JP5781262B2 - Production method of petroleum products - Google Patents

Description

  The present invention relates to a method for producing a petroleum product and a petroleum product obtained thereby.

  Highly aromatic mineral oils are used in rubber compositions such as natural rubber and synthetic rubber because they have a high affinity with rubber components, and are excellent in processability and softening properties of rubber compositions and in economic efficiency. It is used. For example, synthetic rubber such as SBR is blended with extender oil (extender oil) at the time of synthesis, and rubber processed products such as tires are processed oil (in order to improve processability and quality of the rubber processed product). Process oil).

  As a method for producing such a rubber compounding oil, it is known that a highly aromatic component such as a vacuum distillation fraction or a solvent extraction extract of a debris oil is used as disclosed in Patent Document 1, for example. Yes.

  By the way, in Europe, a regulation that DMSO extract or a specific carcinogenic polycyclic aromatic compound containing a specific amount or more must not be used for manufacturing tires or tire parts has been applied since 2010. Therefore, a rubber compounding oil that meets these regulations is required.

  As a method for producing such a rubber compounding oil, for example, as disclosed in Patent Document 2, it has been proposed to perform the solvent extraction step in two stages.

By the way, in a normal oil refining process, a series of petroleum products are co-produced from crude oil. For example, in parallel with the production of highly aromatic base oils used for rubber compounding oils, lubricating base oils obtained by refining deflocced oil are produced. This debris oil is made from a residual oil obtained by distilling off a normal lubricating oil fraction by distillation under reduced pressure. Therefore, a high-viscosity lubricating base oil having a kinematic viscosity at 40 ° C. of 450 mm ² / s or more, so-called Bright stock can be obtained. In addition, the impregnated oil having a high asphaltene content after deasphalting treatment is used as an asphalt or asphalt base material.

  Therefore, if some manufacturing processes of the oil refining process are changed, the properties of other co-products and other manufacturing processes will be affected. For this reason, there is a need for a process that can produce other petroleum products together with highly aromatic base oils that satisfy the above-mentioned regulations in Europe.

Japanese Patent No. 3624646 Japanese Patent No. 3658155

  The present invention has been made in view of the above circumstances, and as a petroleum product, a specific carcinogenic polycyclic aromatic compound is sufficiently reduced, together with a highly aromatic base oil useful as a rubber compounding oil, and a lubricating oil. It aims at providing the petroleum product obtained by the manufacturing method of the petroleum product which can obtain a base oil and at least one of asphalt together, and the said manufacturing method.

In the present invention, a first degassing step for separating a first degassed oil and a first impregnated oil by bringing the reduced pressure distillation residue oil of the crude oil atmospheric distillation residue into contact with the degassed solvent; A first polar solvent extraction step in which the first exfoliated oil and the polar solvent are brought into contact with each other to separate the first extract and the first raffinate; and a lubricating base oil is obtained from the first raffinate. A first product production step, and at least one product production step of obtaining at least one selected from asphalt, lubricating base oil, and highly aromatic base oil from impregnated oil. At least one selected from a highly aromatic base oil containing an extract, a lubricating base oil obtained from the first raffinate, and an asphalt obtained from impregnated oil, a lubricating base oil and a highly aromatic base oil; Of petroleum products, including both A granulation method, highly aromatic base oil derived from highly aromatic base oils and / or containing gravel oil containing the first extract, the kinematic viscosity of 600 mm 2 / ^s or more at 40 ° C., an aniline point of 90 ° C. or less, a flash point of 250 ° C. or higher, the asphaltene content of 3 mass% or less,% by ASTM D3238 _{C a} is 20 to 45,% _{C N} is 5 to 25, the content of benzo (a) pyrene less than 1 ppm by mass And a total content of the specific aromatic compound (PAH) is 10 mass ppm or less.

  According to the method for producing a petroleum product of the present invention, a specific base carcinogenic polycyclic aromatic compound is sufficiently reduced, a highly aromatic base oil useful as a rubber compounding oil, a lubricating base oil and an asphalt It is possible to provide a method for producing a petroleum product that can be obtained by combining at least one of them. Such a production method is extremely useful industrially because a plurality of types of petroleum products including a highly aromatic base oil with sufficiently reduced harmful components can be produced simultaneously.

