KR20120004407A - Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same - Google Patents

Abstract

According to the present invention, the total aromatic content according to ASTM D 2007 or ASTM D 2549 is 50% by mass or more, the flash point is 250 ° C or more, the difference between the pour point and the glass transition point is 45 ° C or more, and the content of benzo (a) pyrene is 1 ppm by mass. Hereinafter, and the rubber compounding oil whose sum of content of the specific aromatic compound of following 1) -8) is 10 mass ppm or less. 1) Benzo (a) pyrene (BaP) 2) Benzo (e) pyrene (BeP) 3) Benzo (a) anthracene (BaA) 4) Chrysene (CHR) 5) Benzo (b) fluoranthene (BbFA) 6 ) Benzo (j) fluoranthene (BjFA) 7) benzo (k) fluoranthene (BkFA) 8) dibenzo (a, h) anthracene (DBAhA)

Description

Rubber compounding oils and aromatic-containing base oils, and methods for their preparation {Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same}

The present invention relates to rubber compounding oils and aromatic containing base oils, and methods for their preparation.

Since high aromatic mineral oil has high affinity with a rubber component, and is excellent in workability, softening property, and economical efficiency of a rubber composition, it is used for manufacture of rubber compositions, such as natural rubber and synthetic rubber. For example, synthetic rubber such as SBR is blended with extender oil (extender oil) at the time of its synthesis, and rubber processed products such as tires have processed oils to improve their processability and quality of rubber processed products. Process oil) is blended (for example, patent document 1).

On the other hand, in Europe, a regulation has been applied since 2010 that a certain amount of DMSO extract or a specific carcinogenic polycyclic aromatic compound should not be used for the production of tires or tire parts. For this reason, the extract obtained by extracting a vacuum distillate fraction with a polar solvent generally has a high content of polycyclic aromatic fractions, and according to the above regulation, it cannot be used as a rubber compounding oil in that state. Therefore, there is a demand for rubber compounding oil that conforms to these regulations.

A rubber compounding oil to conform to these regulations, the Patent Document 1, an aromatic hydrocarbon content (C _A) of 20 to 35 wt%, and -55 to -30 ℃ glass transition temperature (T _g), having a kinematic viscosity (100 ℃) Petroleum process oils of 20 to 50 mm 2 / s and having a polycyclic aromatic component amount (PCA) of 3% by weight or less in petroleum process oil have been proposed. When the rubber obtained by blending this petroleum process oil with a diene rubber is used for a tire, both low fuel consumption and grip characteristics can be achieved, and heat aging resistance and heat abrasion resistance can be improved.

By the way, as a rubber compounding oil, the high aromatic aromatic base oil containing the vacuum distillate fraction, the solvent extraction extract of deasphalted oil, etc. is known normally (for example, patent document 2). The solvent extraction extract of the distillate under reduced pressure generally contains many polycyclic aromatics, and due to the above restrictions, it cannot be used as a rubber compounding oil in that state. As a technique corresponding to such a situation, a method of improving the extract yield is also known for the purpose of low aromaticization by hydrogenation of aromatic compounds and dilution effect of polycyclic aromatics. However, in such a method, there is a concern that the economical deterioration due to the addition of hydrogenation equipment, the low aromaticity, or the deterioration of the yield of the lubricating oil base oil produced by-products are concerned.

On the other hand, in order to improve handleability and handling property, rubber compounding oil is required to have a high flash point (250 degreeC or more) which becomes the object of dangerous goods 4th petroleum.

Moreover, in order to improve the low temperature characteristic (low temperature elasticity modulus etc.) of rubber | gum, a rubber compounding oil is also required to make low glass transition point. For example, in patent documents 1 and 3, the rubber compounding oil with the glass transition point low in -55--30 degreeC and -45--20 degreeC, respectively is proposed.

However, in general, since the glass transition point and the aromatic content exhibit opposite characteristics, it is generally difficult to make both the high aromatic content and the low glass transition point compatible. For example, the rubber compounding oil whose aromatic content by ASTM D 2007 is 50 mass% or more and whose glass transition point is -45 degrees C or less is not obtained (for example, refer the Example of patent document 3, a comparative example). In addition, as the glass transition point of the rubber compounding oil is lowered, not only the aromatics but also the flash point tends to be lowered.

Here, a high aromatic containing base oil containing a conventional crude extract has a high pour point and a high glass transition point. In addition, although the lubricating oil base oil obtained by refine | purifying the raffinate obtained by distilling a vacuum distillate fraction under reduced pressure has a low pour point but low aromatic content and high aniline point, it is especially used for the extender oil used for manufacture of SBR etc. It is difficult.

For this reason, as a manufacturing method of a non-carcinogenic rubber compounding oil, a manufacturing method (1) the method of hydrogenating an extract and reducing polycyclic aromatics, a manufacturing method (2) of extract extraction in the extraction process by a polar solvent, for example. The method of making a yield high, diluting polycyclic aromatic, and manufacturing method (3) solvent extraction of the vacuum distillation fraction in two steps (patent document 2), etc. are known.

Moreover, as such aromatic containing base oil, when a flash point is 250 degreeC or more, it becomes outside the target of dangerous goods 4th petroleum, and since handling becomes easy, it is also required to have a high flash point. Moreover, the rubber compounding oil which has a low glass transition point is also proposed (for example, patent document 1, 3).

Among them, in Patent Document 1, a diene-based rubber compounding oil is blended into the rubber, the aromatic hydrocarbon content (C _A) of 20 to 35% by weight, a glass transition temperature (T _g) is -55 to -30 ℃, kinematic viscosity ( 100 degreeC) is proposed to use petroleum process oil of 20-50 mm <2> / s and polycyclic aromatic component amount (PCA) of 3 weight% or less. When the rubber obtained by blending this petroleum process oil with a diene rubber is used for a tire, both low fuel consumption and grip characteristics can be achieved, and heat aging resistance and heat abrasion resistance can be improved.

Japanese Unexamined Patent Publication No. 2004-155959 Japanese Patent Publication No. 3658155 Japan International Publication No. 97/35462

However, in the said manufacturing method (1), with the deterioration of the economics by adding a hydrogenation installation, there exists a tendency for the aromatic content of the obtained product to fall, and in the manufacturing method (2), the lubricating oil obtained from raffinate There exists a tendency for the yield of base oil to fall, and the aromatic content also falls. Also in the manufacturing method (3), although the density is less than 0.94 g / cm <3>, there are few polycyclic aromatics, and the yield of the extract which is a high aromatic content increases, the yield of raffinate is significantly low, and the aromatic content also tends to fall. have.

Thus, from raffinate and extract obtained by the polar solvent extraction method which uses the vacuum distillate fraction as a raw material, it has a high flash point and a low glass transition point, respectively, high total aromatic content, and the specific carcinogenic polycyclic aromatic compound is sufficient. There is no known method for producing a reduced aromatic-containing base oil in high yield. In particular, non-carcinogenic aromatic aromatic base oils obtained from raffinate, which are also useful as rubber compounding oils or bases and lubricating oil base oils, are obtained while obtaining non-carcinogenic high aromatic base oils obtained from rubber compounding oils or extracts useful as substrates thereof. The method of obtaining in high yield is not known.

Accordingly, the present invention provides a rubber compounding oil having a high flash point and a low glass transition point while sufficiently reducing the content of a specific polycyclic aromatic compound while keeping the total aromatic content high, and a method for producing such a rubber compounding oil. 1 aim.

In addition, the present invention has a high flash point, low glass transition point, high total aromatic content, and high carcinogenic substance content from raffinate and extract obtained by a polar solvent extraction method using vacuum distillate as a raw material. It is a second object to provide a sufficiently reduced aromatic-containing base oil, and to provide a method for producing an aromatic-containing base oil capable of producing such aromatic-containing base oil in high yield.

In the first aspect, in the first aspect, the total aromatic content according to ASTM D 2007 or ASTM D 2549 is 50% by mass or more, the flash point is 250 ° C or more, and the difference between the pour point and the glass transition point is 45 ° C or more, and benzo (a) The rubber compounding oil whose content of pyrene is 1 mass ppm or less and the sum total of content of the specific aromatic compound of following 1) -8) is 10 mass ppm or less is provided.

1) Benzo (a) pyrene (BaP)

2) benzo (e) pyrene (BeP)

3) benzo (a) anthracene (BaA)

4) Chrysene (CHR)

5) benzo (b) fluoranthene (BbFA)

6) benzo (j) fluoranthene (BjFA)

7) benzo (k) fluoranthene (BkFA)

8) dibenzo (a, h) anthracene (DBAhA)

The rubber compounding oil of the present invention has a high flash point and a low glass transition point while keeping the total aromatic content high, and the content of the specific polycyclic aromatic compound is sufficiently reduced.

The rubber compounding oil of the present invention contains a raffinate or refined oil obtained by separating the vacuum distillation fraction of the atmospheric distillation residue of crude oil in a solvent extraction step, and has a kinematic viscosity at 40 ° C. of 60 to 600 mm 2 / s, Aromatic-containing base oil having aniline point of 70 ° C or higher, 10% point of GC distillation of 400 to 500 ° C, 90% point of 500 to 600 ° C,% C _A of ASTM D 3238 of 3 to 20, and glass transition point of -30 ° C or less ( a), and the extract or the refined oil thereof obtained by separating the vacuum distillation fraction of the atmospheric distillation residue in the solvent extraction step, and having a kinematic viscosity at 40 ° C of 200 mm 2 / s or more, aniline point of 90 ° C or less, 15 The aromatic-containing base oil (b) is contained in the aromatic-containing base oil (b) having a density of 0.94 g / cm 3 or more and a total aromatic content of 30 mass% or more according to ASTM D 2549, and the aromatic-containing base oil (a) 95 mass% or less content and direction It contains the content of the base oil (b) at least 5% by weight is preferred.

In the present invention, the solvent extraction step, the bottom extraction temperature is 30 to 90 ℃, the top temperature is higher than the bottom temperature, the vacuum distillation fraction and the polar solvent in contact with the first raffinate, In the first solvent extraction step of obtaining the first extract, and in the second extraction column where the bottom temperature and the top temperature are each 10 ° C. or more higher than the first extraction column, the first raffinate and the polar solvent are brought into contact with each other to obtain the second rape. It has a 2nd solvent extraction process which obtains a nate and a 2nd extract, It is preferable that an aromatic containing base oil (b) contains a 2nd extract or refined oil thereof.

