TWI471415B - Rubber blending oil and its manufacturing method - Google Patents

Description

Rubber blending oil and manufacturing method thereof

The present invention relates to a rubber blending oil and a method of producing the same.

The high aromatic mineral oil has high affinity with the rubber component, and the rubber composition is excellent in workability, softening property, and economical efficiency, and therefore is used for the production of a rubber composition such as natural rubber or synthetic rubber. For example, in a synthetic rubber such as SBR (Styrene-Butadiene Rubber, styrene-butadiene rubber), an extender oil is blended during the synthesis, and in a rubber processed product such as a tire, the workability is improved. A process oil is blended with the quality of the rubber-processed product (for example, Patent Document 1).

Patent Document 1 proposes the use of petroleum-based processing oil having an aromatic hydrocarbon content (C _A ) of 20 to 35 wt%, a glass transition temperature T _g of -55 ° C to -30 ° C, and a dynamic viscosity (100 ° C) of 20 to 50 mm ² /s, and the amount of polycyclic aromatic components (PCA, Principal Component Analysis) is 3% by weight or less of petroleum-based processing oil. When the rubber obtained by blending the petroleum-based processing oil with a diene rubber is used for a tire, it can have both low fuel economy and grip, and can improve heat aging resistance and heat resistance.

As the rubber blending oil, a highly aromatic base oil such as a vacuum distillation residue, a deasphalted oil, a deasphalted oil, or a solvent extract of a lubricating fraction is known (for example, Patent Document 2). However, it is highly viscous and flows if it is made of a high-base oil, because it is a target of the fourth petroleum class, which is a dangerous substance in the Japanese fire protection law, for the sake of safety. The point becomes higher, and the workability during storage, transportation, and handling decreases. Here, in order to lower the pour point, it is also proposed to dewax the high aromatic base oil, but the manufacturing process becomes complicated and the economic efficiency is remarkably deteriorated. Therefore, there is a need for a rubber blending oil that does not require cumbersome manufacturing steps and that is highly viscous and has a high flash point and has a low flow point.

On the other hand, in Europe, since 2010, it has not been possible to use a certain amount of DMSO (Dimethyl Sulfoxide) or a specific carcinogenic polycyclic aromatic compound for tires or tire parts. The manufacturing regulations require a rubber blending oil that meets these requirements.

Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-155959

[Patent Document 2] Japanese Patent No. 3658155

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a high flash point and high aromaticity, to sufficiently reduce the content of a specific carcinogenic polycyclic aromatic compound, and to have a low pour point and excellent economic efficiency. Rubber blending oil and its manufacturing method.

The present inventors have conducted intensive studies on the substrate of the rubber blending oil, and as a result, it has been found that by using a specific extract and a specific lubricating base oil, high viscosity, high flash point, high aromaticity, At the same time, the rubber blended oil having a low pour point of a specific carcinogenic polycyclic aromatic compound (hereinafter referred to as "specific aromatic compound") and excellent in economical efficiency is sufficiently reduced, and the present invention has been completed.

That is, the present invention provides a rubber blending oil which contains the extract (A) and the lubricating base oil (B); the extract (A) has an aniline point of 40 to 90 ° C, and the % obtained according to ASTM D3238 C _A is 25 to 45 and % C _N is 5 to 20, the nitrogen content is 0.01% by mass or more, the pour point is +30 ° C or lower, and the content of benzo (a) pyrene is 1 ppm by mass or less. The total content is 10 mass ppm or less, and the dynamic viscosity at 40 ° C is 650 mm ² /s or more; the lubricating base oil (B) has a pour point of -10 ° C or less, and the aniline point is 70 ° C or more, according to ASTM D3238. The obtained % C _A is 3 to 20 and the % C _N is 15 to 35, the nitrogen content is 0.01% by mass or less, the 90% point in the GC distillation is 500 ° C or more, the flash point is 250 ° C or more, and the benzo (a) The content of the cerium is 1 ppm by mass or less, and the total content of the specific aromatic compound is 10 ppm by mass or less.

According to the present invention, by containing the specific extract (A) and the lubricating base oil (B), it is possible to produce a high flash point and a high aromaticity, sufficiently reduce the content of the specific aromatic compound, and the pour point. Lower rubber blending oil. Moreover, since it is possible to manufacture without not being complicated in the manufacturing steps, it is possible to produce an economical one.

The rubber blending oil of the present invention preferably has a flash point of 250 ° C or more, an aniline point of 90 ° C or less, a dynamic viscosity of 40 mm ² /s or more at 40 ° C, and a pour point of +30 ° C or less. (a) The content of barium (BaP) is 1 mass ppm or less, and the total content of the specific aromatic compound is 10 mass ppm or less. Further, the rubber blending oil of the present invention is excellent in low fuel economy, grip property and heat aging resistance in the case of producing a diene rubber composition as mentioned in Patent Document 1, and particularly preferably % C _A is 20~35, glass transition temperature T _g is -55 ° C ~ -30 ° C, dynamic viscosity (100 ° C) is 20 ~ 50 mm ² / s, and benzo (a) bismuth (BaP) content is 1 mass ppm or less The total content of the specific aromatic compound is 10 ppm by mass or less. Further, the pour point is preferably +20 ° C or lower, particularly preferably + 15 ° C or lower.

The rubber blending oil of the present invention is preferably: the extract (A) is a deasphalted oil obtained by deasphalting a vacuum distillation residue of atmospheric crude distillation residue of crude oil in a one-stage or two-stage process with a polar solvent. The extract obtained by contacting with the extraction is carried out.

The rubber blending oil of the present invention is preferably: the extract (A) contains an extract obtained by a two-stage polar solvent extraction step; the extract is obtained by using a bottom temperature of 30 to 90 ° C, and the top of the column The first extraction tower having a temperature higher than the temperature of the bottom of the column makes the raffinate obtained by contacting the vacuum distillation residue of the atmospheric crude distillation residue with the polar solvent and the polar solvent at the bottom temperature and the top temperature respectively. The second extraction column having an extraction column height of 10 ° C or higher is obtained by contacting; the density of the extract at 15 ° C is 0.94 g / cm ³ or more, and the total aromatic content obtained according to ASTM D2549 is 30% by mass or more.

The rubber blending oil of the present invention is preferably: the lubricating base oil (B) contains the dewaxed oil (c) of the first raffinate obtained by the one-stage polar solvent extraction step and/or by 2 Dewaxed oil (d) of the second raffinate obtained in the polar solvent extraction step of the stage; the dewaxed oil (c) is the first at the bottom of the column at a temperature of 30 to 90 ° C and the temperature at the top of the column is higher than the temperature at the bottom of the column The first raffinate obtained by contacting the vacuum distillation fraction of the atmospheric crude distillation residue of the crude oil with the polar solvent in the extraction column is subjected to a purification treatment including a dewaxing step; the dewaxed oil (d) is a pair Purifying the second raffinate obtained by contacting the first raffinate with the polar solvent in the second extraction column having a bottom temperature and a column top temperature higher than the first extraction column by 10 ° C or higher, respectively, including a dewaxing step The winner of the process.

Moreover, the present invention provides a method for producing a rubber blending oil comprising the steps of blending the extract (A) with a lubricating base oil (B); and the extract (A) having an aniline point of 40 to 90 ° C, The % C _A obtained according to ASTM D3238 is 25 to 45 and the % C _N is 5 to 25, the nitrogen content is 0.01% by mass or more, the pour point is +30° C. or less, and the content of benzo (a) antimony is 1 ppm by mass or less. The total content of the specific aromatic compound is 10 ppm by mass or less, and the dynamic viscosity at 40 ° C is 650 mm ² /s or more; the lubricating base oil (B) has a pour point of -10 ° C or less, and the aniline point is Above 70 ° C, the % C _A obtained according to ASTM D3238 is 3 to 20 and the % C _N is 15 to 35, the nitrogen content is 0.01% by mass or less, the 90% point in the GC distillation is 500 ° C or more, and the flash point is 250 ° C. In the above, the content of the benzo(a)pyrene is 1 ppm by mass or less, and the total content of the specific aromatic compound is 10 ppm by mass or less.

According to the above-described production method of the present invention, by blending the specific extract (A) with the lubricating base oil (B), it is possible to produce a high flash point and a high aromaticity, and to sufficiently reduce the content of a specific aromatic compound, Rubber blended oil with lower pour point. Moreover, the manufacturing method of the present invention can be manufactured without cumbersome manufacturing steps, and therefore is excellent in economy.

According to the present invention, it is possible to provide a rubber blending oil which has a high flash point and high aromaticity, sufficiently lowers the content of a specific aromatic compound, has a low pour point, and is excellent in economy, and a method for producing the same.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In addition, the same or equivalent numbers are denoted by the same reference numerals, and overlapping descriptions are omitted as appropriate.

