 ° C. of 373 mm ² / s was obtained.
Specifically, 1 L of ethylene bottom oil was charged into the kettle using a shelf-type Oldershaw (10 stages), the reflux ratio was set to 5 under vacuum conditions of several Torr, the kettle temperature was raised to 220 ° C., and distilled. The residual oil (distillation residue liquid) was obtained by removing the components.
Table 1 shows the properties of the obtained residual oil (distillation residue liquid).

(Hydrodesulphurization process, Hydrogenation process)
The residual oil (distilled residue liquid) was dissolved in decahydronaphthalene to obtain a 5 wt% residual oil solution (1). And the following reaction was performed with the reaction apparatus provided with reaction tube-1 and reaction tube-2.
Reaction tube-1 (reaction tube for hydrodesulfurization; inner diameter 20 mm) was filled with 20 g of HDMAX 300 manufactured by Zude Chemie Catalysts. The main components of this catalyst are molybdenum oxide 15 to 20 wt%, nickel oxide 3.0 to 6.0 wt%, and aluminum oxide (balance). The alumina support has molybdenum as the main catalyst element and nickel as the promoter element. Is a hydrodesulfurization catalyst supported.
On the other hand, reaction tube-2 (nuclear hydrogenation reaction tube; inner diameter 20 mm) was charged with 10 g of NiSAT310RS manufactured by Zude Chemie Catalysts. This catalyst contains nickel 52 ± 4.0 wt%, silica 28.0 ± 3.0 wt%, alumina 10.0 ± 1.0 wt%, and a nickel catalyst supported on a carrier made of an inorganic compound. It is.
The catalyst charged in the reaction tube-1 was sulfurized at 340 ° C. using a decahydronaphthalene liquid containing dimethyl disulfide at a hydrogen pressure of 2.1 MPaG.
Thereafter, the catalyst layer temperature of the reaction tube-1 is set to 300 ° C., and the hydrogen gas is supplied with a hydrogen pressure of 3.0 MPaG, a hydrogen flow rate of 10 NL / h = 8000 Nm ³ / t (hydrogen gas supply amount per ton of raw material residual oil), Residual oil solution (1) was continuously fed in parallel flow at 25 g / h to reaction tube-1 to carry out the reaction step of the hydrodesulfurization step. The reactor outlet fluid was gas-liquid separated under atmospheric pressure to obtain liquid component (2) (desulfurized oil / decahydronaphthalene). The liquid space velocity (LHSV) at this time was 0.035.
The total sulfur concentration in the liquid component 24 hours after the start of the reaction was 16 wtppm in terms of substrate (in a state where decahydronaphthalene was removed).
The catalyst charged in the reaction tube-2 was subjected to hydrogen reduction treatment at 300 ° C. and atmospheric pressure. Next, the catalyst layer temperature of the reaction tube-2 is set to 150 ° C., hydrogen gas is supplied at a hydrogen pressure of 3.0 MPaG, a hydrogen flow rate of 10 NL / h = 8000 Nm ³ / t (hydrogen gas supply amount per ton of raw desulfurized oil), the liquid The component (2) was continuously supplied in parallel flow to the reaction tube-2 at 25 g / h to carry out a nuclear hydrogenation reaction. The reactor outlet fluid was gas-liquid separated under atmospheric pressure to obtain a liquid component (3) which was a mixture of nuclear hydrogenated oil (rubber compounded oil) and decahydronaphthalene. The liquid space velocity (LHSV) at this time was 0.075.
The total PAH8 content in terms of substrate in the liquid component (3) 24 hours after the start of the reaction was 3.1 ppm, and the benzo [a] pyrene concentration was 0 ppm. Other properties are shown in Table 1.
Each reaction described above was continued for 4000 hours, and the total sulfur concentration in terms of substrate and PAH8 of the condensate (liquid components (2) and (3)) after separation of the gas and liquid at the outlet of reaction tube-1 and reaction tube-2 The time-dependent data of the substance concentration is shown in FIG. From the data of reaction tube-2 in FIG. 1, it can be seen that the total PAH8 content is maintained at 10 ppm or less even after 4000 hours.