In addition, in the present invention, the vacuum distillation fraction of the atmospheric distillation residue of crude oil contains raffinate or refined oil obtained by separating in a solvent extraction step, and the kinematic viscosity at 40 ° C is 60 to 600 mm 2 / s, and the aniline point Aromatic-containing base oil (a) having 70 ° C. or more, 10% point by GC distillation, 400-500 ° C., 90% point 500-600 ° C.,% C _A by ASTM D 3238, 3-20, glass transition point -30 ° C. , And the extract or the refined oil thereof obtained by separating the vacuum distillation fraction of the atmospheric distillation residue in the solvent extraction step, and having a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, an aniline point of 90 ° C. or less, and 15 ° C. Has a blending step of blending an aromatic-containing base oil (b) having a density of 0.94 g / cm 3 or more and a total aromatic content of at least 30 mass% according to ASTM D 2549, and 50 masses of total aromatic content according to ASTM D 2007 or ASTM D 2549. %, Flash point 250 degreeC or more, the difference of a pour point and a glass transition point is 45 degreeC or more, content of benzo (a) pyrene is 1 mass ppm or less, and the sum total of content of the specific aromatic compound of following 1) -8) is 10 mass ppm or less Moreover, content of aromatic-containing base oil (a) provides the manufacturing method of the rubber compounding oil whose content of more than 0 mass% and 95 mass% or less and aromatic-containing base oil (b) are 5 mass% or more and less than 100 mass%.

1) Benzo (a) pyrene (BaP)

2) benzo (e) pyrene (BeP)

3) benzo (a) anthracene (BaA)

4) Chrysene (CHR)

5) benzo (b) fluoranthene (BbFA)

6) benzo (j) fluoranthene (BjFA)

7) benzo (k) fluoranthene (BkFA)

8) dibenzo (a, h) anthracene (DBAhA)

The rubber compounding oil obtained by the above-mentioned production method of the present invention has a high flash point and a low glass transition point while keeping the total aromatic content high, and the content of the specific polycyclic aromatic compound is sufficiently reduced. In addition, since the difference of a pour point and a glass transition point is 45 degreeC or more, especially 60 degreeC or more, the rubber compounding oil containing the aromatic containing base oil (b) of this invention is 50 mass% or more, for example, Even if a pour point is 15 degreeC or more, the rubber compounding oil whose glass transition point is -45 degrees C or less can be obtained. Moreover, since it is not necessary to add refine | purification, such as a dewaxing process and a hydrogenation process, to aromatic containing base oil (b), it is also excellent in economy.

According to a second aspect of the present invention, in a first extraction tower having a bottom temperature of 30 to 90 ° C. and a top temperature higher than the bottom temperature, the vacuum distillation fraction of the atmospheric distillation residue of crude oil is contacted with a polar solvent. The first raffinate and the polar solvent are brought into contact with each other in the first solvent extraction step for obtaining the raffinate and the first extract, and in the second extraction column having a column bottom temperature and a tower temperature higher than or equal to the first extraction column by 10 ° C. or more. A second solvent extraction step for obtaining a second extract having a second raffinate and a second extract having a density at 15 DEG C of at least 0.94 g / cm &lt; 3 &gt; and a total aromatic content of at least 30% by mass, a second extract, a second raffinate or The manufacturing method of the aromatic containing base oil containing at least one part of this refined oil and whose total aromatic content is 30 mass% or more is provided.

According to the present invention, an aromatic-containing base oil having a high flash point, a low glass transition point, and a high total aromatic content and sufficiently reduced content of a specific carcinogenic substance can be produced in high yield. Such aromatic-containing base oils can be suitably used as rubber compounding oils or raw materials thereof.

The present invention has a base oil preparation step of obtaining a refined oil comprising a dewaxing treatment to a second raffinate after the second solvent extraction step, and containing refined oil, having a pour point of -5 ° C or lower, and aniline It is preferable to produce aromatic containing base oil whose point is 90 degreeC or more, a viscosity index is 90 or more, and a flash point of 250 degreeC or more.

In the present invention, after the second solvent extraction step, the second raffinate has a base oil preparation step of obtaining refined oil including dewaxing treatment to obtain refined oil, containing refined oil, having a kinematic viscosity at 40 ° C. of 60 to 120 mm 2 It is preferable to produce aromatic-containing base oils having a s / s and a 10% point of 400 to 460 ° C and a 90% point of 500 to 540 ° C by gas chromatography distillation.

In the present invention, after the second solvent extraction step, there is a base oil preparation step of obtaining a refined oil including dewaxing treatment to the second raffinate to obtain refined oil, containing refined oil, kinematic viscosity at 40 ℃ 120 to 250 mm 2 It is preferable to produce an aromatic-containing base oil having a / s and a 10% point of 450 to 520 ° C and a 90% point of 540 to 600 ° C by gas chromatography distillation.

The aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, has a kinematic viscosity at 40 ° C of 200 mm 2 / s or more, a flash point of 250 ° C or more, a pour point of 30 ° C or less, and aniline It is preferable that a point is 90 degrees C or less, a glass transition point is -30 degrees C or less, and the difference of a pour point and a glass transition point is 50 degrees C or more. In addition, this aromatic containing base oil may consist of a 2nd extract.

The aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, has a kinematic viscosity at 40 ° C. of not less than 200 mm 2 / s and is less than 500 mm 2 / s, and a glass transition point of -60 It is preferable that it is -40 degreeC. Such aromatic-containing base oils are, for example, natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubbers (IR), butyl rubbers (BR) and arbitrary blends thereof. It can be used especially suitably as petroleum process oil or extender oil mix | blended with diene rubber | gum, such as rubber | gum, especially the diene rubber | gum containing at least 1 type of styrene-butadiene copolymer rubber. In addition, this aromatic containing base oil may consist of a 2nd extract.

The aromatic-containing base oil obtained by the production method of the present invention contains at least a part of the second extract, the kinematic viscosity at 40 ° C is preferably 500 mm 2 / s or more, and the glass transition point is -50 to -30 ° C. Do. Such aromatic containing base oil can be used especially suitably as petroleum process oil or extender oil mix | blended with the above-mentioned diene rubber, for example. In addition, this aromatic containing base oil may consist of a 2nd extract.

As for the aromatic containing base oil obtained by the manufacturing method of this invention, content of benzo (a) pyrene is 1 mass ppm or less, and the sum total content of the specific aromatic compound of 1) -8) shown below is 10 mass ppm or less. desirable.

1) Benzo (a) pyrene (BaP)

2) benzo (e) pyrene (BeP)

3) benzo (a) anthracene (BaA)

4) Chrysene (CHR)

5) benzo (b) fluoranthene (BbFA)

6) benzo (j) fluoranthene (BjFA)

7) benzo (k) fluoranthene (BkFA)

8) dibenzo (a, h) anthracene (DBAhA)

Since such aromatic-containing base oils have sufficiently reduced contents of specific carcinogenic polycyclic aromatic compounds, they can be particularly suitably used as petroleum-based process oils or extender oils or rubber substrates of rubber processed products such as tires.

Moreover, this invention provides the aromatic containing base oil obtained by the manufacturing method which has the said characteristic. This aromatic-containing base oil has a high flash point, a low glass transition point, a high total aromatic content, a sufficiently low content of carcinogenic substances, and safety with excellent properties as a petroleum process oil or extender oil or a substrate thereof. Is also excellent enough.

Moreover, this invention provides the rubber compounding oil containing the aromatic containing base oil which has the said characteristic in 3rd aspect.

According to the present invention, it is possible to provide a rubber compounding oil having a high flash point and a low glass transition point while sufficiently reducing the content of a specific polycyclic aromatic compound while keeping the total aromatic content high, and a method for producing such a rubber compounding oil.

Since the rubber compounding oil of this invention has a high aromatic content, it is very compatible with rubber | gum or rubber materials, such as styrene butadiene type rubber. Further, for example, when the glass transition point is used as extender oil or processed oil of rubber or rubber material such as styrene-butadiene rubber having a glass transition point of about -57 to -44 ° C, rubber having excellent low temperature characteristics can be produced. Moreover, since a flash point is high and content of carcinogenic polycyclic aromatic compound is fully reduced, safety is also high. In particular, as in Patent Document 1, the aromatic hydrocarbon content (C _A ) is 20 to 35% by mass (C _A by ASTM D 3238 is identical to 20 to 35), and the glass transition temperature (T _g ) is -55 to -30 ℃, the kinematic viscosity (100 ℃) is a rubber compounding oil of 20 to 50 mm 2 / s, for example, natural rubber (NR), various butadiene rubber (BR), various styrene-butadiene copolymer rubber (SBR), poly A diene rubber, such as isoprene rubber (IR), butyl rubber (BR), and any blend rubber thereof, is blended with a diene rubber including at least one styrene-butadiene copolymer rubber, and the rubber obtained thereby is tire When used in, it is possible to make both low fuel consumption and grip property compatible, and to improve heat aging resistance and heat wear resistance.

Moreover, according to this invention, content of a carcinogenic substance is high from a raffinate and an extract obtained by the polar solvent extraction method which uses a vacuum distillate fraction as a raw material, having a high flash point, a low glass transition point, and high total aromatic content. This sufficiently reduced aromatic containing base oil can be provided. Moreover, the manufacturing method of the aromatic containing base oil which can manufacture such an aromatic containing base oil in high yield can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS The process drawing which shows suitable embodiment of the manufacturing method of the rubber compounding oil which concerns on this invention.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described with reference to drawings. The rubber compounding oil of this embodiment is excellent in affinity with a rubber, softening property, a flash point, and safety, and it has a high level of the characteristics of the rubber composition, such as low fuel consumption, grip property, heat-aging resistance, and heat-wear resistance. In order to do so, it is preferable to have the following properties.

Aromatic content according to ASTM D 2007 (clay gel method): usually 50 to 90 mass%, preferably 55 mass% or more, more preferably 57 mass% or more, particularly preferably 60 mass% or more, preferably 80 It is mass% or less, More preferably, it is 70 mass% or less.

Saturated content according to ASTM D 2007 (clay gel method): usually 5-50% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, preferably 40% by mass or less, more preferably 30 It is mass% or less.

Polar compound powder by ASTM D 2007 (clay gel method): Usually 1-20 mass%, Preferably it is 2 mass% or more, More preferably, it is 5 mass% or more, Preferably it is 15 mass% or less, More preferably, It is 12 mass% or less, More preferably, it is 10 mass% or less.

Saturation / polar compound fraction by ASTM D 2007 (clay gel method): usually 0.25-50, preferably 1 or more, more preferably 2.5 or more, still more preferably 3 or more, preferably 20 or less More preferably, it is 10 or less, More preferably, it is five or less.

Content of benzo (a) pyrene (BaP) is 1 mass ppm or less, and sum total content of the specific aromatic compound (PAH) of 1) -8) shown below is 10 mass ppm or less. This makes it possible to obtain a rubber compounding oil having a higher safety, in which the risk of carcinogenicity is sufficiently reduced.