The rubber blending oil of the present embodiment contains an extract (A) having a specific property (hereinafter, simply referred to as "(A) component") and a lubricating base oil (B) having a specific property (hereinafter, simply referred to as "( B) Ingredients") rubber blended oil.

The component (A) has an aniline point of 40 to 90 ° C, a % C _A of 25 to 45 according to ASTM D3238, a % C _N of 5 to 20, a nitrogen content of 0.01% by mass or more, and a pour point of +30 ° C or less. The benzo (a) fluorene is an extract having a mass ratio of 1 ppm by mass or less, a total of a specific aromatic compound of 10 ppm by mass or less, and a dynamic viscosity at 40 ° C of 650 mm ² /s or more.

As the extract of the component (A), as long as the above regulation is satisfied, the extract obtained in the polar solvent extraction step may be used as it is, or the extract may be subjected to purification treatment. Here, examples of the purification treatment include dewaxing, hydrogenation decomposition, hydrogenation purification, and distillation. Further, as the component (A), from the viewpoint of the production cost and the use of the rubber blending oil to form a suitable property, it is preferred to directly use the extract obtained in the polar solvent extraction step without performing the purification treatment. The reason for this is that a rubber blending oil excellent in low-temperature performance can be obtained without performing a dewaxing treatment; in the case of hydrogenation decomposition, the aromaticity tends to decrease; and when the purification treatment is carried out, the production method becomes complicated.

The aniline point of the component (A) is 40 to 90 ° C, preferably 45 to 70 ° C, more preferably 50 to 65 ° C. When the aniline point is in the above range, even if the lubricating base oil having a high aniline point is contained as the component (B), the compatibility with the rubber is excellent, and the properties of the rubber composition are maintained, so that it is easy to produce a suitable aniline point. Rubber blended oil. Further, the aniline point in the present specification means an aniline point measured in accordance with JIS K 2256-1985.

As the composition of the component (A), % C _A is 25 to 45, preferably 30 to 40, and % C _N is 5 to 20, preferably 6 to 12. Further, % C _{P is} determined according to % C _A and % C _N , preferably 35 to 70, more preferably 48 to 64. When the composition of the component (A) is in the above range, even if the lubricating base oil having a high paraffin content is contained as the component (B), the compatibility with the rubber is excellent, and the properties of the rubber composition are maintained, so that it is easy to manufacture. A suitable blend of rubbers. Further, the terms "% C _P , % C _N and % C _A " as used herein mean the percentage of the carbon number of the paraffin wax relative to the total carbon number obtained by the method according to ASTM D 3238-85 (ndM ring analysis). , the percentage of the carbon number of the naphthenic ring relative to the total carbon number, and the percentage of the aromatic carbon number to the total carbon number.

The nitrogen content of the component (A) is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. From the viewpoint that the nitrogen content of the by-products of the polar solvent extraction becomes low and the purification efficiency of the lubricating base oil becomes high, it is preferred that the nitrogen content of the component (A) is high, and it is economical. In view of the above, it is preferred to use the component (A) having a high nitrogen content as the rubber blending oil. Further, the nitrogen content in the present invention means the nitrogen content obtained by the chemiluminescence method measured in accordance with JIS K2609.

The flow point of the component (A) is +30 ° C or less, preferably +5 to +25 ° C. From the viewpoint of further reducing the flow point of the rubber blending oil, it is more preferably +5 to +20 ° C. Especially good is +7.5~+15°C.

Since the rubber blending oil of the present embodiment contains the component (B) described later, it has a sufficiently low flow point even when the unpurified (A) component having a high pour point is contained. In addition, the flow point in this specification shows the flow point measured by JIS K2269.

The component (A) sufficiently reduces the content of the eight kinds of aromatic compounds (collectively referred to as "specific aromatic compounds") listed below.

1) Benzo(a)pyrene (BaP)

2) Benzo(e)pyrene (BeP)

3) Benzo(a)pyrene (BaA)

4) (CHR)

5) Benzo(b)fluoranthene (BbFA)

6) Benzo(j)fluoranthene (BjFA)

7) Benzo(k)fluoranthene (BkFA)

8) Dibenzo(a,h)pyrene (DBAhA)

Here, the benzo(a)pyrene in the present specification means benzo(a)pyrene (BaP) of the above 1), and the specific aromatic compound means the aromatic compound of the above 1) to 8) ( PAH).

The content of benzo(a)pyrene (BaP) in 1) of the component (A) is 1 ppm by mass or less, and the total content of the specific aromatic compounds in 1) to 8) is 10 ppm by mass or less. Thereby, a rubber blending oil having higher carcinogenicity and higher safety can be obtained. Further, the specific aromatic compound can be separated and concentrated, and a sample to which an internal standard substance is added can be prepared and analyzed by GC-MS (Gas Chromatograph-Mass Spectrometry). Perform quantitative analysis.

The dynamic viscosity of the component (A) at 40 ° C is 650 mm ² /s or more, preferably 800 mm ² /s or more, more preferably 2000 mm ² /s or more, and further preferably 5000 mm ² / Above s, it is preferably 20,000 mm ² /s or less, more preferably 10,000 mm ² /s or less.

When the dynamic viscosity at 40 ° C of the component (A) is less than 650 mm ² /s, even if the component (B) is contained, there is a tendency that a sufficiently low flow point cannot be obtained. By making the dynamic viscosity of the component (A) at 40 ° C 700 mm ² /s or more, preferably 800 mm ² /s or more, the flow point of the rubber blending oil is easily 15 ° C or less. In this case, the flow point of the component (A) is preferably +5 to +20 ° C, more preferably +7.5 to + 15 ° C.

In the present embodiment, the (A) component and the (B) component having a dynamic viscosity at 40 ° C of 650 mm ² /s or more, preferably a flow point of +5 to +20 ° C, can be made low. Rubber blending oil at the pour point. Furthermore, when the dynamic viscosity of the component (A) exceeds 20,000 mm ² /s, the dynamic viscosity suitable for the rubber blending oil cannot be obtained (the dynamic viscosity at 100 ° C is 10 to 70 mm ² /s). Preferably, the tendency of the rubber blending oil is 15 to 50 mm ² /s, particularly preferably 20 to 32 mm ² /s. Further, the dynamic viscosity at each temperature referred to in the present specification means the dynamic viscosity at each temperature measured in accordance with JIS K2283.

The content of the pitch of the component (A) is preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less. Further, the so-called asphalt content in the present specification means the asphalt content measured in accordance with IP-143.

For the sake of safety, or the point that the flash point of the rubber blending oil is above 250 ° C, making it a dangerous substance in the Japanese fire protection law, the object of the fourth petroleum category, (A) The flash point is preferably 250 ° C or higher, more preferably 270 ° C or higher, further preferably 290 ° C or higher, and particularly preferably 300 ° C or higher. Further, the flash point referred to in the present specification means a flash point obtained by a Cleveland Open Cup Tester (COC) measured in accordance with JIS K2265.

The total aromatic content of the component (A) is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and particularly preferably 65% by mass or more. On the other hand, the total aromatic content of the component (A) is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less. When the total aromatic content of the component (B) is less than 50% by mass, there is a tendency that it is difficult to obtain a rubber blending oil having a high aromaticity, and if the total aromatic content exceeds 90% by mass, there is a polar solvent extraction step. The yield is lowered and the manufacturing cost is increased. Incidentally, the total aromatic content referred to in the present specification means the content of the aromatics fraction measured in accordance with ASTM D 2549.

The component (B) contained in the rubber blending oil of the present embodiment has a pour point of -10 ° C or less, an aniline point of 70 ° C or more, and a % C _A of NDM analysis of 3 to 20 and a % C _N of 15 ~35, the nitrogen content is 0.01% by mass or less, the 90% point in the GC distillation is 500 ° C or higher, the flash point is 250 ° C or higher, the benzo (a) hydrazine is 1 ppm by mass or less, and the total of the specific aromatic compounds is 10 Lubricating base oil of less than ppm by mass.

The flow point of the component (B) is -10 ° C or less, or may be less than -20 ° C. Among them, from the viewpoint of maintaining the pour point of the rubber blending oil low and reducing the manufacturing cost, it is preferably -10 to -20 °C. A rubber blending oil having a lower pour point can be obtained by using the component (B) having a pour point of -10 ° C or less.

The aniline point of the component (B) is 70 ° C or higher, preferably 90 ° C or higher, more preferably 100 ° C or higher. On the other hand, in the case of being excellent in compatibility with rubber and maintaining the properties of the rubber composition, it is preferred to produce a rubber blended oil having a suitable aniline point at 120 ° C or lower.