The present invention also provides a first deburring step in which the reduced-pressure distillation residue oil of the crude oil atmospheric distillation residue oil is brought into contact with the debridging solvent to separate the first deburred oil and the first impregnated oil. And the first impregnated oil and the desorbed solvent are brought into contact with each other under a desorbing condition different from that of the first deburring step to separate the second debris oil and the second impregnated oil. Degreasing step, a first polar solvent extracting step of bringing the first desorbed oil and the polar solvent into contact with each other to separate the first extract and the first raffinate, and a second degreased oil And a polar solvent are brought into contact with each other, a second polar solvent extraction step for separating the second extract and the second raffinate, and a lubricating base oil is obtained from the first raffinate and / or the second raffinate. Asphalt from the first productizing step and the first impregnated oil and / or the second impregnated oil A high aromatic base oil containing the first extract and / or the second extract, and at least one of a lubricant base oil and asphalt. A method for producing petroleum products is provided.

  According to the method for producing a petroleum product of the present invention, a specific base carcinogenic polycyclic aromatic compound is sufficiently reduced, a highly aromatic base oil useful as a rubber compounding oil, a lubricating base oil and an asphalt It is possible to provide a method for producing a petroleum product that can be obtained by combining at least one of them. Such a production method is extremely useful industrially because a plurality of types of petroleum products including a highly aromatic base oil with sufficiently reduced harmful components can be produced simultaneously.

In the method for producing a petroleum product according to the present invention, the yield of the first defragmented oil is 1 to 30% by volume based on the vacuum distillation residue oil in the first deburring step, and It is preferable to adjust the solvent ratio and / or the deflaking temperature so that the kinematic viscosity at 100 ° C. is 15 to 30 mm ² / s.

In the method for producing a petroleum product of the present invention, the kinematic viscosity at 40 ° C. is less than 400 mm ² / s and the flash point is 280 by subjecting the first raffinate to a refining treatment including a dewaxing treatment in the production step. It is preferable to obtain a lubricating base oil having a aniline point of 100 ° C or higher, a pour point of -5 ° C or lower, and a basic nitrogen content of 0.01 mass% or lower.

Moreover, in the manufacturing method of the petroleum product of this invention, the yield of the 2nd debris oil is 15-50 volume% on the basis of vacuum distillation residue oil in the 2nd deburring process, It is preferable to adjust the solvent ratio and / or the deflaking temperature so that the kinematic viscosity at 100 ° C. of the oil is 30 to 60 mm ² / s.

In the method for producing a petroleum product of the present invention, the kinematic viscosity at 40 ° C. is 400 mm ² / s or more and the flash point is 280 by subjecting the second raffinate to a refining treatment including a dewaxing treatment in the production step. It is preferable to obtain a lubricating base oil having a aniline point of 100 ° C or higher, a pour point of -5 ° C or lower, and a basic nitrogen content of 0.01 mass% or lower.

In the method for producing a petroleum product of the present invention, in the second polar solvent extraction step, the yield of the second extract is 15 to 50% by volume based on the second desorbed oil, The kinematic viscosity at 40 ° C. of the extract is 600 mm ² / s or more, the aniline point is 90 ° C. or less, the flash point is 250 ° C. or more, the asphaltene content is 3 mass% or less, and the content of benzo (a) pyrene is 1 mass ppm or less. And the total content of the specific aromatic compound (PAH) is preferably 10 ppm by mass or less.

  The present invention also provides a petroleum product comprising at least one selected from a lubricating base oil, a highly aromatic base oil and asphalt obtained by the method for producing a petroleum product having the above characteristics.

  According to the present invention, as a petroleum product, a specific base carcinogenic polycyclic aromatic compound is sufficiently reduced, and together with a highly aromatic base oil useful as a rubber compounding oil, at least one of a lubricating base oil and asphalt is used. The manufacturing method of the petroleum product which can be obtained together, and the petroleum product obtained by the said manufacturing method can be provided.

It is process schematic of the manufacturing method of the petroleum product which is one Embodiment of this invention. It is process schematic of the manufacturing method of the petroleum product which is another embodiment of this invention.

  In the following, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. In the drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a process schematic diagram of a method for producing a petroleum product of the present embodiment.