1) Benzo (a) pyrene (BaP)

2) benzo (e) pyrene (BeP)

3) benzo (a) anthracene (BaA)

4) Chrysene (CHR)

5) benzo (b) fluoranthene (BbFA)

6) benzo (j) fluoranthene (BjFA)

7) benzo (k) fluoranthene (BkFA)

8) dibenzo (a, h) anthracene (DBAhA)

Benzo (a) pyrene in this specification means benzo (a) pyrene (BaP) of said 1), and a specific aromatic compound means aromatic compound (PAH) of said 1) -8). After separating and concentrating a target component, these specific aromatic compounds can prepare the sample which added the internal standard substance, and can quantitatively analyze by GC-MS analysis.

Flash point is 250 degreeC or more, Preferably it is 260 degreeC or more, More preferably, it is 280 degreeC or more, Preferably it is 350 degrees C or less, More preferably, it is 320 degrees C or less, More preferably, it is 310 degrees C or less. In addition, the flash point in this specification means the flash point by Cleveland opening type (COC) measured based on JISK2265.

The difference between the pour point and the glass transition point is at least 45 ° C, preferably at least 50 ° C, more preferably at least 60 ° C, even more preferably at least 65 ° C, preferably at most 100 ° C, more preferably at most 80 ° C. to be.

The pour point is preferably at most 30 ° C, more preferably at most 25 ° C, preferably at least -10 ° C, more preferably at least 5 ° C, even more preferably at least + 10 ° C, particularly preferably at least + 12.5 ° C. to be. In addition, a pour point in this specification means the pour point measured based on JISK2269.

The glass transition point (T _g ) is preferably -30 ° C or lower, more preferably -40 ° C or lower, even more preferably -45 ° C or lower, particularly preferably -48 ° C or lower, particularly more preferably- It is 50 degrees C or less, Preferably it is -80 degreeC or more, More preferably, it is -60 degreeC or more, More preferably, it is -55 degreeC or more.

"Glass transition point (T _g )" in this specification is obtained from the calorie change peak in a glass transition area | region measured when heated up at constant temperature increase rate (10 degree-C / min) by DSC (differential scanning calorimeter). Means a glass transition point. The initial temperature is usually about 30 to 50 ° C. or lower than the expected glass transition point, and the temperature is maintained after holding for a certain time at the initial temperature. In this embodiment, it can measure on the following conditions specifically.

Apparatus: Thermal analysis system DSC Q100 made by T.A. Instruments.

Initial temperature: -90 ℃, hold for 10 minutes

Temperature rise rate: 10 ℃ / min

Termination temperature: 50 ℃, hold for 10 minutes

In addition, the method of calculating a glass transition point from a calorie change peak can be determined by the method of JISK7121.

The density at 15 ° C is usually 0.9 g / cm 3 to 1.0 g / cm 3, preferably 0.94 g / cm 3 or more, more preferably 0.945 g / cm 3 or more, preferably 0.98 g / cm 3 or less, more preferably Preferably 0.96 g / cm 3 or less.

The kinematic viscosity at 40 ° C. is usually 200 to 3000 mm 2 / s, preferably 300 mm 2 / s or more, more preferably 400 mm 2 / s, still more preferably 500 mm 2 / s or more, preferably 2000 mm 2 / s or less, More preferably, it is 1000 mm <2> / s or less, More preferably, it is 800 mm <2> / s or less. In addition, dynamic viscosity in each temperature said in this specification means dynamic viscosity in each temperature measured based on JISK2283.

Kinematic viscosity in 100 degreeC is 10-100 mm <2> / s normally, More preferably, it is 15 mm <2> / s or more, More preferably, it is 20 mm <2> / s or more, Preferably it is 60 mm <2> / s or less, More preferably, It is 50 mm <2> / s, More preferably, it is 32 mm <2> / s or less.

Aniline point is 50-100 degreeC normally, Preferably it is 60 degreeC or more, More preferably, it is 65 degreeC or more, More preferably, it is 70 degreeC or more, Preferably it is 90 degrees C or less, More preferably, it is 85 degrees C or less. . In addition, the aniline point in this specification means the aniline point measured based on JISK2256-1985.

Nitrogen content is 0.01-0.2 mass% normally, Preferably it is 0.03 mass% or more, More preferably, it is 0.05 mass% or more, Preferably it is 0.15 mass% or less, More preferably, it is 0.1 mass% or less. In addition, nitrogen content in this specification means nitrogen content by the chemiluminescence method measured based on JISK2609.

% _CN is 5-30 normally, Preferably it is 10 or more, More preferably, it is 14 or more, Preferably it is 25 or less, More preferably, it is 20 or less. % C _A is 10-40 normally, Preferably it is 17 or more, More preferably, it is 20 or more, Preferably it is 35 or less, More preferably, it is 30 or less, More preferably, it is 25 or less. % C _P is 30-85 normally, Preferably it is 40 or more, More preferably, it is 50 or more, Preferably it is 73 or less, More preferably, it is 66 or less. In addition,% C _P ,% C _N and% C _A in the present specification are paraffins obtained by the method (ndM ring analysis) according to ASTM D 3238-85, respectively, unless otherwise specified. It means the percentage of the carbon number by the total carbon number, the percentage of the naphthene carbon number by the total carbon number, and the percentage of the aromatic carbon number by the total carbon number.

The total aromatic content is usually 30 to 90 mass%, preferably 40 mass% or more, more preferably 50 mass% or more, preferably 80 mass% or less, and more preferably 70 mass% or less. In addition, all aromatics in this specification mean content of the aromatics fraction measured based on ASTMD 2007 or ASTMD 2549 except the case where it states specially.

The rubber compounding oil of the present embodiment contains raffinate or refined oil obtained by separating the vacuum distillation fraction of the atmospheric distillation residue of crude oil in the solvent extraction step, and has a kinematic viscosity at 40 ° C. of 60 to 600 mm 2 / s. aromatic, aniline point less than 70 ℃, 400 to 500 ℃ 10% by GC distillation point, 90% point of 500 to 600 ℃, the% C _a by the ASTM D 3238 3 to 20, a glass transition point of the base oil containing -30 ℃ An aromatic-containing base oil (a) containing the extract, and an extract or a refined oil thereof obtained by separating the vacuum distillation fraction of the atmospheric distillation residue in a solvent extraction step, and having a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, The aniline point contains the aromatic containing base oil (b) whose density | concentration in 90 degrees C or less, 15 degreeC is 0.94 g / cm <3> or more and 30 mass% or more of total aromatics by ASTMD 2549. Hereinafter, aromatic containing base oil (a) (henceforth base oil (a)) and aromatic containing base oil (b) (henceforth base oil (b)) are demonstrated.

The base oil (a) is contacted with a polar solvent in a first extraction column having a bottom temperature of 30 to 90 ° C. and a top temperature higher than the bottom temperature of the vacuum distillation fraction of the atmospheric distillation residue of crude oil. The first raffinate is contacted with a polar solvent in a first solvent extraction step for obtaining one extract, and in a second extraction tower in which the bottom temperature and the top temperature are each 10 ° C. or more higher than the first extraction column, and the second raffine Total aromatics obtained by purifying the second raffinate obtained by a second solvent extraction step of obtaining a second extract having a density of at least 0.94 g / cm 3 and a total aromatic content of at least 30% by mass and a total aromatic content at 15 ° C. It is preferable that it is aromatic containing base oil whose powder is 30 mass% or more.

The base oil (a) is an aromatic-containing base oil obtained by subjecting a second raffinate to a refining process including a dewaxing treatment, and has a kinematic viscosity at 40 ° C. of 60 to 120 mm 2 / s and a 400% 10% point by GC distillation. To 460 ° C, 90% of base oil (a1) having 500 to 540 ° C and / or kinematic viscosity at 40 ° C of 120 to 250 mm 2 / s, 10% of GC distillation of 450 to 520 ° C, 90% of 540 to 600 It is preferable that it is base oil (a2) which is ° C.

The base oil (b) has a kinematic viscosity at 40 ° C of 200 mm 2 / s or more, a flash point of 250 ° C or more, a pour point of 30 ° C or less, an aniline point of 90 ° C or less, a glass transition point of -30 ° C or less, It is preferable that the difference of glass transition point is aromatic containing base oil of 45 degreeC or more.

The base oil (b) is an aromatic-containing base oil (b1) having a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more and less than 500 mm 2 / s and a glass transition point of -60 to -40 ° C. and / or a kinematic viscosity at 40 ° C. of 500 mm 2 It is preferable that the aromatic transition base oil (b2) has a glass transition point of -50 to -30 占 폚 or more.

The preferable property of said base oil (a) and base oil (b) is explained in full detail.

Preferably the pour point of base oil (a) is -10 degrees C or less, and may be less than -20 degreeC. However, from the viewpoint of the production cost of the rubber compounding oil, the pour point of the base oil (a) is more preferably -10 to -20 ° C. By using the base oil (a) whose pour point is -10 degrees C or less, the rubber compounding oil which has a much lower glass transition point can be obtained easily.

The glass transition point of base oil (a) becomes like this. Preferably it is -30 degrees C or less, More preferably, it is -50 degrees C or less, Preferably it is -100 degrees C or more, More preferably, it is -80 degrees C or more, More preferably, it is -70 It is more than ℃. If the glass transition point is too high, it is difficult to obtain a rubber compounding oil having a low glass transition point, and if the glass transition point is too low, the manufacturing cost tends to increase because the dewaxing conditions need to be excessively strict.

The aniline point of base oil (a) becomes like this. Preferably it is 70 degreeC or more, More preferably, it is 90 degreeC or more, More preferably, it is 100 degreeC or more. Preferably it is 120 degrees C or less from a viewpoint of being easy to manufacture the rubber compounding oil which is excellent in compatibility with rubber and has a suitable aniline point in order to maintain the characteristic of a rubber composition.

As the composition of the base oil (a),% C _A is preferably 3 to 20, more preferably from 5 to 10, and,% C _N is preferably 15 to 35, more preferably 20 to 30. In addition,% C _P of the base oil (a) is, is determined by the% C _A,% C _N, and preferably from 45 to 82, more preferably from 60 to 75, more preferably from 65 to 70. By using the base oil (a) whose composition is in the above range, it is possible to easily prepare a rubber compounding oil having a composition suitable for compatibility with rubber and maintaining the properties of the rubber composition.

The nitrogen content of base oil (a) becomes like this. Preferably it is 0.01 mass% or less, More preferably, it is 0.008 mass% or less, and may be less than 0.001 mass%. However, since the manufacturing cost of a rubber compounding oil can be reduced when using a lubricating oil base oil with low refinement | purity, from a viewpoint of economy, Preferably it is 0.002 mass% or more, More preferably, it is 0.003 mass% or more.