As the composition of the component (B), % C _A is 3 to 20, preferably 5 to 10, and % C _N is 15 to 35, preferably 20 to 30. Further, % C _{P is} determined according to % C _A and % C _N , preferably 45 to 82, more preferably 60 to 75, and still more preferably 65 to 70. By using the component (B) having the above composition, the compatibility with the rubber is excellent, and the properties of the rubber composition are maintained, so that it is easy to produce a rubber blending oil having a suitable composition.

The nitrogen content of the component (B) is 0.01% by mass or less, preferably 0.008% by mass or less. Further, the nitrogen content of the component (B) may be less than 0.001% by mass, but from the viewpoint of lowering the manufacturing cost of the rubber blending oil by using a lubricating base oil having a lower degree of purification, it is preferred that 0.002% by mass or more, more preferably 0.003% by mass or more.

The flash point of the component (B) is 250 ° C or higher, preferably 255 ° C, from the viewpoint that the flash point of the rubber blended oil reaches 250 ° C or higher and becomes a dangerous object. the above. Further, since the flash point of the component (A) is also high, it is necessary to increase the flash point of the component (B) to a temperature higher than necessary, preferably 290 ° C or lower, more preferably 280 ° C or lower.

The 90% point in the GC distillation of the component (B) is 500 ° C or higher, preferably 500 to 600 ° C. In the present embodiment, it is preferred that the 90% point in the GC distillation using the component (B) is 510 to 550 °C. On the other hand, as another embodiment, it is preferred that the 90% point in the GC distillation using the component (B) is 550 to 590 °C. The 10% point in the GC distillation of the component (B) is not particularly limited. For safety reasons, or the flash point of the rubber blending oil is 250 ° C or more, it becomes a dangerous substance in the Japanese fire protection law. In terms of the objects of the four petroleum objects, it is preferably 400 to 510 ° C, more preferably 440 to 500 ° C. As an aspect, 440 to 470 ° C can be used, and as another aspect, 450 to 500 ° C can be used.

The content of the benzo(a)pyrene (BaP) of the above 1) in the component (B) is 1 ppm by mass or less, and the total content of the specific aromatic compound is 10 ppm by mass or less. Thereby, a rubber blending oil having lower carcinogenicity and higher safety can be produced.

The dynamic viscosity at 40 ° C of the component (B) is preferably from 50 to 500 mm ² /s, more preferably from 60 to 300 mm ² /s, and still more preferably from 70 to 200 mm ² /s. In the present embodiment, in the case of using the component (A) having a dynamic viscosity of not more than 2000 mm ² /s at 40 ° C, in order to obtain a suitable dynamic viscosity rubber blending oil, it is preferred to use at 40 ° C. The dynamic viscosity is 50-150 mm ² /s (B), and it is better to use the dynamic viscosity at 40 ° C of 80-120 mm ² /s (B). Further, as another embodiment, in the case where the (A) component having a dynamic viscosity of less than 2000 mm ² /s at 40 ° C is used, in order to obtain a suitable dynamic viscosity rubber blending oil, it is preferred to use 40 ° C. The dynamic viscosity is 50-500 mm ² /s (B), and the dynamic viscosity at 40 ° C is 60-80 mm ² /s and / or 120-250 mm ² /s (B). )ingredient.

The total aromatic content of the component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass or more. On the other hand, the total aromatic content of the component (B) is preferably 50% by mass or less, more preferably 45% by mass or less. When the total aromatic content of the component (B) is less than 20% by mass, it is difficult to obtain a rubber blending oil having a high aromaticity. On the other hand, when the total aromatic content is more than 50% by mass, the oxidation stability when the component (B) is used as the lubricating base oil is remarkably deteriorated, and it is difficult to achieve the balance between the use of the lubricating base oil and the rubber blending oil. There is a tendency for the overall economics of the petroleum purification process to decline.

The rubber blending oil of the present embodiment can be obtained by blending the above components (A) and (B). Further, the rubber blending oil of the present embodiment may be blended with a substrate other than the component (A) and a substrate other than the component (B), within a range that does not significantly impair the effects of the present invention.

In order to have affinity with rubber, softness, high flash point, safety, handleability, and low fuel economy, grip and heat aging resistance in the production of a rubber composition, rubber blending of the present embodiment The oil preferably has the following properties.

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, and preferably 0.98 g/ Below cm ³ , more preferably 0.96 g/cm ³ or less.

‧ Flash point: usually 250 to 350 ° C, preferably 260 ° C or higher, more preferably 280 ° C or higher, more preferably 320 ° C or lower, and further preferably 310 ° C or lower.

Dynamic viscosity at ‧40 ° C: usually 200~3000 mm ² /s, preferably 300 mm ² /s or more, more preferably 400 mm ² /s, and more preferably 500 mm ² /s or more Preferably, it is 2000 mm ² /s or less, more preferably 1000 mm ² /s or less, and further preferably 800 mm ² /s or less.

Dynamic viscosity at ‧100 °C: usually 10~100 mm ² /s, preferably 15 mm ² /s or more, more preferably 20 mm ² /s or more, preferably 60 mm ² /s or less More preferably, it is 50 mm ² /s, and more preferably 32 mm ² /s or less.

‧ Aniline point: usually 50 to 100 ° C, preferably 60 ° C or higher, more preferably 65 ° C or higher, further preferably 70 ° C or higher, preferably 90 ° C or lower, more preferably 85 ° C the following.

‧ Nitrogen content: usually 0.01 to 0.2% by mass, preferably 0.03% by mass or more, further preferably 0.05% by mass or more, more preferably 0.15% by mass or less, still more preferably 0.1% by mass or less.

‧% C _N : usually 5 to 30, preferably 10 or more, more preferably 14 or more, more preferably 25 or less, still more preferably 20 or less.

‧% C _A : usually 10 to 40, preferably 17 or more, more preferably 20 or more, more preferably 35 or less, still more preferably 30 or less, and still more preferably 25 or less.

‧% C _P : 30 to 85, preferably 40 or more, more preferably 50 or more, preferably 73 or less, more preferably 66 or less.

‧ Total aromatic content (ASTM D2549): usually 30 to 90% by mass, preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass Below mass%.

‧ Saturated content according to ASTM D2007 (clay gel adsorption chromatography): usually 5 to 50% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, and most preferably 40% by mass Hereinafter, it is more preferably 30% by mass or less.

‧ Aromatic content obtained according to ASTM D2007 (clay gel adsorption chromatography): usually 40 to 90% by mass, preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 57% by mass The mass% or more is particularly preferably 60% by mass or more, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

‧ The content of the polar compound obtained according to ASTM D2007 (clay gel adsorption chromatography): usually 1 to 20% by mass, preferably 2% by mass or more, more preferably 5% by mass or more, and most preferably 15% by mass % or less is more preferably 12% by mass or less, further preferably 10% by mass or less.

‧ The ratio of the saturated content/polar compound content obtained according to ASTM D2007 (clay gel adsorption chromatography): usually 0.25 to 50, preferably 1 or more, more preferably 2.5 or more, and still more preferably 3 or more It is preferably 20 or less, more preferably 10 or less, further preferably 5 or less.

‧ The content of benzo(a)pyrene (BaP): 1 mass ppm or less.

‧ The total content of the specific aromatic compound is 10 ppm by mass or less.

‧ Flow point: -10 ° C ~ +30, preferably -5 ° C or more, preferably + 15 ° C or less, more preferably + 5 ° C or less, and further preferably 0 ° C or less.

‧ glass transfer point (T _g ): -60 ~ -10 ° C, preferably -55 ° C or more, preferably -30 ° C or less, more preferably -40 ° C or less, and more preferably -45 Below °C, especially preferably below -48 °C.

The "glass transition point (T _g )" of the aromatic-containing base oil in the present specification means a glass measured by a DSC (differential scanning calorimeter) at a constant temperature increase rate (10 ° C / min). The glass transition point obtained by the peak change in heat in the transfer zone. The initial temperature is usually set to a temperature lower than the expected glass transition point by about 30 ° C to 50 ° C or lower, and the temperature is raised after the initial temperature is maintained for a fixed period of time. In the present embodiment, specifically, it can be measured by the following conditions.

Device: Thermal Analysis System DSC Q100 manufactured by TA Instruments

Initial temperature: -90 ° C, hold for 10 minutes

Heating rate: 10 ° C / min

End temperature: 50 ° C, keep for 10 minutes

Further, the method of calculating the glass transition point based on the peak value of the heat change can be determined by the method described in JIS K 7121.

The rubber blending oil of the present embodiment can be obtained by blending the components (A) and (B). The content ratio of the component (A) to the component (B) is not particularly limited. For example, the content of the component (A) is 5 to 95% by mass, preferably 40 to 90% by mass based on the total amount of the rubber blending oil. %. Among them, since the actual flow point is lower than the flow point expected from the flow point of the component (A) and the component (B) as the substrate, it is preferably 55 to 85% by mass. Further, from the viewpoint of producing a rubber blending oil having a suitable viscosity and a lower flow point, it is preferably from 40 to 75% by mass, more preferably from 55 to 75% by mass.