  In the method for producing a petroleum product according to the present embodiment, the first degassed oil and the first degassed oil are brought into contact with each other in the first degassing tower 10 between the vacuum distillation residue oil of the crude oil atmospheric distillation residue oil and the degassed solvent. The first desorbing step for separating the first debris oil and the desorbing solvent at the second deburring tower 20 under the deburring conditions different from those of the first deburring step. Then, the second defrosting step for separating the second desorbed oil and the second impregnated oil, the first desorbed oil and the polar solvent are contacted in the first extraction tower 30, The first extract of the first polar solvent that separates the first extract and the first raffinate, the second desorbed oil and the polar solvent are brought into contact with each other in the second extraction tower 40, and the second extract is obtained. A second polar solvent extraction step that separates into a second raffinate and a first raffinate and / or a second raffinate With obtaining Aburamotoyu has commercialized obtaining a bitumen from a first free gravel oil and / or the second containing gravel oil.

  According to the production method of the present embodiment, a petroleum product comprising a highly aromatic base oil for rubber compounding oil not containing a specific amount or more of a specific carcinogenic polycyclic aromatic compound, a lubricating base oil and asphalt. A method for producing a petroleum product suitable for production can be provided. Details of each step will be described below.

(First removal process)
In the first degassing step, the reduced-pressure distillation residue oil of the crude oil atmospheric distillation residue and the degassed solvent are brought into countercurrent contact within the first degassing tower 10 to bring the first degassed oil and the first degassed oil into contact with each other. This is a step of separating into impregnated oil to obtain a first desorbed oil and a first impregnated oil. The desorbing solvent is appropriately recovered using a recovery tower (not shown) provided on the downstream side of the first degassing tower 10 and recycled.

  The removal solvent is supplied from the pipe 14 to the first removal tower 10. On the other hand, the vacuum distillation residue oil is supplied from the pipe 12 to the first degassing tower 10. Then, the first drained oil is obtained from the pipe 16 and the first impregnated oil is obtained from the pipe 18.

As a desolving solvent, nonpolar light hydrocarbons such as propane and butane, preferably propane is used. As for the condition for removal, the kinematic viscosity at 100 ° C. of the first removal oil is preferably 10 to 35 mm ² / s, more preferably 15 to 30 mm ² / s, and still more preferably 18 to 28 mm ² / s. The degassing temperature can be adjusted by changing the top temperature and / or bottom temperature of the first degassing tower 10. The removal conditions of the first removal process can be, for example, as follows.

-Solvent ratio: As volume ratio on the basis of vacuum distillation residue oil, Preferably it is 1-6, More preferably, it is 1.5-4, More preferably, it is 2-4.
-The tower top temperature of the first degassing tower 10: Preferably it is 60-120 degreeC, More preferably, it is 80-100 degreeC, More preferably, it is 85-95 degreeC.
-The bottom temperature of the first degassing tower 10: Preferably it is 50-100 degreeC, More preferably, it is 60-90 degreeC, More preferably, it is 70-85 degreeC.
-Yield of first desorbed oil: preferably 1 to 30% by volume, more preferably 2 to 20% by volume, and still more preferably 3 to 15% by volume, based on the vacuum distillation residue oil.

  The first desorbed oil thus obtained may be used in a first polar solvent extraction step, which will be described later, and separated into a first raffinate and a first extract. On the other hand, the first impregnated oil is used as a raw material for obtaining a petroleum product containing asphalt, but is used as a raw material for the second deburring step to obtain asphalt, a highly aromatic base oil, or a lubricating base oil. It may be used as it is as a raw material for asphalt. The highly aromatic base oil and the lubricating base oil made from the first impregnated oil are respectively obtained from the second extract and the second raffinate separated in the second polar solvent extraction step described later. It is preferable. Asphalt can be produced by a conventional method using the first impregnated oil.

(Second removal process)
In the second degreasing step, the first debris oil and the demarcation solvent are brought into countercurrent contact in the second deburring tower 20 to be separated into the second debris oil and the second debris oil. And a second exfoliated oil and a second impregnated oil. The desolving solvent is appropriately recovered by using a recovery tower (not shown) provided on the downstream side of the second degassing tower 20 and recycled.