The flash point of the base oil (a) is 250 degreeC or more from the viewpoint of making the flash point of a rubber compounding oil 250 degreeC or more and out of the target of dangerous goods 4th petroleum, Preferably it is 255 degreeC or more. Moreover, since the flash point of base oil (b) can also be made high, it is not necessary to make the flash point of base oil (a) more than necessary, Preferably it is 290 degrees C or less, More preferably, it is 280 degrees C or less.

The 90% point in GC distillation of base oil (a) is 500 degreeC or more, Preferably it is 500-600 degreeC. As the base oil a1 which is one form of base oil (a), what is 510-550 degreeC and what is 550-590 degreeC can be used as base oil (a2) which is another form of base oil (a). In addition, there is no restriction | limiting in particular in the 10% point in GC distillation of base oil (a), Since the flash point of a rubber compounding oil can be 250 degreeC or more, it can be excluded from the dangerous goods 4th petroleum, Preferably it is 400-510 ° C, preferably 440 to 500 ° C. As base oil (a1), what is 10% point in GC distillation is 440-470 degreeC, and as base oil (a2), what is 10% point in GC distillation can be used 450-500 degreeC.

It is preferable that content of said 1) benzo (a) pyrene (BaP) is 1 mass ppm or less, and the sum total of content of the specific aromatic compound (PAH) of said 1) -8) is 10 mass ppm of base oil (a). It is preferable that it is the following. This makes it possible to produce a rubber compounding oil having a higher safety, in which carcinogenicity is sufficiently reduced.

The kinematic viscosity at 40 ° C of the base oil (a) is preferably 60 to 600 mm 2 / s, more preferably 60 to 300 mm 2 / s, still more preferably 70 to 200 mm 2 / S.

In the case of using a base oil (b) having a kinematic viscosity at 40 ° C. of less than 2000 mm 2 / s, in order to obtain a suitable kinematic rubber compounding oil, the kinematic viscosity at 40 ° C. is preferably 50 to 500 mm 2 / s, more preferably It is preferable to use the base oil (a1) which is 60-80 mm <2> / s, and / or the base oil (a2) which is 120-250 mm <2> / s.

There is no restriction | limiting in particular in the total aromatics of base oil (a), Usually, 20 mass% or more, Preferably it is 30 mass% or more, More preferably, it is 35 mass% or more, Preferably it is 50 mass% or less, More preferably, It is 45 mass% or less. When the total aromatic content of the base oil (a) is less than 20% by mass, it is difficult to obtain a high aromatic rubber compounding oil. On the other hand, when the total aromatic content of the base oil (a) exceeds 50 mass%, the oxidative stability in the case of using it as a lubricating oil base oil will fall, and it becomes difficult to use it as a lubricating oil base oil and a rubber compounding oil use, and the economics of the whole petroleum refining process This tends to be lowered.

The aniline point of base oil (b) becomes like this. Preferably it is 40-90 degreeC, More preferably, it is 45-70 degreeC, More preferably, it is 50-65 degreeC. If the aniline point is in this range, even if a lubricating oil base oil having a high aniline point is blended, a rubber compounding oil having an aniline point which is excellent in compatibility with rubber and suitable for maintaining the properties of the rubber composition can be easily produced.

As the composition of the base oil (b),% C _A is preferably 25 to 45, more preferably 30 to 40 and,% C _N is preferably from 5 to 20, more preferably 6 to 12. In addition,% C _P is, depends on the% C _A,% C _N, and preferably from 35 to 70, more preferably from 48 to 64. When the composition of the base oil (b) is within the above range, even when the base oil (a) having high paraffinity is blended, a rubber compounding oil having a composition excellent in compatibility with rubber and suitable for maintaining the properties of the rubber composition can be easily produced. can do.

The nitrogen content of base oil (b) becomes like this. Preferably it is 0.01 mass% or more, More preferably, it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Especially preferably, it is 0.15 mass% or more. The higher the nitrogen content of the base oil (b) is, the lower the nitrogen content of the raffinate obtained by the solvent extraction step is, thereby improving the refinement of the lubricating oil base oil. Therefore, using the base oil (b) with high nitrogen content as a rubber compounding oil is preferable at the point which can utilize the whole vacuum distillation fraction effectively.

The pour point of base oil (b) becomes like this. Preferably it is 30 degrees C or less, More preferably, it is 25 degrees C or less. Moreover, the pour point of base oil (b) becomes like this. Preferably it is 5 degreeC or more, More preferably, it is 10 degreeC or more, More preferably, it is 15 degreeC or more, Especially preferably, it is 20 degreeC or more.

The base oil (b) may be a crude extract having a high pour point, and preferably has a low glass transition point. The difference between the pour point and the glass transition point (flow point-glass transition point) of the base oil (b) is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, even more preferably 55 ° C. or higher, particularly preferably 60 ° C. As mentioned above, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less.

The glass transition point of the base oil (b) is preferably -30 ° C or lower, preferably -60 ° C or higher. The glass transition point of the aromatic containing base oil (b1) which is one form of base oil (b) is -60--40 degreeC, and the glass transition point of the aromatic containing base oil (b2) which is another form is -50--30 degreeC.

Moreover, it is preferable that content of said 1) benzo (a) pyrene (BaP) is 1 mass ppm or less, and, as for base oil (b), the sum total of content of the specific aromatic compound (PAH) of said 1) -8) is It is preferable that it is 10 mass ppm or less. This makes it possible to produce a rubber compounding oil having a higher safety, in which carcinogenicity is sufficiently reduced.

The flash point of the base oil (b) is not particularly limited, but is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, in order to set the flash point of the rubber compound oil to be 250 ° C. or higher to exclude the dangerous substance fourth petroleum. Preferably it is 290 degreeC or more, Especially preferably, it is 300 degreeC or more.

The total aromatics of the base oil (b) are preferably at least 30% by mass, more preferably at least 50% by mass, even more preferably at least 55% by mass, particularly preferably at least 60% by mass, even more preferably It is 65 mass% or more, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.

If the total aromatic content of the base oil (b) is less than 50 mass%, it is difficult to obtain a high aromatic rubber compounding oil. If the total aromatic content is more than 90 mass%, the yield of the extract is deteriorated. It is not preferable in view of.

Next, suitable embodiment of the manufacturing method of the rubber compounding oil of this invention is described.

In this embodiment, it has the 1st solvent extraction process and the 2nd solvent extraction process which produce base oil (a) and base oil (b), and the compounding process which mix | blended the produced base oil (a) and base oil (b). First, the 1st solvent extraction process and the 2nd solvent extraction process which manufacture base oil (a) and base oil (b) are demonstrated.

In the first solvent extraction step, the bottom extraction temperature is 30-90 ° C. and the top temperature is higher than the bottom temperature, and the reduced pressure distillation fraction of the atmospheric distillation residue of crude oil is brought into contact with the polar solvent to form the first raffinate. Obtain the first extract. In the second solvent extraction step, the first raffinate and the polar solvent are brought into contact with each other in the second extraction column having a bottom temperature and a top temperature higher by 10 ° C. or more than the first extraction column, respectively, and the density at the second raffinate and 15 ° C. A second extract having a value of 0.94 g / cm 3 or more and a total aromatic content of 30 mass% or more is obtained. Hereinafter, the detail of each process is demonstrated.

(1st solvent extraction process)

FIG. 1: is process drawing for demonstrating the 1st solvent extraction process and the 2nd solvent extraction process in the manufacturing method of the rubber compounding oil in this embodiment. In the first solvent extraction step, first, the vacuum distillation fraction of the atmospheric distillation residue of crude oil is subjected to countercurrent contact with the polar solvent in the first extraction column 30 whose bottom temperature is 30 to 90 ° C. and the top temperature is higher than the bottom temperature. The first raffinate and the first extract are separated. The polar solvent is supplied from the pipe 34 to the first extraction tower 30. On the other hand, the distillation under reduced pressure is supplied to the first extraction tower 30 through the pipe 16.

The vacuum distillation fraction is an oil fraction obtained by introducing a normal distillation residue of ordinary crude oil into a vacuum distillation apparatus. The vacuum distillation fraction is not particularly limited, and light lubricating oil fraction, heavy lubricating oil fraction, heavy lubricating oil fraction, mixtures thereof, or all of the vacuum distillation fraction may be used. From the viewpoint of increasing the flash point of the finally obtained aromatic-containing base oil and at the same time obtaining an aromatic-containing base oil in an appropriate viscosity range without causing the viscosity to become too high, for example, 200 to 1500 N, preferably 250 to 1200 N, more preferably Uses a lubricant oil of 300 to 600N or 600 to 1200N. In addition, "N" in this specification means that it is neutral oil obtained from vacuum distillation fraction, and for example, when it is 300N, the viscosity in 100 degreeF (37.8 degreeC) is 300 Seybolt universal herb (SUS). Means that.

In this embodiment, it is preferable to select a vacuum distillation fraction so that base oil (a) may become a viscosity of 200-1500 N, Preferably 250-600 N or 600-1200 N, More preferably, 300-450 N or 700-1000 N.

The bottom temperature of the 1st extraction tower 30 used in a 1st solvent extraction process is 30-90 degreeC, Preferably it is 50-70 degreeC, More preferably, it is 55-65 degreeC. The top temperature of the first extraction column 30 is higher than the bottom temperature, preferably 10 to 50 ° C higher, more preferably 15 to 40 ° C higher, and even more preferably 25 to 35 ° C higher. Specifically, the top temperature is preferably 60 to 120 ° C, more preferably 80 to 100 ° C, still more preferably 85 to 95 ° C.

The solvent ratio in a 1st solvent extraction process becomes like this. Preferably it is 0.5-3, More preferably, it is 0.7-2, More preferably, it is 1-1.5. In addition, the "solvent ratio" in this specification means the capacity ratio (solvent capacity / raw material capacity) of the solvent with respect to a raw material.

Under the above conditions, the polar solvent and the vacuum distillation fraction are in countercurrent contact with each other in the first extraction tower 30, and the polarity of the first extract is passed through the pipe 38 from the bottom of the first extraction tower 30. A mixture of solvent is obtained and a mixture of the first raffinate and the polar solvent is obtained by passing through the pipe 36 from the tower portion. In addition, the mixture of a 1st extract and a polar solvent is classified into a 1st extract and a polar solvent in the fractionation tower which is not shown in figure. The mixture of the first raffinate and the polar solvent may be classified into the first raffinate and the polar solvent in a fractionation column (not shown), or may be introduced into the second extraction column 40 without being fractionated.

In a fractionation tower (not shown), the polar solvent classified into the first extract and the first raffinate is recovered and reused. Examples of the polar solvent include polar solvents such as furfural, phenol, cresol, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, formylmorpholine, and glycol solvents. In this embodiment, it is preferable to use furfural from the point which can use the solvent extraction equipment of general lubricating oil base oil as it is.