Similarly, the blending ratio of the component (B) is from 5 to 95% by mass, preferably from 10 to 60% by mass based on the total amount of the rubber blending oil. Based on the total amount of the rubber blended oil, the content ratio is 5 to 95% by mass, preferably 40 to 90% by mass. Among them, since the actual flow point of the rubber blended oil is lower than the flow point expected from the flow point of the component (A) and the component (B) as the substrate, it is preferred that the content ratio of the component (B) is 15~45% by mass. Further, from the viewpoint of producing a rubber blending oil having a suitable viscosity and a lower flow point, it is preferably from 25 to 60% by mass, more preferably from 25 to 45% by mass.

The rubber blending oil of the present embodiment can be obtained by blending the components (A) and (B) in the above ratio. Next, a method for producing the component (A) and the component (B) which are substrates of the rubber blending oil will be described.

[Method for producing (A) component]

The method for producing the component (A) is not particularly limited as long as it satisfies the properties of the component (A). For example, a vacuum distillation residue of atmospheric crude distillation residue of crude oil in one or two stages or more may be mentioned. Deasphalting, a method in which the obtained deasphalted oil is contacted with a polar solvent for extraction.

Hereinafter, two manufacturing methods of the component (A) (conveniently referred to as "first aspect" and "second aspect") will be described in detail with reference to the drawings.

(1st aspect)

Fig. 1 is a schematic view showing the steps of an example of a method for producing the component (A). In the first aspect, the deasphalting step of deasphalting the vacuum distillation residue is first performed. The deasphalting step can be either one stage or more than two stages. Among them, it is preferable to use a deasphalting step of two or more stages in the following viewpoints: two or more kinds of raffinates having different dynamic viscosities which are useful as lubricating base oil raw materials, and suitable as rubber blending oils can be obtained separately. The extracts with different dynamic viscosities increase the variety of manufacturing of lubricating oil products and rubber blending oils. On the other hand, in terms of avoiding the cumbersome process, the deasphalting step is preferably two or less stages. Hereinafter, a method of performing the deasphalting step in the second stage of the first deasphalting step and the second deasphalting step will be described.

(1st deasphalting step)

The first deasphalting step is a step of separating the vacuum distillation residue of the atmospheric crude distillation residue of the crude oil with the deasphalting solvent in the first deasphalting tower 10 to separate into the first deasphalted oil and the first asphalt. Oil, and the first deasphalted oil and the first bituminous oil are obtained. The deasphalting solvent is appropriately recovered by a recovery tower (not shown) provided on the downstream side of the first deasphalting tower 10, and recycled.

The deasphalted solvent is supplied from the pipe 14 to the first deasphalting tower 10. On the other hand, the vacuum distillation residue is supplied from the pipe 12 to the first deasphalting tower 10. Then, the first deasphalted oil is obtained from the pipe 16, and the first bituminous oil is obtained from the pipe 18.

As the deasphalting solvent, a nonpolar light hydrocarbon such as propane or butane is used, and propane is preferably used. The deasphalting condition is preferably set to 10 to 35 mm ² /s at a temperature of 100 ° C of the first deasphalted oil, more preferably 15 to 30 mm ² /s, and further preferably Set to 18~28 mm ² /s. The deasphalting temperature can be adjusted by changing the temperature at the top of the first deasphalting column 10 and/or the temperature at the bottom of the column. The deasphalting condition of the first deasphalting step can be set, for example, as follows.

‧ Solvent ratio: The volume ratio based on the vacuum distillation residue is preferably from 1 to 6, more preferably from 1.5 to 4, and still more preferably from 2 to 4.

‧ The top temperature of the first deasphalting tower 10: preferably 60 to 120 ° C, more preferably 80 to 100 ° C, and even more preferably 85 to 95 ° C.

‧ The bottom temperature of the first deasphalting tower 10: preferably 50 to 100 ° C, more preferably 60 to 90 ° C, and even more preferably 70 to 85 ° C.

‧ The yield of the first deasphalted oil: based on the vacuum distillation residue, it is preferably from 1 to 30% by volume, more preferably from 2 to 20% by volume, and more preferably from 3 to 15% by volume.

The first deasphalted oil thus obtained is used in the first polar solvent extraction step described later, and is separated into a first raffinate and a first extract. On the other hand, the first bituminous oil (residual oil not extracted into the deasphalted solvent: oil containing a large amount of bitumen) can be directly used as a raw material of the bitumen. Further, it is preferred that the second bituminous oil obtained by separating the first bituminous oil into the second deasphalted oil by the second deasphalting step described later is directly used as the raw material of the pitch.

(Second deasphalting step)

The second deasphalting step is a step of separating the first bituminous oil and the deasphalted solvent into a second deasphalted oil and a second bituminous oil by convective contact in the second deasphalting tower 20 to obtain a second deasphalted oil. With the second bituminous oil. The deasphalting solvent is appropriately recovered by a recovery tower (not shown) provided on the downstream side of the second deasphalting tower 20, and recycled.

The deasphalted solvent is supplied from the pipe 24 to the second deasphalting tower 20. On the other hand, the first bituminous oil is supplied from the pipe 18 to the second deasphalting tower 20. Further, the second deasphalted oil is obtained from the pipe 26, and the second bituminous oil is obtained from the pipe 28.

As the deasphalting solvent, a nonpolar light hydrocarbon such as propane or butane is used in the same manner as in the first deasphalting step, and propane is preferably used. The deasphalting solvent used in the second deasphalting step may be the same as or different from the first deasphalting step, and it is more preferable to use the same deasphalting solvent from the viewpoint of simplifying the process.

The deasphalting conditions in the second deasphalting step are not particularly limited as long as they are different from the deasphalting conditions in the first deasphalting step. The deasphalting condition in the second deasphalting step is, for example, preferably adjusted so that the dynamic viscosity at 100 ° C of the second deasphalted oil is 30 to 60 mm ² /s, preferably 35 to 50 mm ² /s. More preferably, it is 36~45 mm ² /s. As the above conditions, for example, the following conditions can be mentioned.

‧ Solvent ratio: The volume ratio based on the first asphalt-containing oil is, for example, 1 to 10, preferably 4 to 8, more preferably 5 to 7.

‧ The top temperature of the second deasphalting tower 20 is 50 to 110 ° C, preferably 60 to 80 ° C. The temperature of the first deasphalting tower top is preferably 10 to 30 ° C, and more preferably 15 to 25 ° C.

‧ The bottom temperature of the second deasphalting tower 20 is 40 to 80 ° C, preferably 50 to 60 ° C.

‧ Yield of the second deasphalted oil: 15 to 50% by volume, preferably 20 to 45% by volume, more preferably 25% by volume, based on the first bituminous oil as the raw material of the second deasphalting step ~40% by volume.

The solvent in the second deasphalting step is preferably 1.5 to 10 times the solvent ratio in the first deasphalting step, more preferably 2 to 5 times, and more preferably 2.5 to 4 times. Times.

The temperature at the top of the second deasphalting step is preferably 10 to 30 ° C lower than the temperature at the top of the first deasphalting step, and more preferably 15 to 25 ° C lower. The bottom temperature in the second deasphalting step is preferably 10 to 30 ° C lower than the bottom temperature in the first deasphalting step, and more preferably 15 to 25 ° C lower.

(1st polar solvent extraction step (1))

The first polar solvent extraction step (1) is a step of convecting the first deasphalted oil and the polar solvent in the first extraction column 30, and separating the first deasphalted oil into the first raffinate and the first extract. And the first raffinate and the first extract are obtained. The polar solvent is appropriately collected and recycled using a recovery tower (not shown) provided on the downstream side of the first extraction column 30. Examples of the polar solvent include furfural, phenol, cresol, cyclobutyl hydrazine, N-methylpyrrolidone, dimethyl hydrazine, and formazan. In the present embodiment, it is preferred to use furfural as a solvent extraction device which can be used for a general lubricating base oil.

The polar solvent is supplied from the pipe 34 to the first extraction column 30. On the other hand, the first deasphalted oil is supplied to the first extraction column 30 through the pipe 16 . Then, the first raffinate is obtained from the pipe 36, and the first extract is obtained from the pipe 38.

The extraction conditions are not particularly limited. For example, the extraction conditions are adjusted so that the dynamic viscosity at 100 ° C of the first extract is preferably 30 to 70 mm ² /s, more preferably 40 to 60 mm ² /s. . The extraction conditions of the first polar solvent extraction step can be set, for example, as follows.