  The removal solvent is supplied from the pipe 24 to the second removal tower 20. On the other hand, the first impregnated oil is supplied from the pipe 18 to the second escape tower 20. Then, the second drained oil is obtained from the pipe 26 and the second impregnated oil is obtained from the pipe 28.

  As the removal solvent, nonpolar light hydrocarbons such as propane and butane, preferably propane, are used as in the first removal process. The removal solvent used in the second removal process may be the same as or different from that in the first removal process, but it is more preferable to use the same removal solvent from the viewpoint of simplifying the process.

There are no particular restrictions on the escape conditions as long as they are different from the escape conditions in the first removal process. For example, the solvent ratio, tower, and the like so that the kinematic viscosity at 100 ° C. of the second exfoliated oil is 30 to 60 mm ² / s, preferably 35 to 50 mm ² / s, more preferably 36 to 45 mm ² / s. It is preferable to adjust the top temperature and / or the bottom temperature. The degassing temperature can be adjusted by changing the top temperature and / or bottom temperature of the second degassing tower 20. The removal conditions of the second removal process can be, for example, as follows.

Solvent ratio: 1 to 10, preferably 4 to 8, more preferably 5 to 7 as a volume ratio based on the first impregnated oil.
-The top temperature of the second degassing tower 20: 50 to 110 ° C, preferably 60 to 80 ° C.
-The bottom temperature of the 2nd removal tower 20: 40-80 degreeC, Preferably it is 50-60 degreeC.
-Yield of the second desorbed oil: 15 to 50% by volume, preferably 20 to 45% by volume, more preferably 25 to 40% by volume based on the vacuum distillation residue oil that is the raw material of the first deburred step %.

  The solvent ratio in the second removal process is preferably 1.5 to 10 times, more preferably 2 to 5 times, and 2.5 to 4 times the solvent ratio in the first removal process. More preferably.

  The tower top temperature in the second degassing step is preferably lower by 10 to 30 ° C and more preferably 15 to 25 ° C than the tower top temperature in the first degassing step. The tower bottom temperature in the second degassing step is preferably lower by 10 to 30 ° C and more preferably 15 to 25 ° C than the tower bottom temperature in the first deburring step.

  The second desorbed oil thus obtained may be separated into a second raffinate and a second extract by using it as a raw material for a second polar solvent extraction step described later. On the other hand, the second impregnated oil has a higher asphaltene content than the first impregnated oil, and is particularly suitable as a raw material for asphalt. Asphalt can be produced by a conventional method using the second impregnated oil.

(First polar solvent extraction step)
In the first polar solvent extraction step, the first desorbed oil and the polar solvent are brought into countercurrent contact with each other in the first extraction tower 30, and the first desorbed oil is converted into the first raffinate and the first extract. And obtaining a first raffinate and a first extract. The polar solvent is appropriately recovered by using a recovery tower (not shown) provided on the downstream side of the first extraction tower 30 and recycled. 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, a general lubricating oil is used. It is preferable to use furfural in that the solvent extraction equipment for the base oil can be diverted.

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

There is no restriction | limiting in particular in the extraction conditions of a 1st polar solvent extraction process, For example, the kinematic viscosity in 100 degreeC of the 1st extract becomes like this. Preferably it is 30-70 mm < ² > / s, More preferably, it is 40-60 mm < ² > / s. The extraction conditions can be adjusted as follows. The extraction conditions of the first polar solvent extraction step can be, for example, as follows.

-Solvent ratio: As a volume ratio on the basis of the first degassed oil, it is preferably 1 to 5, more preferably 2 to 4, more preferably 2.5 to 3.5.
-The top temperature of the 1st extraction tower 30: Preferably it is 100-150 degreeC, More preferably, it is 120-140 degreeC, More preferably, it is 126-136 degreeC.
-The bottom temperature of the 1st extraction tower 30: Preferably it is 60-130 degreeC, More preferably, it is 80-125 degreeC, More preferably, it is 86-120 degreeC.
-Yield of 1st extract: Preferably it is 15-50 volume%, More preferably, it is 20-40 volume%, More preferably, it is 25-33 volume% on the basis of the 1st dehulled oil.