As described above, in the first solvent extraction step, the vacuum distillation fraction is separated into the first raffinate and the first extract. The yield of the first raffinate obtained in the first solvent extraction step is preferably 50 to 90% by volume, more preferably 60 to 85% by volume, even more preferably 70 to 80 based on the vacuum distillation fraction. Capacity%. The yield of the 1st extract obtained by the 1st solvent extraction process becomes like this. Preferably it is 10-50 volume%, More preferably, it is 15-40 volume%, More preferably, 20-30 based on the vacuum distillate fraction Capacity%.

Since the specific aromatic compound (PAH) mentioned later is extracted by the 1st solvent extraction process to the 1st extract side, the specific aromatic compound of the 2nd extract of the latter stage, the 2nd raffinate, and the aromatic containing base oil obtained from these are extracted. Content of (PAH) can fully be reduced. Moreover, since a 1st extract contains specific aromatic compound (PAH), it exists in the tendency which is not suitable for lubricating oil base oil and rubber compounding oil. Therefore, by making the yield of this 1st extract into 30 volume% or less, the 2nd raffinate useful as lubricating oil base oil, rubber compounding oil, or its base material, and 2nd extract can be obtained in high yield. For example, the total of the second raffinate and the second extract can be 70% by volume or more based on the vacuum distillate fraction, and the method for producing the aromatic-containing base oil of the present embodiment effectively utilizes resources. It is also very useful in that.

In the second solvent extraction step, the first raffinate or the mixture of the first raffinate and the polar solvent and the polar solvent obtained in the first solvent extraction step are transferred from the pipe 36 and the pipe 44 to the second extraction tower 40. ) And each of the first raffinate and the polar solvent in the second extraction column 40. The bottom extraction temperature and the top temperature of the 2nd extraction tower 40 are 10 degreeC or more higher than the 1st extraction tower 30, respectively.

The bottom temperature of the 2nd extraction tower 40 used for a 2nd solvent extraction process is 10 degreeC or more higher than the top bottom temperature of the 1st extraction tower 30 in a 1st solvent extraction process, Preferably it is 10-50 degreeC It is high, More preferably, it is 15-40 degreeC high, More preferably, it is 20-30 degreeC high. Specifically, the bottom temperature of the second extraction column 40 is preferably 40 to 140 ° C, more preferably 60 to 100 ° C, still more preferably 80 to 95 ° C.

The top temperature of the second extraction column 40 is preferably 10 to 50 ° C higher than the bottom temperature, more preferably 15 to 40 ° C higher, still more preferably 25 to 35 ° C higher. Specifically, the top temperature of the second extraction column 40 is preferably 50 to 150 ° C, more preferably 80 to 140 ° C, still more preferably 110 to 130 ° C.

The solvent ratio in the 2nd solvent extraction process becomes like this. Preferably it is 1-4, More preferably, it is 1.3-3.5, More preferably, it is 1.5-3.3. It is preferable to make the solvent ratio in a 2nd solvent extraction process into 1.5 times or more of the solvent ratio in a 1st solvent extraction process.

Under the above conditions, the polar solvent and the first raffinate are in countercurrent contact with each other in the second extraction tower 40, and the second extract is passed through the pipe 48 from the bottom of the second extraction tower 40. A mixture of polar solvent is obtained, and a mixture of the second raffinate and the polar solvent is obtained from the tower section through the pipe 46. In addition, the mixture of a 2nd extract and a polar solvent is classified into a 2nd extract and a polar solvent in the fractionation tower which is not shown in figure. In addition, the mixture of a 2nd raffinate and a polar solvent is classified into a 2nd raffinate and a polar solvent in the fractionation tower which is not shown in figure. In the fractionation tower (not shown), the polar solvent separated from the second extract and the second raffinate is recovered and reused.

As described above, in the second solvent extraction step, the first raffinate is separated into the second raffinate and the second extract. The yield of the second raffinate obtained in the second solvent extraction step is preferably from 50 to 90% by volume, more preferably from 60 to 90, based on the first raffinate introduced into the second extraction column 40. 85 volume%, More preferably, it is 70-85 volume%. The yield of the 2nd extract obtained by the 2nd solvent extraction process becomes like this. Preferably it is 10-50 volume%, More preferably, it is 15-40 volume%, More preferably, it is 15-30 volume%.

In addition, in this embodiment, it is not necessary to use separate extraction towers as the first and second extraction towers, and one extraction tower may be used as the first extraction tower 30 and the second extraction tower 40. In this case, the raffinate (preferably the polar solvent is removed) obtained in the first solvent extraction step is once stored in a tank or the like, and the extraction condition is adjusted to the second extraction tower 40 adjusted to the conditions of the second solvent extraction step. It is good to introduce and implement a 2nd solvent extraction process. By doing in this way, excess facility investment can be performed.

By the second solvent extraction step, the first raffinate and the second extract having a density at 15 ° C of 0.94 g / cm 3 or more and total aromatic content of 30% by mass or more can be obtained. When the density of the second extract at 0.9C is 0.94 g / cm 3 or more, a tire using a diene rubber having a high total aromatic content, a low aniline point, a high flash point, and a large difference between the pour point and the glass transition point is obtained. It is useful as petroleum process oil in the manufacturing process of a rubber | gum product, or its base material, or extender oil in the diene rubber manufacturing process, or its base material. Moreover, from the second raffinate obtained at the same time, it becomes possible to obtain in high yield an aromatic-containing base oil which is also useful as a lubricating oil base oil, a petroleum-based process oil, an extender oil or a substrate thereof having a total aromatic content of 30% by mass or more.

The density of the second extract at 15 ° C. is preferably 0.94 g / cm 3 or more, more preferably 0.95 to 1 g / cm 3 and still more preferably 0.95 to 0.98 g / cm 3. The total aromatic content is preferably 30% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, and preferably 90% by mass or less. In addition, the "all aromatic content" in this specification is a value measured based on ASTMD2549.

The second extract has a% C _{A as} measured by ASTM D 2140, preferably 15 to 35, more preferably 20 to 33, still more preferably 22 to 32.

It is preferable that this 2nd extract has the following characteristics.

Flash point: Preferably it is 250 degreeC or more, More preferably, it is 260 degreeC or more, Preferably it is 310 degrees C or less.

Pour point: Preferably it is 30 degrees C or less, More preferably, it is 10-30 degreeC.

Aniline point: Preferably it is 90 degrees C or less, More preferably, it is 40-80 degreeC, More preferably, it is 50-70 degreeC.

Glass transition point: Preferably it is -30 degrees C or less, More preferably, it is -40 degrees C or less, More preferably, it is -60 degrees C or more.

Difference between pour point and glass transition point (flow point-glass transition point): preferably at least 45 ° C, more preferably at least 50 ° C, even more preferably at least 55 ° C, preferably at most 100 ° C, more preferably 80 degrees C or less.

Benzo (a) pyrene content: Preferably it is 1 mass ppm or less.

Total content of specific aromatic compound (PAH): Preferably it is 10 mass ppm or less.

Next, a lubricating oil base oil which is a refined oil can be obtained by adding a refining treatment comprising a dewaxing treatment by the dewaxing apparatus 50 and a hydrofinishing treatment by the hydrofinishing apparatus 60 to the second raffinate. The aromatic-containing base oil (lubricating oil base oil) thus obtained can be used as the base oil (a). The base oil (a) may be a mixture of two or more aromatic-containing base oils (lubricating oil base oils) obtained as described above.

As for the base oil (a) obtained in this way, all aromatic content becomes like this. Preferably it is 30 mass% or more, More preferably, it is 30-60 mass%. The base oil (a) is preferably 200 to 1500N, more preferably 250N to less than 600N base oil (a1) and / or 600 to 1200N base oil (a2), still more preferably 300 to 450N base oil (a1) And / or base oil (a2) of 700 to 1000 N.

The vacuum distillation fraction for obtaining an aromatic-containing base oil of 500N may contain many of the eight specific aromatic compounds (PAH) described above, and two or more kinds of aromatic-containing base oils having different flash points at the same time may be obtained at the same time. There is a tendency to be difficult. For this reason, it is preferable to obtain aromatic containing base oil using 300-450 N base oil (a1) and / or 700-1000 N base oil (a2).

In the method for producing an aromatic-containing base oil of the present embodiment, after the second solvent extraction step, an aromatic-containing base oil having a total aromatic content of 30% by mass or more is obtained using at least one selected from the second extract and the second raffinate. You may have a base oil preparation process.

In a base oil preparation process, the aromatic containing base oil whose total aromatic content is 30 mass% or more is obtained using at least one selected from a 2nd extract and a 2nd raffinate. Further, a refined treatment including dewaxing treatment was added to the second raffinate to obtain refined oil (wax oil) having a pour point of −5 ° C. or lower, an aniline point of 90 ° C. or higher, a viscosity index of 90 or higher, and a flash point of 250 ° C. or higher, You may make this into aromatic containing base oil. As the purification treatment, it is preferable to perform dewaxing treatment and hydrogenation finishing. Thereby, the aromatic containing base oil whose total aromatic content is 30 mass% or more can be obtained easily. The refined oil obtained by applying the above refining treatment can be suitably used as a lubricating oil base oil, a rubber compounding oil or a substrate thereof.

When the refined oil of 200-1500 N is obtained from 2nd raffinate, for example, when the said 1st and 2nd solvent extraction process is performed using the vacuum distillation fraction corresponding to this viscosity as a raw material, It is possible to obtain a second extract having a kinematic viscosity of preferably at least 200 mm 2 / s, more preferably at least 250 mm 2 / s, even more preferably at most 5000 mm 2 / s, particularly preferably at most 2000 mm 2 / s. .

By the above process, the aromatic-containing base oil (henceforth "aromatic-containing base oil a") which is 30 mass% or more from the 2nd raffinate and / or its refined oil, and / or the 2nd extract from the 2nd extract An aromatic containing base oil (henceforth "aromatic containing base oil b") which is 30 mass% or more can be obtained.

In the base oil preparation step, the oil is appropriately fractionated from the second raffinate and the second extract by distillation, and then a part of the second raffinate and a part of the second extract are respectively divided into base oil (a) and base oil (b). ) May be used. In addition, the second raffinate and the second extract obtained in the second solvent extraction step may be used as the base oil (a) and the base oil (b) without performing the base oil preparation step.

It is preferable to obtain the base oil (a) and the base oil (b) which have a desired property as a production product by selecting the vacuum distillate fraction which is a raw material suitably according to desired base oil (a) and base oil (b). For example, when obtaining lubricating oil base oil of 300N or more and less than 600N as base oil (a), the above-mentioned 1st and 2nd solvent extraction process using the vacuum distillation fraction corresponding to this oil as a raw material, and optionally After the refining process, a lubricating oil base oil of 300 N or more and less than 600 N is obtained as the base oil (a), and the kinematic viscosity at 40 ° C. as the base oil (b) is 200 mm 2 / s or more and less than 500 mm 2 / s, preferably 250 to 350 mm <2> / s, More preferably, the thing of 250-300 mm <2> / s can be obtained.