‧ Solvent ratio: The volume ratio based on the first deasphalted oil is preferably from 1 to 5, more preferably from 2 to 4, more preferably from 2.5 to 3.5.

‧ The temperature at the top of the first extraction column 30: preferably from 100 to 150 ° C, more preferably from 120 to 140 ° C, and even more preferably from 126 to 136 ° C.

‧ The temperature at the bottom of the first extraction column 30: preferably 60 to 130 ° C, more preferably 80 to 125 ° C, and even more preferably 86 to 120 ° C.

‧ Yield of the first extract: Based on the first deasphalted oil, it is preferably 15 to 50% by volume, more preferably 20 to 40% by volume, and further preferably 25 to 33% by volume.

(2nd polar solvent extraction step (1))

The second polar solvent extraction step is a step of convecting the second deasphalted oil and the polar solvent in the second extraction column 40 to separate the second extract and the second raffinate to obtain the second extract and the second extract. 2 extract residue. The polar solvent is appropriately recovered and recycled using a recovery tower (not shown) provided on the downstream side of the second extraction column 40. As the polar solvent, the same one as the above first polar solvent extraction step (1) can be used. Further, from the viewpoint of process simplification, it is preferred that the polar solvent used in the first and second polar solvent extraction steps is the same.

The polar solvent is supplied from the pipe 44 to the second extraction column 40. On the other hand, the second deasphalted oil is supplied to the second extraction column 40 through the pipe 26. Further, the second raffinate is obtained from the pipe 46, and the second raffinate is obtained from the pipe 48.

The extraction conditions are not particularly limited. For example, it is preferred to adjust so that the dynamic viscosity at 100 ° C of the second extract is preferably 70 to 150 mm ² /s, more preferably 80 to 120 mm ^{2 .} /s, and it is better to reach 90~100 mm ² /s. Further, the extraction conditions can be set in the same manner as in the above first polar solvent extraction step (1). Specifically, it can be set as follows.

‧ Solvent ratio: The volume ratio based on the second deasphalted oil is preferably from 1 to 5, more preferably from 2 to 4, more preferably from 2.5 to 3.5.

‧ The temperature of the top of the second extraction column 40: preferably from 100 to 150 ° C, more preferably from 120 to 140 ° C, and even more preferably from 126 to 136 ° C.

‧ The bottom temperature of the second extraction column 40: preferably 60 to 130 ° C, more preferably 80 to 125 ° C, and more preferably 86 to 120 ° C.

‧ The second extract yield is 15 to 50% by volume, preferably 20 to 40% by volume, more preferably 25 to 33% by volume, based on the second deasphalted oil.

The component (A) in the present embodiment can be obtained from the first extract in the first polar solvent extraction step (1) and/or the second extract in the second polar solvent extraction step (1). Further, from the viewpoint of improving the yield, it is preferred that the component (A) is the second extract.

(the second aspect)

The component (A) of the present embodiment can also be obtained by the production method described below other than the first aspect. In the second aspect, the second extract as the component (A) is obtained from the vacuum distillation fraction of the atmospheric crude distillation residue of crude oil by a two-stage polar solvent extraction step.

(1st polar solvent extraction step (2))

Fig. 2 is a schematic view showing the steps of the second aspect of the method for producing the component (A). First, in the first polar solvent extraction step (2), the vacuum distillation fraction of the atmospheric crude distillation residue of the crude oil and the polar solvent are at a temperature of 30 to 90 ° C at the bottom of the column, and the temperature at the top of the column is higher than the temperature at the bottom of the column. 1 The extraction tower 30 is brought into contact with each other to obtain a first raffinate and a first extract.

The vacuum distillation fraction used as a raw material in the first polar solvent extraction step (2) is not limited to the fraction, and a light lubricating oil fraction, a medium lubricating oil fraction, a heavy lubricating oil fraction, or the like may be used. The mixture, or all fractions of the distillation fraction under reduced pressure.

In order to increase the flash point of the aromatic-containing base oil and to form a suitable viscosity range of the viscosity which is not too high, for example, 200 to 1500 N, preferably 250 to 1200 N, and more preferably 300 to 300 is used. 600 N and / or 600 ~ 1200 N lubricant fraction.

In addition, the "N" in the present specification means that a neutral oil is obtained from a vacuum distillation fraction, and if it is 300 N, it means that the viscosity at 100 °F (37.8 °C) is 300 Saibo seconds (SUS). .

In this aspect, in order to obtain a lubricating base oil of 200 to 1500 N, preferably 250 to 600 N and/or 600 to 1200 N, more preferably 300 to 450 N and/or 700 to 1000 N. As the component (B), it is preferred to select a vacuum distillation fraction of atmospheric distillation residue of crude oil.

In the first polar solvent extraction step (2), the vacuum distillation fraction and the polar solvent are convectively contacted in the first extraction column 30, and the first deasphalted oil is separated into the first raffinate and the first extract. The first raffinate and the first extract were obtained. The polar solvent is appropriately collected and recycled using a recovery tower (not shown) provided on the downstream side of the first extraction column 30. The kind of the polar solvent is the same as that of the first polar solvent extraction step (1) described above.

The polar solvent is supplied from the pipe 34 to the first extraction column 30. On the other hand, the vacuum distillation fraction is supplied to the first extraction column 30 through the pipe 16. Then, the first raffinate is obtained from the pipe 36, and the first extract is obtained from the pipe 38.

The temperature at the bottom of the first extraction column 30 is 30 to 90 ° C, preferably 50 to 70 ° C, and more preferably 55 to 65 ° C. The temperature at the top of the first extraction column 30 is higher than the temperature at the bottom of the column, preferably 10 to 50 ° C higher, more preferably 15 to 40 ° C higher, and more preferably 25 to 35 ° C higher. More specifically, the temperature at the top of the column is preferably from 60 to 120 ° C, more preferably from 80 to 100 ° C, and still more preferably from 85 to 95 ° C.

The solvent ratio in the first polar solvent extraction step (2) is from 0.5 to 3, preferably from 0.7 to 2, and more preferably from 1 to 1.5. In addition, the solvent ratio in this specification shows the capacity ratio (solvent amount / raw material) of a solvent with respect to a raw material.

The yield of the first raffinate obtained by the above extraction conditions is usually 50 to 90% by volume, preferably 60 to 85% by volume, more preferably 70 to 80% by volume. Further, the yield of the first extract is usually 10 to 50% by volume, preferably 15 to 40% by volume, more preferably 20 to 30% by volume.

The specific aromatic compound can be extracted on the first extract side by the above extraction conditions. Therefore, the amount of the specific aromatic compound of the lubricating base oil (component (B)) obtained by reducing the second extract and the second raffinate obtained in the subsequent step can be sufficiently reduced.

(2nd polar solvent extraction step (2))

The second polar solvent extraction step (2) uses the first raffinate obtained in the first polar solvent extraction step (2) as a raw material. The first raffinate and the polar solvent are convectively contacted in the second extraction column 41, and separated into a second extract and a second raffinate to obtain a second extract and a second raffinate. The polar solvent can be used in the same manner as the first polar solvent extraction step (2). Further, from the viewpoint of process simplification, it is preferred that the polar solvent used in the first and second polar solvent extraction steps is the same.

The polar solvent is supplied from the pipe 44 to the second extraction column 41. On the other hand, the first raffinate is supplied to the second extraction column 41 through the pipe 36. Further, the second raffinate is obtained from the pipe 47, and the second extract is obtained from the pipe 49.

The bottom temperature of the second extraction column 41 is higher than the bottom temperature of the first extraction column 30 in the first polar solvent extraction step (1) by 10 ° C or more, preferably 10 to 50 ° C higher, more preferably high. 15 to 40 ° C, and more preferably 20 to 30 ° C. More specifically, the temperature at the bottom of the second extraction column 41 is preferably 40 to 140 ° C, more preferably 60 to 100 ° C, and still more preferably 80 to 95 ° C.

The temperature at the top of the second extraction column 41 is preferably 10 to 50 ° C higher than the temperature at the bottom of the column, more preferably 15 to 40 ° C higher, and more preferably 25 to 35 ° C higher. Specifically, the temperature at the top of the second extraction column 41 is preferably from 50 to 150 ° C, more preferably from 80 to 140 ° C, and still more preferably from 110 to 130 ° C.

The solvent ratio in the second polar solvent extraction step (2) is from 1 to 4, preferably from 1.3 to 3.5, more preferably from 1.5 to 3.3, and preferably it is the first polar solvent extraction step (2). The solvent in the) is more than 1.5 times.

By setting the above extraction conditions, the yield of the second raffinate is usually 50 to 90% by volume, preferably 60 to 85% by volume, more preferably 70 to 85% by volume, and the second extract is produced. The rate is usually 10 to 50% by volume, preferably 15 to 40% by volume, more preferably 15 to 30% by volume.