The first extract thus obtained preferably has the following properties.
Aniline point: 90 ° C. or lower, preferably 80 ° C. or lower, more preferably 75 ° C. or lower. Preferably it is 40 degreeC or more, More preferably, it is 60 degreeC or more, More preferably, it is 65 degreeC or more.
· ASTM D3238 by the _measured% C A: 20 to 45, preferably 20 to 40, preferably 25 to 35, more preferably 27-32.
· ASTM D3238 by the _measured% C N: 5 to 25, preferably 5 to 15, more preferably 5 to 12.
Asphaltene content: 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
• Kinematic viscosity at 100 ° C .: 30 to 70 mm ² / s, preferably 40 to 60 mm ² / s.
Kinematic viscosity at 40 ° C .: 600 mm ² / s or more, preferably 800 to 5000 mm ² / s, more preferably 1000 to 3000 mm ² / s
-Benzo (a) pyrene content: 1 mass ppm or less.
-Total content of specific aromatic compound (PAH): 10 mass ppm or less.

The specific aromatic compound (PAH) in the present specification means the aromatic compound (PAH) of the following 1) to 8).
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)
Moreover, the benzo (a) pyrene as used in this specification means the benzo (a) pyrene (BaP) of said 1).

  These specific aromatic compounds (PAH) can generally be analyzed quantitatively by GC-MS analysis by preparing a sample to which an internal standard substance has been added after separating and concentrating the target component.

  Using this first extract, a highly aromatic base oil is obtained. Since the first extract is aromatic, has a low aniline point, and the specific carcinogenic polycyclic aromatic compound is sufficiently low, the highly aromatic base oil containing the first extract is a rubber compounding oil. It is suitable as. Moreover, since the 1st extract is a high calorie, it can be used also as a heating fuel of the apparatus which has the 1st extraction tower 30 in this manufacturing method, or another apparatus.

  On the other hand, the first raffinate obtained by the first polar solvent extraction step is processed in the productization step using the dewaxing device 50 and the hydrofinishing device 60 through the pipe 36. In the commercialization process, the first raffinate can be refined by dewaxing and hydrofinishing to produce a lubricating base oil. The lubricating base oil thus obtained is between a solvent-purified lube base oil obtained from a normal vacuum distillation fraction and a solvent-purified lube base oil (bright stock) obtained from a normal debris oil. The kinematic viscosity is different from that of the conventional lubricating base oil. That is, the method for producing the lubricating base oil is the second debris obtained by adjusting the desorption conditions in the first and second deburring steps without using the usual fractionation method by distillation. Since oil is used as a raw material, the production method and the properties of the obtained lubricant base oil are different from those of the conventional one. And since it is highly paraffinic compared with conventional solvent-refined lubricating base oil, it is useful as one of the base materials for various lubricating oil products.

The lubricating base oil thus obtained has the following properties, for example.
Density (15 ° C.): 0.88 to 0.92 g / cm ³ .
Flash point (COC): 280 ° C or higher, preferably 300 ° C or higher.
-Kinematic viscosity (40 degreeC): Less than 400 mm < ² > / s, Preferably it is 200-350 mm < ² > / s.
-Kinematic viscosity (100 degreeC): 15-30 mm < ² > / s, Preferably it is 18-25 mm < ² > / s.
-Viscosity index: 90 or more, preferably 95-105.
-Aniline point: 100 degreeC or more, Preferably it is 115-125 degreeC.
-Basic nitrogen content: less than 0.01 mass%.
Pour point: −5 ° C. or lower, preferably −20 to −10 ° C.
% C _P : 65-75, preferably 68-72.
-% C _A : 10 or less, preferably 3-8, more preferably 5-7.
% C _P /% C _A : 8 or more, preferably 10 to 20, more preferably 11 to 15.
-Benzo (a) pyrene content: 1 mass ppm or less.
-Total content of specific aromatic compound (PAH): 10 mass ppm or less.

(Second polar solvent extraction step)
In the second polar solvent extraction step, the second desorbed oil and the polar solvent are brought into countercurrent contact with the second extraction tower 40 to be separated into the second extract and the second raffinate, In this step, a second extract and a second raffinate are obtained. The polar solvent is appropriately recovered by using a recovery tower (not shown) provided on the downstream side of the second extraction tower 40 and recycled. 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, a general lubricating oil is used. It is preferable to use furfural in that the solvent extraction equipment for base oil can be used as it is. Moreover, from the viewpoint of process simplification, it is preferable to use the same polar solvent used in the first and second polar solvent extraction steps.