For example, when obtaining 600-1200 N lubricating oil base oil as a base oil (a), the above-mentioned 1st and 2nd solvent extraction process, and the case are carried out using the vacuum distillation fraction corresponding to this oil as a raw material, and Accordingly, the lubricating oil base oil of 600-1200 N is obtained as base oil (a), and the kinematic viscosity in 40 degreeC as base oil (b) is 500-5000 mm <2> / s, Preferably it is 800-2000 mm <2> / s, More preferably, what is 900-1500 mm <2> / s can be obtained.

As described above, the base oil (a) of the present embodiment may be obtained by subjecting the second raffinate to a purification treatment including dewaxing, hydrogenation, and the like. The base oil (a) (lubricating oil base oil) obtained in this way is 30 mass% or more in total aromatic content, Preferably it is 30-60 mass%. The base oil (a) is preferably obtained as a lubricating oil base oil of 200 to 1500N, more preferably 250N or more and also less than 600N or 600 to 1200N, still more preferably 300 to 450N or 700 to 1000N.

The base oil (a) is 300 to 450 N or 700 from the viewpoint of reducing the content of the eight kinds of specific aromatic compounds (PAH) and at the same time obtaining a base oil (a) and a base oil (b) having high flash points different from each other. It is especially preferable that they are 1000N.

In the case where the base oil (a) is 600 to 1200 N, preferably 700 to 1000 N, in addition to the specific properties described above, it is preferable to further have the following properties.

Kinematic viscosity at 40 ° C .: 120 to 250 mm 2 / s, preferably 150 to 200 mm 2 / s.

10% point by gas chromatography distillation: 450-520 degreeC, Preferably it is 460-500 degreeC.

90% point by gas chromatography distillation: 540-600 degreeC, Preferably it is 560-590 degreeC.

Total aromatic component (ASTM D 2549): 30 mass% or more, Preferably it is 35-60 mass%, More preferably, it is 40-50 mass%.

According to this embodiment, base oil (a) and base oil (b) whose content of a specific aromatic compound (PAH) is below a predetermined amount can be obtained. In addition, "specific aromatic compound (PAH)" in this specification means eight specific aromatic compounds (PAH) listed below. In the base oil (a) and the base oil (b) of the present embodiment, the content of benzo (a) pyrene (BaP) of 1) is 1 mass ppm or less, and eight specific aromatic compounds (PAH) of 1) to 8) below The sum total of content of) can be 10 mass ppm or less.

1) Benzo (a) pyrene (BaP)

2) benzo (e) pyrene (BeP)

3) benzo (a) anthracene (BaA)

4) Chrysene (CHR)

5) benzo (b) fluoranthene (BbFA)

6) benzo (j) fluoranthene (BjFA)

7) benzo (k) fluoranthene (BkFA)

8) dibenzo (a, h) anthracene (DBAhA)

Generally, these specific aromatic compounds (PAH) isolate | separate and concentrate the target component, and prepare the sample which added the internal standard substance, and can quantitatively analyze by GC-MS analysis.

Base oil (a) and base oil (b) are suitable as lubricating oil base oil, rubber compounding oil, or these base materials. The base oil (a) is suitable as a lubricating oil base oil because the content of the specific aromatic compound (PAH) is sufficiently reduced and the flash point is 250 ° C or more and the pour point is -5 ° C or less. Moreover, since total aromatic content is 30 mass% or more and a glass transition point is -30 degrees C or less, it can use as petroleum process oil or extender oil, or its base material.

The base oil (b) has a sufficiently low content of a specific aromatic compound (PAH), a flash point of 250 ° C or more, a total aromatic content of 30% by mass or more, and a glass transition point of -30 ° C or less. It can be used as an extender oil or a substrate thereof.

The diene system is prepared by using a base oil (a), a base oil (b) or a mixture thereof, for example, by preparing a glass transition temperature of -55 to -30 ° C and a kinematic viscosity (100 ° C) of 20 to 50 mm 2 / s. It may be a petroleum process oil or an extender oil which is particularly suitable for blending rubber. A tire produced by blending such petroleum process oil or extender oil with a diene rubber can achieve both low fuel consumption and grip characteristics, and can improve heat aging resistance and wear resistance.

As described above, according to the production method of the present embodiment, an aromatic-containing base oil having a high flash point, a low glass transition point, and a high total aromatic content and sufficiently reduced content of carcinogenic substances can be obtained in high yield. . In addition, it is particularly useful in the industry because it is possible to simultaneously produce plural kinds of aromatic-containing base oils having properties suitable for lubricating oil base oils, petroleum process oils or extender oils or substrates thereof, and having different viscosities.

It is preferable that base oil (a) has the following properties.

Pour point: Preferably it is -5 degrees C or less, More preferably, it is -10 degrees C or less, More preferably, it is -20 degrees C or more.

Glass transition point: Preferably it is -30 degrees C or less, More preferably, it is -40 degrees C or less, More preferably, it is -50 degrees C or less, Preferably it is -60 degrees C or more, More preferably, it is -100 degrees C or more, More preferably Preferably -80 ° C or higher, particularly preferably -70 ° C or higher.

Aniline point: Preferably it is 70 degreeC or more, More preferably, it is 90 degreeC or more, More preferably, it is 105 degreeC or more, Preferably it is 120 degrees C or less.

Viscosity index: Preferably it is 90 or more, More preferably, it is 95 or more, Preferably it is 120 or less, More preferably, it is 105 or less.

Flash point: Preferably it is 250 degreeC or more, Preferably it is 310 degrees C or less.

Base oil composition according to ASTM D 3238:% C _P is preferably 60 to 70,% C _N is preferably 20 to 30, and% C _A is preferably 5 to 10.

Benzo (a) pyrene content: Preferably it is 1 mass ppm or less.

Total content of specific aromatic compound (PAH): Preferably it is 10 mass ppm or less.

As the aromatic-containing base oil of 300 N or more and less than 600 N, preferably 300 to 450 N, which is the base oil (a1), it is preferable to have the following properties in addition to the above properties.

Kinematic viscosity at 40 ° C .: preferably 60 to 120 mm 2 / s, more preferably 65 to 90 mm 2 / s, still more preferably 70 to 80 mm 2 / s.

10% point by GC distillation, Preferably it is 400-460 degreeC, More preferably, it is 430-450 degreeC.

90% point by GC distillation: Preferably it is 500-540 degreeC, More preferably, it is 510-530 degreeC.

Total aromatic fraction (ASTM D 2549): Preferably it is 30 mass% or more, More preferably, it is 30-50 mass%.

In addition, the value of the gas chromatography distillation in this specification is a value measured based on ASTMD2887.

It is preferable that the aromatic-containing base oil of 600-1200 N, preferably 700-1000 N which is base oil (a2) has the following properties in addition to the said properties.

Kinematic viscosity at 40 ° C: Preferably it is 120-250 mm <2> / s, More preferably, it is 150-200 mm <2> / S.

10% point by GC distillation: Preferably it is 450-520 degreeC, More preferably, it is 460-500 degreeC.

90% point by GC distillation: Preferably it is 540-600 degreeC, More preferably, it is 560-590 degreeC.

Total aromatic component (ASTM D 2549): Preferably it is 30 mass% or more, More preferably, it is 35-60 mass%, More preferably, it is 40-50 mass%.

As base oil (b), the aromatic containing base oil which is a 2nd extract or its refined oil obtained by adding the said 1st and 2nd solvent extraction process can be used. In addition, the base oil (b) may mix 2 or more types of 2nd extract or its refined oil obtained as mentioned above.

The base oil (b) has a kinematic viscosity at 40 ° C of 200 mm 2 / s or more and less than 500 mm 2 / s, a base oil (b1) having a glass transition point of -60 to -40 ° C and / or a kinematic viscosity at 40 ° C of 500 mm 2 / s or more It is preferable that it is base oil (b2) whose glass transition point is -50--30 degreeC.

As the base oil (b1), in addition to the above properties, it is preferable to have the following properties.

Kinematic viscosity at 40 ° C .: Preferably it is 200 mm 2 / s or more and less than 500 mm 2 / s, more preferably 400 mm 2 / s or less, still more preferably 350 mm 2 / s or less, particularly preferably 300 mm 2 / s or less .

Glass transition point: preferably -60 to -40 ° C, more preferably -55 to -48 ° C.

Pour point: Preferably it is 0-30 degreeC, More preferably, it is 15 degreeC or more, More preferably, it is 20 degreeC or more.

Difference between pour point and glass transition point (flow point-glass transition point): preferably at least 60 ° C., more preferably at least 65 ° C., even more preferably at least 70 ° C., preferably at most 100 ° C., more preferably 80 degrees C or less.

Total aromatic content: 50 mass% or more, Preferably it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Preferably it is 90 mass% or less.

As the base oil (b2), in addition to the above properties, it is preferable to have the following properties.

Kinematic viscosity at 40 ° C .: preferably 500 mm 2 / s or more, more preferably 800 mm 2 / s or more, more preferably 1000 mm 2 / s or more, preferably 5000 mm 2 / s or less, more preferably 2000 Mm 2 / s or less, more preferably 1500 mm 2 / s or less.

Glass transition point: Preferably it is -50--30 degreeC, More preferably, it is -45-35 degreeC.

Total aromatic content: 50 mass% or more, Preferably it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Preferably it is 90 mass% or less.

In the case of obtaining the aromatic-containing base oil of 200 to 1500 N as the base oil (a) by the first and second solvent extraction steps described above, by using the vacuum distillation fraction corresponding to this fraction as the raw material, simultaneously as the base oil (b) The kinematic viscosity at 40 ° C is preferably 200 mm 2 / s or more, preferably 250 mm 2 / s or more, preferably 5000 mm 2 / s or less, more preferably 2000 mm 2 / s or less. The base oil (a) and the base oil (b) may be ones obtained by appropriately distilling the desired oil component by distillation. In this case, the viscosity of the vacuum distillation fraction which is a raw material is not specifically limited.

However, since it is preferable to obtain desired base oil (a) and desired base oil (b) as a product, the vacuum distillation fraction suitable for the properties of the base oil (a) and the base oil (b) is selected, and the same vacuum distillation fraction is started. It is preferable to use it as a raw material.

For example, when obtaining 250N or more and less than 600N aromatic containing base oil as base oil a1, the vacuum distillation fraction corresponding to this oil fraction is used as a raw material. By the first and second solvent extraction steps, an aromatic-containing base oil of 250N or more and less than 600N is obtained as the base oil (a1), and the kinematic viscosity at 40 ° C as the base oil (b1) is 200 mm 2 / s or more and 500 mm 2. It is preferable to obtain an extract (aromatic containing base oil) of less than / s, preferably 250 to 350 mm 2 / s, more preferably 250 to 300 mm 2 / s.