The density of the obtained second extract at 15 ° C was 0.94 g/cm ³ or more, and the total aromatic content obtained in accordance with ASTM D2549 was 30% by mass or more. The above second extract can be used as the component (A).

The density of the second extract at 15 ° C is preferably from 0.95 to 1 g/cm ³ , more preferably from 0.95 to 0.98 g/cm ³ . Further, the total aromatic content of the second extract is 30% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or less. Further, the total aromatic content in the present specification is measured in accordance with ASTM D2549.

The % C _{A of} the second extract measured by ASTM D2140 is preferably from 15 to 35, more preferably from 20 to 33, and still more preferably from 22 to 32.

Further, the second extract has the following properties.

‧ Flash point: 250 ° C or more, preferably 260 ° C or more, more preferably 310 ° C or less.

‧ Flow point: 30 ° C or less, preferably 10 to 30 ° C.

‧ Aniline point: below 90 ° C, preferably 40 ~ 80 ° C, more preferably 50 ~ 70 ° C.

‧Benzene (a) hydrazine content: 1 mass ppm or less.

‧ Total content of specific aromatic compounds: 10 ppm by mass or less.

(Method of manufacturing component (B))

The method for producing the component (B) in the present embodiment is not particularly limited. The component (B) can be obtained, for example, by deasphalting the decompressed oil obtained by subjecting a vacuum distillation fraction of a crude oil distillation residue of crude oil or a vacuum distillation residue of a crude oil to atmospheric distillation residue. The extraction treatment is carried out using a polar solvent such as furfural, and the obtained raffinate is subjected to a purification treatment including dewaxing or hydrogenation processing.

Further, as the component (B), hydrogenation-decomposing mineral oil or hydroisomerized mineral oil may be used, and it is not necessary to have a remarkable high quality. It can be said that the use of a lubricating base oil having a total aromatic content of 30% by mass or more obtained by a relatively moderate purification condition is preferable in terms of improvement in suitability as a rubber blending oil and economy.

In the case of using the component (A) having a dynamic viscosity of 2000 mm ² /s or more at 40 ° C, in order to obtain a suitable dynamic viscosity rubber blending oil, it is preferred to use a dynamic viscosity of 50 ° at 40 ° C. The component (B) of 150 mm ² /s is more preferably a component (B) having a dynamic viscosity of 40 to 120 mm ² /s at 40 ° C.

On the other hand, in the case of using the component (A) having a dynamic viscosity of less than 2000 mm ² /s at 40 ° C, in order to obtain a suitable dynamic viscosity rubber blending oil, it is preferred to use a dynamic at 40 ° C. The component (B) having a viscosity of 50 to 500 mm ² /s is more preferably a component having a dynamic viscosity at 40 ° C of 60 to 80 mm ² /s and/or 120 to 250 mm ² /s.

Hereinafter, two manufacturing methods (conveniently referred to as "first aspect" and "second aspect") will be described in detail with reference to the drawings.

(1st aspect) (1st polar solvent extraction step (3))

Fig. 3 is a schematic view showing the steps of the first aspect of the method for producing the component (B).

In the first polar solvent extraction step (3), a vacuum distillation fraction of atmospheric crude distillation residue of crude oil is used as a raw material. The vacuum distillation fraction and the polar solvent are convectively contacted in the first extraction column 30, and separated into a first extract and a first raffinate to obtain a first extract and a first raffinate. The polar solvent is appropriately collected and recycled using a recovery tower (not shown) provided on the downstream side of the first extraction column 30. The polar solvent to be used is the same as the method for producing the above component (A).

As a vacuum distillation fraction, in order to obtain a lubricating base oil having a relatively high flash point, it is preferably a fraction corresponding to 200 to 800 N, preferably a fraction corresponding to 350 to 700 N, more preferably equivalent to 400~ 600 N fraction.

The polar solvent is supplied from the pipe 34 to the first extraction column 30. On the other hand, the vacuum distillation fraction is supplied to the first extraction column 30 through the pipe 16. Then, the first raffinate is obtained from the pipe 36, and the first extract is obtained from the pipe 38.

The first raffinate obtained is subjected to purification treatment by the dewaxing device 50 and the hydroprocessing device 60 to obtain a lubricating base oil as the component (B). Further, as the dewaxing device 50 and the hydroprocessing device 60, a general device can be used.

The temperature of the bottom of the first extraction column 30 in the first polar solvent extraction step (3) is 30 to 90 ° C, preferably 60 to 80 ° C, and more preferably 65 to 75 ° C. On the other hand, the temperature at the top of the first extraction column 30 is higher than the temperature at the bottom of the column, preferably 20 to 80 ° C higher, more preferably 30 to 70 ° C higher, and more preferably 40 to 60 ° C higher. More specifically, the temperature at the top of the first extraction column 30 is preferably from 80 to 160 ° C, more preferably from 100 to 140 ° C, and still more preferably from 110 to 130 ° C.

The solvent ratio in the first polar solvent extraction step (3) is from 0.5 to 4, preferably from 1 to 3, and more preferably from 1.5 to 2.5.

The yield of the first raffinate obtained by the above extraction conditions is usually 40 to 80% by volume, preferably 50 to 70% by volume, more preferably 55 to 65% by volume, of the first extract. The rate is usually 20 to 60% by volume, preferably 30 to 50% by volume, more preferably 35 to 45% by volume.

Since the specific aromatic compound is extracted on the first extract side by the above extraction conditions, the content of the specific aromatic compound of the lubricating base oil obtained from the first raffinate can be sufficiently reduced.

Next, the first raffinate is subjected to purification treatment such as solvent dewaxing or hydrogenation to obtain a dynamic viscosity at 40 ° C of 50 to 150 mm ² /s, preferably 80 to 120 mm ² /s. Lubricating base oil (component (B)).

Further, when a vacuum distillation fraction equivalent to 400 to 600 N is used as a raw material, a flash point of 250 ° C or higher and a dynamic viscosity at 40 ° C of 50 to 150 mm ² /s, preferably 80 ° can be obtained. 120 mm ² /s, 10% point of GC distillation is 430~480 °C, and 90% point is 520~560 °C (B).

(the second aspect)

Fig. 2 is a schematic view showing the second aspect of the method for producing the component (B). This aspect is a step of obtaining a second raffinate by a two-stage polar solvent extraction step, and then subjecting the second raffinate to a desulfurization treatment to obtain a lubricating base as the component (B). oil.

(1st polar solvent extraction step (4))

In the first polar solvent extraction step (4), a vacuum distillation fraction of atmospheric crude distillation residue of crude oil is used as a raw material. The vacuum distillation fraction and the polar solvent are convectively contacted in the first extraction column 30, and separated into a first extract and a first raffinate to obtain a first extract and a first raffinate. The polar solvent is appropriately collected and recycled using a recovery tower (not shown) provided on the downstream side of the first extraction column 30. The type of the polar solvent is the same as that of the first aspect described above.

In the first polar solvent extraction step (4), the temperature of the bottom of the first extraction column 30 is set to 30 to 90 ° C, so that the temperature at the top of the column is higher than the temperature at the bottom of the column.

(Second polar solvent extraction step (4))

Next, in the second extraction column 41 having a column bottom temperature and a column top temperature which are higher than the bottom temperature and the column top temperature in the first polar solvent extraction step (4) by 10 ° C or higher, the first raffinate is made The second raffinate and the second extract are obtained by contact with a polar solvent. By subjecting the second raffinate to a purification treatment including the dewaxing device 50 and the hydroprocessing device 60, a lubricating base oil as the component (B) can be obtained. Further, as the dewaxing device 50 and the hydroprocessing device 60, a general device can be used.

This production method is a method in which the second raffinate obtained by the same procedure as the two-stage polar solvent extraction step described in detail in the second aspect of the "Production method of the component (A)" is included. The purification treatment of the dewaxing treatment is carried out to obtain a lubricating base oil as the component (B). The first polar solvent extraction step (4) and the second polar solvent extraction step (4) can be carried out in the same manner as the first polar solvent extraction step (2) and the second polar solvent extraction step (2).

By the above manufacturing method, a lubricating base oil of 200 to 1500 N, preferably 250 to 600 N and/or 600 to 1200 N, more preferably 300 to 450 N and/or 700 to 1000 N can be obtained ( (B) Ingredients).

Furthermore, when using a vacuum distillation fraction equivalent to 300 to 400 N as a raw material, a flash point of 250 ° C or higher, a dynamic viscosity at 40 ° C of 60 to 80 mm ² /s, and a GC distillation of 10 can be obtained. The % point is 400~460°C, and the 90% point is 500~540°C (B).