Moreover, it turns out that the average value in reaction time 0-4000hr of the total sulfur concentration in conversion of the substrate of the outlet fluid condensate (liquid component (2)) of reaction tube-1 is about 7 wtppm from FIG. The liquid component (2) is supplied to the reaction tube-2 at 25 g / h. Since the desulfurized oil in the feed liquid is 5% by mass (the remainder is decahydronaphthalene), desulfurized oil is supplied to the reaction tube-2 at 1.25 g / h. Since the sulfur content (total sulfur concentration) is 7 wtppm, the sulfur content is supplied to the reaction tube-2 at 8.75 × 10 ⁻⁶ g / h. If this is multiplied by 8760 hr (1 year), the cumulative amount of sulfur in 1 year will be 0.077 g. Since the amount of catalyst in the reaction tube-2 is 10 g, the cumulative amount of sulfur in the desulfurized oil supplied to the hydrogenation process in one year is 0.0077 ton per ton of hydrogenation catalyst.

[Comparative Example 1]
Instead of the reaction apparatus provided with reaction tube-1 and reaction tube-2, a point using a reaction apparatus provided only with reaction tube-2, and a point where the amount of catalyst charged in reaction tube-2 at that time was 20 g The reaction was conducted by supplying 5 wt% residual oil solution (1) in the same manner as in Example 1 except that the catalyst layer temperature of the reaction tube-2 was 250 ° C.
That is, the catalyst (packing amount: 20 g) charged in the reaction tube-2 was subjected to hydrogen reduction treatment at 300 ° C. and atmospheric pressure. Next, the catalyst layer temperature of the reaction tube-2 is set to 250 ° C., the hydrogen gas is supplied with a hydrogen pressure of 3.0 MPaG, a hydrogen flow rate of 10 NL / h = 8000 Nm ³ / t (hydrogen gas supply amount per ton of raw oil), the residual oil The hydrogenation reaction was carried out by continuously supplying the solution (1) at 25 g / h to the reaction tube-2 in a parallel flow. The reactor outlet fluid was gas-liquid separated under atmospheric pressure to obtain a liquid component (4). The total PAH8 content in terms of substrate in the liquid component (4) 4 hours after the start of the reaction was 9.6 ppm, and the benzo [a] pyrene concentration was 0.1 ppm.
FIG. 2 shows the time-lapse data of the total PAH8 content in terms of substrate of the condensate (liquid component (4)) after separation of the gas / liquid at the outlet of the reaction tube-2 when this reaction is continued for 96 hours. Various properties are shown in Table 1. From the data in FIG. 2, in Comparative Example 1, the PAH8 substance concentration satisfies the European regulation of 10 ppm or less until the 4th hour from the start of the reaction, but after that, it immediately exceeded the regulation value, It turns out that a catalyst activity fall is quick.

[Comparative Example 2]
A 5 wt% residual oil solution (in the same manner as in Example 1 except that a reactor equipped only with the reaction tube-1 was used instead of the reactor equipped with the reaction tube-1 and the reaction tube-2. 1) was fed to carry out the reaction.
That is, the catalyst charged in the reaction tube-1 was sulfurized at 340 ° C. using a dimethyldisulfide-containing decahydronaphthalene solution at a hydrogen pressure of 2.1 MPaG.
Thereafter, the catalyst layer temperature of the reaction tube-1 is set to 300 ° C., and the hydrogen gas is supplied with a hydrogen pressure of 3.0 MPaG, a hydrogen flow rate of 10 NL / h = 8000 Nm ³ / t (hydrogen gas supply amount per ton of raw material residual oil), The residual oil solution (1) was continuously fed in parallel flow at 25 g / h to the reaction tube-1 to carry out a hydrogenation reaction. The reactor outlet fluid was gas-liquid separated under atmospheric pressure to obtain a liquid component (5). The total PAH8 content in terms of substrate in the liquid component (5) 4 hours after the start of the reaction was 138 ppm, and the benzo [a] pyrene concentration was 1.6 ppm.

[Comparative Example 3]
A 5 wt% residual oil solution (1) was supplied and reacted in the same manner as in Comparative Example 2 except that the hydrogen pressure was changed to 5.0 MPaG instead of 3.0 MPa to obtain a liquid component (6). It was. The total PAH8 content in terms of substrate in the liquid component (6) 4 hours after the start of the reaction was 27 ppm, and the benzo [a] pyrene concentration was 0.3 ppm.

  According to the examples, a rubber compounding oil in which the benzo [a] pyrene content and the total PAH8 content were reduced so as to satisfy the above-mentioned European regulations could be produced stably for a long period of time.

  According to the present invention, the bottom component of the pyrolysis process of the naphtha fraction obtained by the atmospheric distillation of crude oil, the raw material source of the rubber compounding oil, which was conventionally limited to the vacuum distillation fraction of crude oil and the vacuum distillation residue, That is, it can be stably obtained from ethylene bottom oil for a long period of time. Since the use of ethylene bottom oil has conventionally been limited to low-value products such as carbon black raw materials and fuels, the production method of the present invention is also beneficial from the viewpoint of effective use of the ethylene bottom oil. In particular, in recent years, there has been a tendency to use raw materials that are combined with naphtha in addition to inexpensive heavy components such as kerosene and light oil as a raw material for pyrolysis, and as a result, the production of ethylene bottom oil has increased. Therefore, the industrial merit of the present invention is very large.