For example, when obtaining 600-1200 N lubricating oil base oil as base oil a2, the vacuum distillation fraction corresponding to this oil fraction is used as a raw material. And by the said 1st and 2nd solvent extraction process, 600-1200N aromatic containing base oil is obtained as base oil (a2), and kinematic viscosity in 40 degreeC as base oil (b2) is 500-5000mm <2> / s, It is preferable. It is preferred to obtain extracts (aromatic containing base oils) of 800 to 2000 mm 2 / s, more preferably 900 to 1500 mm 2 / s. In this method, it is preferable to perform a batch treatment in order to obtain the desired base oil (a) and the base oil (b).

In the compounding step, the base oil (a) and the base oil (b) obtained as described above are blended in a predetermined ratio to prepare a rubber compounding oil. For example, 95 mass% or less (does not contain 0) and base oil (b) are mix | blended at the ratio of 5 mass% or more of base oil (a) on the basis of the rubber compounding oil whole quantity basis. Thereby, the rubber compounding oil containing a base oil (a) and a base oil (b) can be obtained.

In addition, you may prepare rubber compounding oil independently of the base oil (b), without performing the said compounding process. However, from the viewpoint of obtaining a rubber compounding oil having an appropriate kinematic viscosity (kinematic viscosity at 100 ° C. of 10 to 70 mm 2 / s, preferably 15 to 50 mm 2 / s, more preferably 20 to 32 mm 2 / s), and, From the viewpoint of obtaining a rubber compounding oil having a difference between the pour point and the glass transition point of 50 ° C. or more, the blending ratio of the base oil (a) is preferably 10 to 50% by mass, more preferably based on the entire rubber compounding oil. Shall be 20-40 mass%. From the same viewpoint, the blending ratio of the base oil (b) is preferably 90 to 50% by mass, more preferably 80 to 60% by mass.

From the viewpoint of obtaining a rubber compounding oil having a difference between the pour point and the glass transition point of 50 ° C. or more and a glass transition point of −50 ° C. or less, the base oil (a) preferably contains the base oil (a2), and the base oil (b) It is preferable to include a base oil (b1) in that the difference between a pour point and a glass transition point is especially large, for example, 60 degreeC or more. Moreover, in order to enlarge the quantity of the rubber compounding oil which has said suitable kinematic viscosity, it is preferable to contain base oil (b1) and base oil (b2) as base oil (b). From this viewpoint, the content ratio of base oil (a) or base oil (a2), base oil (b1), and base oil (b2) becomes like this. Preferably it is 10-40 mass%, 5-35 mass%, and 85-25 mass %, More preferably, it is 20-30 mass%, 20-30 mass%, and 60-40 mass%.

In addition, the rubber compounding oil of this embodiment can mix | blend base materials other than base oil (a) and base oil (b), unless the effect of this invention is impaired.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to the said embodiment at all.

Example

The present invention will be described in detail using the following examples and reference examples. However, the present invention is not limited to the following examples.

(Example 1)

Atmospheric distillation of crude oil was distilled under reduced pressure using a conventional vacuum distillation apparatus, and fractions of fuel equivalents, fractions of 150 N equivalents or less, fractions of 350 N and fractions 900 N were fractionated. The fractionated 350N equivalent fraction was processed by the polar solvent extraction apparatus as shown in FIG. Specifically, 350N equivalent oil was introduced into the first extraction column 30 whose bottom temperature was lower than the top temperature, and the first solvent extraction step of contacting the polar solvent (furfural) and 350N equivalent oil was performed. By this first solvent extraction step, 350 N equivalent fraction is mixed with the mixture of the first raffinate and the polar solvent obtained from the top portion of the first extraction column 30, and the first extract and the polar solvent obtained from the bottom portion. An aliquot was taken. Thereafter, a polar solvent was recovered by a fractionation tower (not shown) to obtain a first raffinate and a first extract from the mixture.

Then, the 1st raffinate was introduce | transduced into the 2nd extraction tower 40 whose tower bottom temperature is lower than the top temperature, and the 2nd solvent extraction process which contacted with a polar solvent (furfural) was implemented. By this second solvent extraction step, the first raffinate was fractionated into a mixture of the second raffinate and the polar solvent obtained from the top portion and the mixture of the second extract and the polar solvent obtained from the bottom portion. Thereafter, a polar solvent was recovered by a fractionation tower (not shown) to obtain a second extract and a second raffinate from the mixture.

As for 2nd raffinate, the total aromatic content measured according to ASTMD 2549 was 30 mass% or more. In addition, the 2nd extract had a density in 15 degreeC of 0.94 g / cm <3> or more, and the total aromatic content measured according to ASTMD2549 was 30 mass% or more.

Table 1 shows the manufacturing conditions and the yield of the first solvent extraction step and the second solvent extraction step.

Regarding the above second raffinate, purification treatment by MEK dewaxing and hydrogenation finishing treatment was carried out so that the pour point was -10 ° C or lower to obtain an aromatic-containing base oil (lubricating oil base oil) having a total aromatic content of 30% by mass or more. This was set as base oil A1. In addition, the 2nd extract was made into the base oil (B1) and base oil (B3) component. Table 2 shows the properties of the base oil (A1), the base oil (B1), and the base oil (B3). In addition, the 2nd extract did not perform the purification process.

The total content of benzo (a) pyrene and eight specific aromatic compounds (PAH) was measured as follows. First, 1 g of each aromatic-containing base oil was dissolved in hexane in a 50 ml flask to prepare a 2 mass% sample solution. The sample solution was loaded on 5 mass% hydrous silica gel, washed with hexane, and then eluted with the 1 vol% acetone / hexane solution. After the eluate was concentrated, a sample to which the internal standard was added was prepared and identified and quantified by a general gas chromatograph mass spectrometer (GC-MS).

(Example 2)

Atmospheric distillation of crude oil was distilled under reduced pressure using a conventional vacuum distillation apparatus, and fractions of fuel equivalents, fractions of 150 N equivalents or less, fractions of 350 N and fractions 900 N were fractionated. As in Example 1, except that 900N equivalent oil was introduced into the first extraction tower 30 instead of 350N equivalent oil, and the manufacturing conditions of the first and second solvent extraction steps were changed as shown in Table 3. Thus, first and second raffinates and first and second extracts were prepared. In addition, manufacture was performed multiple times under the same conditions, and the manufacture of multiple lots was obtained. Table 3 shows the production conditions and yields of the first solvent extraction step and the second solvent extraction step.

As for the 2nd raffinate in Example 2, the total aromatic content measured according to ASTMD 2549 was 30 mass% or more. In addition, the 2nd extract had a density in 15 degreeC of 0.94 g / cm <3> or more, and the total aromatic content measured according to ASTMD2549 was 30 mass% or more.

Regarding two kinds of second raffinate having different production lots, purification treatment by MEK dewaxing and hydrogenation finishing treatment is carried out so that the pour point is -10 ° C or lower, and two kinds of aromatic-containing base oils having a total aromatic content of 30% by mass or more ( Lubricating oil base oil). This was used as base oil (A2) and base oil (A3). Moreover, the 2nd extract obtained at the 2nd solvent extraction process with the 2nd raffinate used for manufacture of base oil (A2) was made into base oil (B2). Moreover, the 2nd extract obtained by the 2nd solvent extraction process with the 2nd raffinate used for manufacture of base oil (A3) was made into base oil (B4). Table 4 shows the properties of base oil (A2), base oil (A3), base oil (B2), and base oil (B4).

From Tables 1 and 3, in Examples 1 and 2, the total yield of the second blended raffinate and the second extract useful as the rubber compounding oil or the substrate thereof is based on the raw material oil of the first extraction column, 74 to 75% by volume (yield of useful ingredient). Thus, it was confirmed that a rubber compounding oil or a lubricating oil base oil (aromatic containing base oil) useful as a substrate thereof can be produced in high yield.

In addition, from Table 2 and Table 4, base oil (A1), base oil (A2), base oil (A3), base oil (B1), base oil (B2), base oil (B3), and base oil (B4) of Example 1 and Example 2 ) Had a total aromatic content of 30% by mass or more and a flash point of 250 ° C or more. That is, in the present Example, by using several reduced pressure distillate fractions different in viscosity, it was possible to produce a plurality of aromatic-containing base oils having different viscosities with different properties.

In addition, base oil (A1), base oil (A2), base oil (A3), base oil (B1), base oil (B2), base oil (B3), and base oil (B4) are carcinogenic benzo (a) pyrene and eight types. The sum total content of the specific aromatic compound (PAH) of all was fully reduced.

In addition, the difference between the pour point and the glass transition point of the base oil (B1) and the base oil (B2) is 50 degreeC or more, In particular, the base oil (B1) had the characteristic characteristic that the said difference was 70 degreeC or more. That is, although both the base oil B1 and the base oil B2 have a high flow point, it was confirmed that a glass transition point is low.

In addition, the base oil (B1), the base oil (B2), the base oil (B3), and the base oil (B4) of Examples 1 and 2 have an aromatic hydrocarbon content (C _A ) of 20 to 35 mass%, and have a suitable glass transition temperature ( Since it has T _g ), when it mix | blends with a rubber composition, tensile strength and abrasion resistance can be improved.

(Example 3)

Said base oil (A1), base oil (A2), base oil (B1), and base oil (B2) were mix | blended in the compounding ratio shown in Table 5, and the rubber compounding oil of Examples 3-1 to 3-4 was prepared. The properties of each rubber compounding oil are summarized in Table 5 and described.

As shown in Table 5, all of the rubber compounding oils of Examples 3-1, 3-2, 3-3, and 3-4 had high total aromatic fraction and flash point, and carcinogenic harmful substances were sufficiently reduced. . In addition, the difference between a pour point and a glass transition point was 45 degreeC or more. In particular, the rubber blended oils of Examples 3-1 and 3-2 have a difference between the pour point and the glass transition point of 60 ° C. or more, and the total aromatic content of ASTM D 2549 or ASTM D 2007 is 50% by mass or more, and the pour point In spite of being higher than 15 ° C, the glass transition point had a characteristic of -45 ° C or lower.

In Examples 3-1 to 3-4 of rubber compounding oil, all from 20 to 35% C _A by ASTM D 3238, a glass transition temperature (T _g) is -55 to -30 ℃, kinematic viscosity (100 ℃ ) Is 20 to 50 mm 2 / s, and is a petroleum process oil that does not substantially contain a specific aromatic compound (PAH), so is used for the processing of the extender oil or diene rubber used in the production process of the diene rubber. When it mix | blends as process oil to make, it is clear that the low fuel consumption and grip property are compatible, and also the outstanding effect that the heat-aging resistance and abrasion resistance can be improved is also shown.