Further, when a vacuum distillation fraction corresponding to 700 N to 1000 N is used as a raw material, a flash point of 250 ° C or higher, a dynamic viscosity at 40 ° C of 120 to 250 mm ² /s, and a GC distillation of 10 can be obtained. The % point is 450 to 520 ° C, and the 90% point is 540 to 600 ° C (B).

The above is a description of suitable embodiments of the present invention, but the present invention is not limited to the above embodiments. For example, the manufacturing apparatus shown in Fig. 1 used in the first aspect of the method for producing the component (A) may be provided on the downstream side of the first extraction column 30 and the second extraction column 40, respectively. The dewaxing apparatus 50 and the hydroprocessing apparatus 60 purify the first and second extracts to obtain a lubricating base oil as the component (B).

Example

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1 to 3, Comparative Example 1) [Manufacture of (A) component]

The component (A) was produced using a manufacturing apparatus as shown in FIG. Specifically, the vacuum distillation residue of the atmospheric pressure distillation residue of the crude oil is brought into convection contact with the propane in the first deasphalting tower 10, and the vacuum distillation residue is subjected to propane deasphalting, and the first deasphalted oil and the first 1 Separation of bituminous oil (residual oil extracted from propane) (first deasphalting step).

In the first deasphalting step, the deasphalting conditions (solvent ratio, column top temperature, and bottom temperature) are adjusted so that the yield of the first deasphalted oil (the dechlorinated product) is relative to the above vacuum distillation slag. The oil reaches 1 to 20% by volume, and the dynamic viscosity of the first deasphalted oil at 100 ° C reaches 15 to 30 mm ² /s. The solvent ratio is adjusted within a range of 1 to 4 by volume of the vacuum distillation residue as a reference, and the temperature of the top of the deasphalting tower is adjusted within a range of 80 to 100 ° C, and the temperature at the bottom of the column is adjusted. Adjust within the range of 60 to 90 °C.

Next, the first bituminous oil and the propane are convectively contacted in the second deasphalting tower 20, the first bituminous oil is subjected to propane deasphalting, and the second deasphalted oil and the second bituminous oil are extracted by propane. Residual oil) separation (second deasphalting step).

In the second deasphalting step, the deasphalting conditions (solvent ratio, overhead temperature, and bottom temperature) are adjusted so that the yield of the 2 deasphalted oil (the propane is distilled) is relative to the first deasphalting step. The vacuum distillation residue as a raw material reaches 15 to 50% by volume, and the dynamic viscosity at 100 ° C of the second deasphalted oil reaches 30 to 60 mm ² /s. The solvent ratio is greater than the first deasphalting step, so that the top temperature and the bottom temperature of the second deasphalting tower 20 are lower than the top temperature and the bottom temperature of the first deasphalting tower 10, respectively. Specifically, the solvent ratio is adjusted within a range of 4 to 8 by volume ratio based on the first asphalt-containing oil, and the temperature at the top of the column and the temperature at the bottom of the column are 60 to 90 ° C and 40 to 80 ° C, respectively. Adjust within the scope.

Table 1 shows the deasphalting conditions of the first deasphalting step and the second deasphalting step, and the yields of the obtained deasphalted oil and the asphalt-containing oil.

In the table, the solvent ratio indicates the volume ratio of the solvent (propane) based on the raw material.

Then, the first deasphalted oil and the second deasphalted oil are convectively contacted with furfural in the first extraction column 30 and the second extraction column 40, respectively, to obtain the first extract A1 and the second extract A2 (first polarity). Solvent extraction step (1) and first polar solvent extraction step (2)).

In the first polar solvent extraction step (1), the extraction conditions (solvent ratio, the top temperature of the first extraction column 30, and the bottom temperature) are adjusted so that the dynamic viscosity of the first extract at 100 ° C is reached. 30~70 mm ² /s, the yield of the first extract is 15 to 45 vol% relative to the first deasphalted oil, the aniline point is below 90 ° C, the flash point is above 250 ° C, and the asphalt content is below 3% by mass. . Specifically, the solvent ratio is adjusted within a range of 2 to 4 in terms of a volume ratio based on the first deasphalted oil, and the temperature at the top of the column is adjusted in the range of 100 to 150 ° C, and the temperature at the bottom of the column is adjusted. Adjust within 60~130 °C.

In the first polar solvent extraction step (2), the extraction conditions (solvent ratio, the top temperature of the second extraction column 40, and the bottom temperature) are adjusted so that the dynamic viscosity of the second extract at 100 ° C is reached. 70~150 mm ² /s, the yield of the second extract is 15 to 45 vol% with respect to the second deasphalted oil, the aniline point is below 90 ° C, the flash point is above 250 ° C, and the asphalt content is below 3% by mass. . Specifically, the solvent ratio is adjusted within a range of 2 to 4 in terms of a volume ratio based on the second deasphalted oil, and the temperature at the top of the column is adjusted in the range of 100 to 150 ° C, and the temperature at the bottom of the column is adjusted. Adjust within 60~130 °C.

Table 2 shows the extraction conditions of the first polar solvent extraction step (1) and the first polar solvent extraction step (2) and the yields of the first extract A1 and the second extract A2. Further, the first extract A1 and the second extract A2 were not subjected to purification treatment.

[Manufacture of (B) component]

The component (B) was produced using a manufacturing apparatus as shown in FIG. Specifically, a fraction corresponding to 500 N is prepared as a vacuum distillation fraction of atmospheric distillation residue of crude oil. The fraction corresponding to 500 N is brought into convection contact with furfural in the first extraction column 30 to obtain a first raffinate and a first extract C (first polar solvent extraction step (3)).

The temperature in the bottom of the first extraction column 30 is set to 30 to 90 ° C, and the temperature at the top of the column is set to be higher than the temperature at the bottom of the column. The obtained first raffinate is subjected to a purification treatment such as a dewaxing treatment or a hydroprocessing treatment to obtain a lubricating base oil B1. The extraction conditions of the first polar solvent extraction step (3) and the yields of the first raffinate and the first extract C are shown in Table 3.

The first extract A1 (base material 1) obtained in the first polar solvent extraction step (1), the second extract A2 (base material 2) obtained in the first polar solvent extraction step (2), and the first The lubricating oil base oil B1 obtained by purifying the first extract C (substrate 3) obtained in the polar solvent extraction step (3) and the first raffinate obtained in the first polar solvent extraction step (3) The properties of the substrate 4) are shown in Table 4.

As shown in Table 4, the content of the specific aromatic compound of the first extract A1 and the second extract A2 was less than a specific amount (10 ppm). On the other hand, the content of the first extract C obtained by the first polar solvent extraction step (3) of the vacuum distillation fraction exceeds the specific aromatic compound by a specific amount.

The rubber mixture oil of Examples 1 to 3 was prepared by blending the second extract A2 and the lubricating base oil B1 obtained in the above manner at a ratio shown in Table 5. Further, the first extract C and the lubricating base oil B1 were blended at a ratio shown in Table 5 to prepare a rubber blended oil of Comparative Example 1. The properties of each rubber blended oil are shown in Table 5.

The expected flow point in Table 5 is based on the assumption that the addition property is established, and is calculated based on the flow point of (A) the second extract A2 and (B) the lubricating base oil B1.

It was confirmed from Table 5 that the rubber blended oils of Examples 1 to 3 showed a flow point which was at least 5 ° C lower than the expected flow point calculated from the flow point of the substrate. Further, the content of the specific aromatic compound of the rubber blending oil of Examples 1 to 3 was less than a specific amount. The rubber blended oil of Example 2 had a pour point of -5 ° C, which was 7.5 ° C lower than the expected flow point. On the other hand, in the rubber blending oil of Comparative Example 1, the content of the specific aromatic compound exceeded a specific amount.

With respect to the rubber blended oil of Example 2, the composition was analyzed according to ASTM D2007 (Clay Gel Adsorption Chromatography), and the saturated content was 30.5 mass%, the aromatic content was 61.3% by mass, and the polar compound was 8.2% by mass. The content/polar compound ratio was 3.7.

(Examples 4 and 5, Comparative Examples 2 and 3) [Manufacture of (A) component]

The component (A) was produced using a manufacturing apparatus as shown in FIG. Specifically, a vacuum distillation fraction (350 N equivalent fraction) of atmospheric crude distillation residue of crude oil is brought into convection contact with furfural in the first extraction column 30, and a fraction corresponding to 350 N is separated into a first raffinate and The first extract D. The temperature at the bottom of the first extraction column 30 is set to 30 to 90 ° C (first polar solvent extraction step (2)).

Next, the first raffinate is brought into convection contact with furfural in the second extraction column 41, and the first raffinate is separated into the second raffinate and the first extract A3 (second polar solvent extraction step (2)) . The top temperature and the bottom temperature of the second extraction column 41 in the second polar solvent extraction step (2) are higher than the top temperature and the bottom temperature of the first extraction column 30 in the first polar solvent extraction step (2). Each is 10 ° C higher.