  The polar solvent is supplied from the pipe 44 to the second extraction tower 40. On the other hand, the second drained oil is supplied to the second extraction tower 40 through the pipe 26. A second raffinate is obtained from the pipe 46 and a second extract is obtained from the pipe 48.

The extraction conditions can be the same as in the first polar solvent extraction step. Specifically, it can be as follows.
-Solvent ratio: As volume ratio on the basis of the 2nd debris oil, Preferably it is 1-5, More preferably, it is 2-4, More preferably, it is 2.5-3.5.
-The top temperature of the second extraction tower 40: preferably 100 to 150 ° C, more preferably 120 to 140 ° C, still more preferably 126 to 136 ° C
-Bottom temperature of the second extraction tower 40: preferably 60 to 130 ° C, more preferably 80 to 125 ° C, still more preferably 86 to 120 ° C.
Second extract yield: 15 to 50% by volume, preferably 20 to 40% by volume, and more preferably 25 to 33% by volume with respect to the second desorbed oil.

  The second extract obtained in the second polar solvent extraction step is heavier than a normal extract. Specifically, the second extract has the following properties.

  The aniline point of the second extract is 40 to 90 ° C, preferably 45 to 70 ° C, more preferably 50 to 65 ° C. If the aniline point is in the above range, even if a lubricating base oil having a high aniline point is blended, the rubber blend has an aniline point that is excellent in compatibility with rubber and suitable for maintaining the properties of the rubber composition. It becomes easy to produce oil. In addition, the aniline point in this specification means the aniline point measured based on JISK2256-1985.

As the composition of the second extract,% _{C A} is 20 to 45, preferably 25 to 45, preferably 30 to 40,% _{C N} 5-25, preferably 5-15, preferably 6-12. Moreover,% _{C P is,% C A,%} C _N is determined depending on, preferably 40-70, more preferably 48-64. If it is the said range, even if it mix | blends lubricating oil base oil with high paraffin property, it will become easy to manufacture the rubber compounding oil which has the compatibility suitable with rubber | gum, and has a suitable composition in order to maintain the characteristic of a rubber composition. . Incidentally, _say% C P in the present invention,% _C A _N and% _{C A,} obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number The percentage of the total number of naphthene carbons to the total number of carbons, and the percentage of the total number of aromatic carbons to the total number of carbons.

  The basic extract has a basic nitrogen content of 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more. A high basic nitrogen content of the second extract means that the nitrogen content of the second raffinate is low, and the purification efficiency of the lubricating base oil is increased. Therefore, from the economical viewpoint, it is preferable to use the second extract having a high basic nitrogen content as the rubber compounding oil. In addition, the basic nitrogen content in this specification means the nitrogen content by the chemiluminescence method measured based on JISK2609.

  The pour point of the second extract is + 30 ° C. or less, preferably +5 to + 25 ° C., more preferably +7.5 to + 20 ° C., and further preferably +7.5 to + 15 ° C. In addition, the pour point as used in this specification means the pour point measured based on JISK2269.

  The second extract preferably has a content of the above-mentioned eight kinds of specific aromatic compounds (PAH) of not more than a specific amount.

  In the second extract, the content of benzo (a) pyrene (BaP) in 1) is 1 ppm by mass or less, and the total content of the specific aromatic compound (PAH) is 10 ppm by mass or less. preferable. As a result, it is possible to produce a rubber compounding oil with higher safety without concern about carcinogenicity.

The kinematic viscosity at 40 ° C. of the second extract is 600 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 / s or more. Moreover, the kinematic viscosity at 40 ° C. of the second extract is preferably 20000 mm ² / s or less, more preferably 10,000 mm ² / s or less. If it is the said range, there exists a tendency which becomes easy to obtain the rubber compounding oil which has appropriate kinematic viscosity. The kinematic viscosity at each temperature referred to in this specification means the kinematic viscosity at each temperature measured according to JIS K2283.

  The asphaltene content of the second extract is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. Thus, from the viewpoint of obtaining the second extract in which the asphaltene content is sufficiently reduced, it is preferable that the asphaltene content in the deasphalted oil is sufficiently reduced in the second deburring step. In addition, the asphaltene content as used in this specification means the asphaltene content measured based on IP-143.