(Reference Example 1)

The atmospheric distillation residue of crude oil was distilled under reduced pressure using a conventional vacuum distillation apparatus, and fractions of fuel equivalents, fractions of 150 N equivalents or less, fractions of 250 N equivalents and fractions (500 equivalents) were fractionated. The fractionated 500N equivalent oil is introduced into the extraction column having the bottom temperature lower than the top temperature, the raffinate yield is increased, the aromatic content of the lubricating oil base oil obtained is 30% by mass or more, and the content of the specific aromatic compound (PAH) is 10% by mass. The solvent extraction process of contacting with a polar solvent (furfural) was implemented on condition to become less than. By this solvent extraction process, 500 N equivalent fractions were fractionated by the 1st raffinate and the 1st extract. Table 6 shows the production conditions and the yield of the solvent extraction step.

The first raffinate thus obtained was subjected to a purification treatment by MEK dewaxing and hydrogenation finishing so that the pour point was -10 ° C or lower. Thereby, two types of aromatic containing base oils (lubricating oil base oil) whose total aromatic content differs by 30 or more by mass are manufactured. This was made into base oil E1 and base oil E2. In addition, the extract was used as base oil (F). The properties of the base oil (E1), the base oil (E2) and the base oil (F) are shown in Table 7.

As shown in Table 6, in this reference example, the yield of the first raffinate based on the raw materials introduced into the extraction column was 60% by volume and the yield of the first extract was 40% by volume. In addition, as shown in Table 7, the total content of the specific aromatic compound (PAH) which is carcinogenic of aromatic containing base oil (F) exceeded 10 mass ppm. It is not suitable to use this aromatic containing base oil (F) as a rubber compounding oil in that state, and even if it mix | blends with other lubricating oil base oil, the compounding ratio cannot usually be 50 mass% or more. .

(Reference Example 2)

The deasphalted oil of the vacuum distillation residue oil of the atmospheric pressure distillation residue oil of crude oil was fractionated by the raffinate and the extract by the same solvent extraction process as in Reference Example 1. This extract has a kinematic viscosity at 100 ° C of 95 mm2 / s, 69% by mass of the total aromatic content according to ASTM D 2549, a pour point of 12.5 ° C, a glass transition point of -29.7 ° C, and a difference between the pour point and the glass transition point (flow point- Glass transition point) was 42.2 ° C.

This extract and the base oil (E1) of the said Reference Example 1 were mix | blended in the mass ratio of 80:20, and the rubber compounding oil was prepared. The pour point of this rubber compounding oil was 0 degreeC, the glass transition point was -44.5 degreeC, and the difference of a pour point and the glass transition point was 44.5 degreeC.

(Reference Example 3)

A solvent extraction step was carried out in the same manner as in Reference Example 1 except that 250 N equivalent oil was introduced into the extraction column instead of 500 N equivalent oil to obtain raffinate and extract. Then, the raffinate was subjected to purification treatment by MEK dewaxing and hydrogenation finishing so that the pour point was -10 ° C or lower to obtain an aromatic-containing base oil. This was set as base oil (G). The base oil (g) had a flash point of less than 250 ° C. That is, in this reference example, only one aromatic-containing base oil having a flash point of 250 ° C. or more (500 N base oil) could be obtained from the reduced pressure distillate fraction (250 N equivalent fraction).

According to the present invention, it is possible to provide a rubber compounding oil having a high flash point and a low glass transition point while sufficiently reducing the content of a specific polycyclic aromatic compound while keeping the total aromatic content high, and a method for producing such a rubber compounding oil. Moreover, according to this invention, content of a carcinogenic substance is high from a raffinate and an extract obtained by the polar solvent extraction method which uses a vacuum distillate fraction as a raw material, having a high flash point, a low glass transition point, and high total aromatic content. This sufficiently reduced aromatic containing base oil can be provided. Moreover, the manufacturing method of the aromatic containing base oil which can manufacture such an aromatic containing base oil in high yield can be provided.

30 ... First extraction column, 40... Second extraction column, 50... Dewaxing device, 60... Hydrogenation finisher.

Claims (10)

50 mass% or more of total aromatic content by ASTM D 2007 or ASTM D 2549, a flash point of 250 degreeC or more, and the difference of a pour point and a glass transition point of 45 degreeC or more,
1 mass ppm or less of content of benzo (a) pyrene, and
The rubber compounding oil whose sum of content of the specific aromatic compound of following 1) -8) is 10 mass ppm or less.
1) Benzo (a) pyrene (BaP)
2) benzo (e) pyrene (BeP)
3) benzo (a) anthracene (BaA)
4) Chrysene (CHR)
5) benzo (b) fluoranthene (BbFA)
6) benzo (j) fluoranthene (BjFA)
7) benzo (k) fluoranthene (BkFA)
8) dibenzo (a, h) anthracene (DBAhA) The raffinate or refined oil thereof obtained by separating the vacuum distillation fraction of the atmospheric distillation residue of crude oil in a solvent extraction step, and having a kinematic viscosity at 40 ° C. of 60 to 600 mm 2 / s and an aniline point. Aromatic-containing base oil (a) having 70 ° C. or more, 10% point by GC distillation, 400-500 ° C., 90% point 500-600 ° C.,% C _A by ASTM D 3238, 3-20, glass transition point -30 ° C. , And
The distillate under reduced pressure of the atmospheric distillation residue oil contains an extract obtained by separating in a solvent extraction step or refined oil thereof, and has a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, an aniline point of 90 ° C. or less and 15 ° C. At least 0.94 g / cm <3> and an aromatic containing base oil (b) whose total aromatic content by ASTM D 2549 is 30 mass% or more contains at least the said aromatic containing base oil (b),
Rubber compounding oil whose content of the said aromatic containing base oil (a) is 95 mass% or less, and content of the said aromatic containing base oil (b) is 5 mass% or more. The method of claim 2, wherein the solvent extraction step,
In a first extraction tower having a column bottom temperature of 30 to 90 ° C. and a column top temperature higher than the column bottom temperature, a first solvent extraction is performed by contacting the vacuum distillation fraction with a polar solvent to obtain a first raffinate and a first extract. Fair,
A second solvent in which a bottom bottom temperature and a top temperature are respectively 10 ° C. or more higher than the first extraction tower by contacting the first raffinate and the polar solvent to obtain a second raffinate and a second extract. Has an extraction process,
The aromatic-containing base oil (b) is a rubber compound oil, the second extract or refined oil thereof. The vacuum distillation fraction of the crude oil atmospheric distillation residue oil contains raffinate or refined oil obtained by separating in the solvent extraction step, and the kinematic viscosity at 40 ° C is 60 to 600 mm 2 / s, the aniline point is 70 ° C or higher, and GC distillation. Aromatic containing base oil (a) having a 10% point of 400 to 500 ° C, a 90% point of 500 to 600 ° C, a% C _A of ASTM D 3238 of 3 to 20, a glass transition point of -30 ° C or less, and
The distillate under reduced pressure of the atmospheric distillation residue oil contains an extract obtained by separating in a solvent extraction step or refined oil thereof, and has a kinematic viscosity at 40 ° C. of 200 mm 2 / s or more, an aniline point of 90 ° C. or less and 15 ° C. It has a compounding process of mix | blending the aromatic containing base oil (b) whose density is 0.94 g / cm <3> or more and 30 aromatic% or more of total aromatics by ASTMD 2549,
50 mass% or more of total aromatic content by ASTM D 2007 or ASTM D 2549, 250 degreeC or more of flash points, 45 degreeC or more of difference between a pour point and a glass transition point, 1 mass ppm or less of benzo (a) pyrene, and the following The sum total of content of the specific aromatic compound of 1) -8) is 10 mass ppm or less, and content of aromatic-containing base oil (a) is more than 0 mass%, 95 mass% or less, and content of aromatic-containing base oil (b) is 5 The manufacturing method of the rubber compounding oil which is more than 100 mass% in mass%.
1) Benzo (a) pyrene (BaP)
2) benzo (e) pyrene (BeP)
3) benzo (a) anthracene (BaA)
4) Chrysene (CHR)
5) benzo (b) fluoranthene (BbFA)
6) benzo (j) fluoranthene (BjFA)
7) benzo (k) fluoranthene (BkFA)
8) dibenzo (a, h) anthracene (DBAhA) In a first extraction tower having a column bottom temperature of 30 to 90 ° C. and a column top temperature higher than the column bottom temperature, a reduced pressure distillation fraction of a crude oil atmospheric distillation residue is contacted with a polar solvent to obtain a first raffinate and a first extract. The first solvent extraction step
In the second extraction tower where the bottom temperature and the top temperature are respectively 10 ° C. or more higher than the first extraction tower, the first raffinate and the polar solvent are brought into contact with each other, so that the density of the second raffinate and 15 ° C. is 0.94 g / It has a 2nd solvent extraction process of obtaining the 2nd extract which is cm <3> or more and total aromatic content is 30 mass% or more,
The manufacturing method of the aromatic containing base oil containing at least one part of the said 2nd extract, the said 2nd raffinate, or refined oil thereof, and whose total aromatic content is 30 mass% or more. The base oil preparation process of Claim 5 which has the base oil preparation process of obtaining the refined oil by adding the refinement | purification process containing a dewaxing process to the said 2nd raffinate after the said 2nd solvent extraction process,
A method for producing an aromatic-containing base oil, wherein the refined oil is contained, the pour point is -5 ° C or less, the aniline point is 90 ° C or more, the viscosity index is 90 or more, and the flash point is 250 ° C or more. The method of claim 5, containing at least a portion of the second extract,
The kinematic viscosity at 40 ° C is 200 mm 2 / s or more, the flash point is 250 ° C or more, the pour point is 30 ° C or less, the aniline point is 90 ° C or less, the glass transition point is -30 ° C or less, and the difference between the pour point and the glass transition point is The manufacturing method of aromatic containing base oil which is 50 degreeC or more. The method for producing an aromatic-containing base oil according to claim 5, wherein the content of benzo (a) pyrene is 1 mass ppm or less, and the total content of specific aromatic compounds of the following 1) to 8) is 10 mass ppm or less.
1) Benzo (a) pyrene (BaP)
2) benzo (e) pyrene (BeP)
3) benzo (a) anthracene (BaA)
4) Chrysene (CHR)
5) benzo (b) fluoranthene (BbFA)
6) benzo (j) fluoranthene (BjFA)
7) benzo (k) fluoranthene (BkFA)
8) dibenzo (a, h) anthracene (DBAhA) The aromatic containing base oil obtained by the manufacturing method in any one of Claims 5-8. The rubber compounding oil containing the aromatic containing base oil of Claim 9.

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