Thereby, the second raffinate, the second extract A3 having a density of 0.94 g/cm ³ or more at 15 ° C and a total aromatic content of 30% by mass or more according to ASTM D2549 was obtained.

Table 6 shows the extraction conditions of the first polar solvent extraction step (2) and the second polar solvent extraction step (2), and the yields of the respective raffinate and extract.

Further, a vacuum distillation fraction (corresponding to a fraction of 900 N) of atmospheric crude distillation residue of crude oil is used as a raw material, and a plurality of extraction conditions are changed, in addition to the first polar solvent extraction step (2) and the second polar solvent. In the same manner as in the extraction step (2), the first polar solvent extraction step (2) and the second polar solvent extraction step (2) are carried out using the production apparatus shown in FIG. 2, and the first raffinate and the first extraction column 30 are obtained. 1 extract E, the second raffinate obtained from the second extraction column 41, and the second extraction having a density of 0.94 g/cm ³ or more at 15 ° C and a total aromatic content of 30% by mass or more according to ASTM D2549 A4.

Table 7 shows the extraction conditions of the first polar solvent extraction step (2) and the second polar solvent extraction step (2) using the fraction corresponding to 900 N as the vacuum distillation fraction, and the respective raffinate and extract. Yield.

The first extracts D and E in Tables 6 and 7 exceeded the content of the specific aromatic compound by more than 10 ppm by mass.

Next, the second raffinates in Tables 6 and 7 were subjected to MEK dewaxing treatment and hydrogenation treatment to obtain lubricating base oils B2 and B3, respectively. Further, the second extract A3 and the second extract A4 obtained by mixing 37.5:62.5 (mass ratio) were used to obtain the second extract A5 having a dynamic viscosity at 40 ° C of less than 650 mm ² /s.

The properties of the second extracts A4 and A5 and the lubricating base oils B2 and B3 obtained in this manner are shown in Table 8.

The rubber-blended oil of Examples 4 and 5 was prepared by blending the second extract A4 and the lubricating base oil B2 or B3 obtained in the above manner at a ratio shown in Table 9. Further, the second extract A5 or the first extract E and (B) the lubricating base oil B3 were blended at a ratio shown in Table 9 to prepare rubber blended oils of Comparative Examples 2 and 3. The properties of each of the rubber blended oils are shown in Table 9.

The expected flow point in Table 9 is based on the premise that the addition is established, and is calculated based on (A) the pour point of the second extract A2 and (B) the flow point of the lubricating base oil B1 and the blending ratio of the blending ratio. .

It was confirmed from Table 9 that the rubber blended oils of Examples 4 and 5 exhibited a flow point which was at least 5 ° C lower than the expected flow point calculated from the flow point of the substrate. Further, the content of the specific aromatic compound of the rubber blending oil of Examples 4 and 5 was less than a specific amount (10 ppm). On the other hand, the rubber blended oil of Comparative Example 2 showed a value higher than the expected flow point, and the content of the specific aromatic compound of the rubber blending oil of Comparative Example 3 exceeded a specific amount.

Further, regarding the rubber blending oils of Example 1, Example 2, and Example 3, and Example 4 and Example 5, a glass transition point (T _g ) was measured by DSC (differential scanning calorimeter) using the above method. The results were -44.5 ° C, -51.3 ° C and -55.0 ° C, and -52.5 ° C and -51.7 ° C, respectively. That is, the rubber blending oils of Examples 1 to 5 can be excellent by mixing a specific extract with a lubricating base oil, which satisfies the % C _A of 20 to 35 mentioned in Patent Document 1, The glass transition temperature T _g is -55 ° C to -30 ° C, the dynamic viscosity (100 ° C) is 20 to 50 mm ² /s, and the total content of the specific aromatic compound (PAH) can be made less than a specific amount. And then the pour point is lower than the expected point of flow.

Therefore, the rubber blending oils of Examples 1 to 5 are blended to contain at least, for example, natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), and poly a diene rubber such as an isoprene rubber (IR), a butyl rubber (BR), or any of these blended rubbers, particularly a diene rubber of a styrene-butadiene copolymer rubber, With low fuel economy and grip, it can improve heat aging resistance and wear resistance.

Industrial availability

According to the present invention, it is possible to provide a rubber blending oil which has a high flash point and high aromaticity, sufficiently lowers the content of a specific aromatic compound, has a low pour point, and is excellent in economy, and a method for producing the same.

10. . . First deasphalting tower

20. . . 2nd deasphalting tower

30. . . First extraction tower

40, 41. . . 2nd extraction tower

50. . . Dewaxing device

60. . . Hydrogenation processing unit

Fig. 1 is a schematic view showing the steps of an example of a method for producing a substrate used in the rubber blending oil of the present invention.

Fig. 2 is a schematic view showing the steps of another example of the method for producing a substrate used in the rubber blending oil of the present invention.

Fig. 3 is a schematic view showing still another example of the method for producing a substrate used in the rubber blending oil of the present invention.

Claims (5)

A rubber blending oil comprising an extract (A) and a lubricating base oil (B); the extract (A) having an aniline point of 40 to 90 ° C and a % C _A of 25 according to ASTM D3238 ~45 and % C _N is 5 to 20, the nitrogen content is 0.01% by mass or more, the pour point is +30 ° C or lower, the content of benzo(a)pyrene is 1 ppm by mass or less, and the total content of specific aromatic compounds is 10 or less. The mass is less than ppm, and the dynamic viscosity at 40 °C is 650 mm ² /s or more; the above lubricating base oil (B) has a pour point of -10 ° C or less, an aniline point of 70 ° C or more, and a % obtained according to ASTM D3238 C _A is 3-20 and % C _N is 15~35, nitrogen content is 0.01% by mass or less, 90% of GC distillation is above 500 °C, flash point is above 250 °C, and content of benzo(a)pyrene It is 1 mass ppm or less, and the total content of the specific aromatic compound is 10 mass ppm or less. The rubber blending oil according to claim 1, wherein the extract (A) is a deasphalted oil obtained by deasphalting the vacuum distillation residue of atmospheric crude distillation residue of crude oil in one or two stages with a polar solvent. The extract obtained by contacting with the extraction is carried out. The rubber blending oil of claim 1, wherein the extract (A) comprises an extract obtained by a two-stage polar solvent extraction step; the extract is obtained by using a bottom temperature of 30 to 90 ° C, and the top of the column The first extraction tower having a temperature higher than the temperature of the bottom of the column, the raffinate obtained by contacting the vacuum distillation residue of the atmospheric crude distillation residue with the polar solvent and the polar solvent at the bottom temperature and the top temperature respectively 1 obtained by contacting the second extraction column having an extraction column height of 10 ° C or higher; the density of the above extract at 15 ° C is 0.94 g / cm ³ or more, and the total aromatic content obtained according to ASTM D2549 is 30% by mass or more. . The rubber blending oil according to any one of claims 1 to 3, wherein the lubricating base oil (B) contains a dewaxed oil of the first raffinate obtained by the one-stage polar solvent extraction step (c) And/or a dewaxed oil (d) of the second raffinate obtained by the two-stage polar solvent extraction step; the above dewaxed oil (c) is at a temperature of 30 to 90 ° C at the bottom of the column, and the temperature at the top of the column a first raffinate obtained by contacting a vacuum distillation fraction of a crude oil atmospheric distillation residue with a polar solvent in a first extraction column having a temperature higher than a bottom temperature, and obtaining the above-mentioned first raffinate obtained by a dewaxing step; The dewaxed oil (d) is obtained by bringing the first raffinate into contact with a polar solvent in a second extraction column having a column bottom temperature and a column top temperature higher than the first extraction column by 10 ° C or higher. The second raffinate is obtained by a purification treatment including a dewaxing step. A method for producing a rubber blending oil comprising the steps of blending an extract (A) with a lubricating base oil (B); the extract (A) having an aniline point of 40 to 90 ° C according to ASTM D3238 % C _A is 25 to 45 and % C _N is 5 to 20, the nitrogen content is 0.01% by mass or more, the pour point is +30 ° C or lower, and the content of benzo (a) lanthanum is 1 ppm by mass or less, specific aromatic compound The total content is 10 ppm by mass or less, and the dynamic viscosity at 40 ° C is 650 mm ² /s or more; the lubricating base oil (B) has a pour point of -10 ° C or less and an aniline point of 70 ° C or more. ASTM D3238 has a % C _A of 3 to 20 and a % C _N of 15 to 35, a nitrogen content of 0.01% by mass or less, a 90% point in GC distillation of 500 ° C or more, and a flash point of 250 ° C or more. (a) The content of cerium is 1 mass ppm or less, and the total content of the specific aromatic compound is 10 mass ppm or less.