  There are no particular restrictions on the flash point of the second extract. However, the flash point of the second extract is preferably 250 ° C. or higher, more preferably 270 ° C. or higher, from the viewpoint that the flash point of the rubber compounding oil is 250 ° C. or higher and excluded from the dangerous substances No. 4 petroleums. More preferably, it is 290 degreeC or more, Most preferably, it is 300 degreeC or more. In addition, the flash point as used in this specification means the flash point by the Cleveland open type (COC) measured based on JIS K2265.

  There is no restriction | limiting in particular in the total aromatic content of a 2nd extract. However, the total aromatic content of the second extract is usually 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and preferably 90% by mass. Hereinafter, it is more preferably 80% by mass or less, and further preferably 75% by mass or less.

  When the total aromatic content is less than 50% by mass, it tends to be difficult to obtain a rubber compounding oil having high aromaticity. On the other hand, when the total aromatic content exceeds 90% by mass, the yield of the second extract in the second polar solvent extraction step is deteriorated, and the above-mentioned specific aromatic compound (PAH) in the second extract is obtained. Tends to be difficult to reduce. In addition, the total aromatic content as used in this specification means content of the aromatic fraction (aromatics fraction) measured based on ASTMD2549.

  As long as the second extract has the above properties, it may be further subjected to dewaxing treatment or purification treatment as necessary. However, from the economical point of view, it is preferable to use the unrefined second extract as it is as a highly aromatic base oil, or to mix with other components to obtain a highly aromatic base oil.

  The second raffinate obtained by the second polar solvent extraction step passes through the pipe 46 and is processed in a productization step using the dewaxing device 51 and the hydrofinishing device 61. In the commercialization process, the second raffinate can be refined by dewaxing and hydrofinishing to produce a lubricating base oil. The lubricating base oil thus obtained corresponds to a lubricating base oil called bright stock. This lubricating base oil has properties different from those of ordinary bright stock because the above-mentioned first raffinate component has been removed. The properties of the lubricating base oil have the following properties, for example.

Density (15 ° C.): 0.88 to 0.92 g / cm ³ .
Flash point (COC): 280 ° C or higher, preferably 300 ° C or higher.
- kinematic viscosity ^{(40 ℃): 400mm 2 /} s or more, preferably 450~600mm ² / s.
-Kinematic viscosity (100 degreeC): 25-40 mm < ² > / s, Preferably it is 28-35 mm < ² > / s.
-Viscosity index: 90 or more, preferably 95-100.
-Aniline point: 100 degreeC or more, Preferably it is 115-125 degreeC.
-Basic nitrogen content: less than 0.01 mass%.
Pour point: −5 ° C. or lower, preferably −20 to −10 ° C.
% C _P : 60-70, preferably 63-68.
-% C _A : 12 or less, preferably 3 to 10, more preferably 6 to 9.
% C _P /% C _A : preferably 5 to 10, more preferably 6 to 9.
-Benzo (a) pyrene content: 1 mass ppm or less.
-Total content of specific aromatic compound (PAH): 10 mass ppm or less.

  In the present embodiment, the first and second raffinates can be used as raw materials for the lubricating base oil. On the other hand, the extract can be used as it is as a highly aromatic base oil or as a highly aromatic base oil by mixing other base materials and extracts. In addition, the first impregnated oil (residual oil not extracted into the solvent to be removed: oil containing a large amount of asphaltenes) is a raw material for asphalt, lubricating base oil, and highly aromatic base oil. That is, the first impregnated oil may be asphalt as it is, or may be a raw material for a lubricating base oil and a highly aromatic base oil. In other words, the first impregnated oil can be refined and efficiently made into each petroleum product or used as a raw material.

  As described above, the method for producing a petroleum product according to the present embodiment is excellent in that it is a production method capable of producing a wide variety of petroleum products as co-products from crude oil.