Claims (17)

  A hydrodesulfurization step in which at least a part of ethylene bottom oil obtained by thermal decomposition of a naphtha-containing raw material is hydrodesulfurized to obtain desulfurized oil, and a hydrogenation step in which the aromatic ring of the desulfurized oil is nuclear hydrogenated. A method for producing a rubber compounding oil, comprising:   In the hydrodesulfurization step, a support mainly composed of any one of alumina, silica, titania, zirconia, silica alumina, and zeolite is added to at least one element selected from molybdenum and tungsten as a main catalyst element. 2. The production of a rubber compounding oil according to claim 1, wherein a hydrodesulfurization catalyst on which at least one element selected from cobalt and nickel is supported as a catalyst element is used, and the raw material is reacted with hydrogen gas at 250 to 400 ° C. 3. Method.   The method for producing a rubber compounding oil according to claim 1 or 2, wherein in the hydrodesulfurization step, the raw material is reacted with hydrogen gas at a pressure of 1.0 to 20.0 MPaG.   In the hydrogenation step, a hydrogenation catalyst in which at least one element selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum is supported on a support made of an inorganic compound, The method for producing a rubber compounding oil according to any one of claims 1 to 3, wherein the desulfurized oil is reacted with hydrogen gas at 100 to 300 ° C.   The method for producing a rubber compounding oil according to any one of claims 1 to 4, wherein in the hydrogenation step, the desulfurized oil is reacted with hydrogen gas at a pressure of 1.0 to 20.0 MPaG.   When the hydrogenation step is performed in a continuous reaction system using a hydrogenation catalyst, the cumulative amount of sulfur in the desulfurized oil supplied to the hydrogenation step in one year is 0.01 ton or less per ton of the hydrogenation catalyst. The method for producing a rubber compounding oil according to any one of claims 1 to 5. The hydrodesulfurization step includes reacting the raw material with hydrogen gas to convert a sulfur compound in the raw material into hydrogen sulfide, and separating the reaction liquid obtained in the reaction step by gas-liquid separation. Gas-liquid separation step of removing the hydrogen sulfide from the liquid as a gas to obtain the desulfurized oil,
The method for producing a rubber compounding oil according to any one of claims 1 to 6, wherein in the gas-liquid separation step, the hydrogen sulfide is removed by reducing the pressure of the reaction solution. The said raw material is a manufacturing method of the rubber compounding oil as described in any one of Claims 1-7 whose 100 degreeC kinematic viscosity is 10 mm < ² > / s or more (C ( _nu )) among the said ethylene bottom oil. The method for producing a rubber compounding oil according to claim 8, wherein the component (C _ν ) is a distillation residue liquid of the ethylene bottom oil.   The said naphtha containing raw material is a manufacturing method of the rubber compounding oil as described in any one of Claims 1-9 containing 1-99 mass% of 1 or more types chosen from the group which consists of kerosene, light oil, and a natural gas liquid.   2. In the hydrodesulfurization step, the raw material diluted with one or more solvents selected from the group consisting of saturated hydrocarbons, saturated ethers and rubber compounding oils is reacted with hydrogen gas. The manufacturing method of the rubber compounding oil as described in any one of 10-10.   The method for producing a rubber compounding oil according to any one of claims 1 to 11, wherein a reaction is performed using a trickle bed reactor in the hydrodesulfurization step and the hydrogenation step.   The rubber compounding oil obtained by the manufacturing method as described in any one of Claims 1-12.   The rubber compounding oil according to claim 13, wherein the total content of PAH8 substances is 0 wtppm or more and 10 wtppm or less, and the content of benzo [a] pyrene is 0 wtppm or more and 1 wtppm or less.   The rubber compounding oil according to claim 13 or 14, wherein the aromatic carbon content is 5 to 50%. The rubber compounding oil according to any one of claims 13 to 15, which has a kinematic viscosity at 100 ° C of 10 to 100 mm ² / s.   The rubber compounding oil according to any one of claims 13 to 16 is mixed with at least one rubber selected from the group consisting of natural rubber, styrene butadiene rubber, polybutadiene rubber, butyl rubber, isoprene rubber and nitrile rubber. The manufacturing method of the rubber composition for tires characterized by the above-mentioned.

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