  In the present 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, one extraction tower is used alternately as the first extraction tower 30 and the second extraction tower 40. Thus, when combining one extraction etc., the raffinate obtained by the 1st polar solvent extraction process (what remove | excluded polar solvent is preferable) is once stored in a tank etc., and extraction conditions are set to 2nd. The second polar solvent extraction step may be performed by reintroducing the extraction column adjusted to the conditions of the solvent extraction step. By doing so, the aromatic-containing base oil of this embodiment can be obtained without excessive capital investment, which is reasonable in terms of economy. Similarly to the extraction tower, it is not necessary to use separate extraction towers as the first and second degassing towers, and one degassing tower is used as the first degassing tower 10 and the second degassing tower 20. It may be used as

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, in the above embodiment, in the commercialization step, the lubricating base oil is obtained from the first raffinate and / or the second raffinate, and the asphalt is obtained from the first impregnated oil and / or the second impregnated oil. However, it is also possible to obtain only one of the lubricating base oil and asphalt.

  FIG. 2 is a process schematic diagram showing another embodiment of the present invention. As shown in FIG. 2, the high aromatic base oil containing the first extract, the lubricating base oil, and the asphalt without performing the second exfoliation step and the second polar solvent extraction step in the above embodiment. It is good also as a manufacturing method of a petroleum product containing at least one of these.

  That is, in the method for producing a petroleum product shown in FIG. 2, the first distillation oil is obtained by bringing the reduced-pressure distillation residue oil of the crude oil atmospheric distillation residue into contact with the removal solvent in the first removal tower 10. The first extract and the first raffinate are obtained by bringing the first desorbed oil and the polar solvent into contact with each other in the first extraction tower 30 to be separated into the first impregnated oil. A first polar solvent extraction step that separates into two and a refining treatment by dewaxing treatment and hydrofinishing treatment to the first raffinate to obtain a lubricating base oil, and to obtain asphalt from the first impregnated oil It has a commercialization process. Each step can be performed in the same manner as in the above embodiment.

  From the first impregnated oil, only asphalt may be obtained as it is, but a lubricating base oil and / or a highly aromatic base oil may be obtained, and the process is not particularly limited. . For example, the first impregnated oil is supplied to the first degassing tower 10 in FIG. 2 and the process as shown in FIG. 2 is repeated to select at least selected from asphalt, lubricating base oil, and highly aromatic base oil. You may get a kind. In addition, the first impregnated oil is supplied to the second degassing tower 20 in FIG. 1 and at least selected from asphalt, lubricating base oil, and highly aromatic base oil through the steps shown in FIG. You may get a kind.

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

[Example 1]
Petroleum products were produced using the production apparatus shown in FIG.
(Process 1)
The reduced-pressure distillation residue oil of crude oil and the propane are introduced into the first degassing tower 10 and brought into countercurrent contact under the conditions shown in Table 1, and the first impregnated oil shown in Table 1 And a first exfoliating oil were obtained. The first impregnated oil is a residual oil that has not been extracted into the solvent to be removed and contains a large amount of asphaltenes.

(Process 2)
Subsequently, the first impregnated oil and propane obtained in step 1 are introduced into the second degassing tower 20 and brought into countercurrent contact under the conditions described in Table 1, and the second Impregnated oil and second exfoliated oil were obtained. The second impregnated oil was an asphalt raw material.

(Steps 3 and 4)
The first drained oil and the polar solvent furfural are introduced into the first extraction tower 30 and brought into countercurrent contact under the conditions shown in Table 2 to obtain the first extract shown in Table 2 and the first extract. And got a raffinate.

  The first raffinate was subjected to solvent dewaxing treatment to obtain a dewaxed oil having a pour point of -10 ° C or lower. Then, the hydrofinishing process of the obtained dewaxed oil was performed and the lubricating base oil was obtained. The properties of the lubricating base oil thus obtained are shown in the column of Step 4 in Table 2.

  The lubricating base oil thus obtained is between a solvent refined lubricating base oil obtained from a conventional vacuum distillation fraction and a solvent refined lubricating base oil (bright stock) obtained from a conventional debris oil. It had a kinematic viscosity. And this lubricating oil base oil is different from the conventional lubricating oil base oil because it can be obtained by using the debris oil obtained by adjusting the debris conditions without using a conventional fractionation method by distillation. It had properties. That is, since it has higher paraffinity than conventional lubricating base oil, it is useful as one of base materials for various lubricating oil products.

(Steps 5 and 6)
The second desorbed oil obtained in the above step 2 and the furfural which is a polar solvent are introduced into the second extraction tower 40 and brought into countercurrent contact under the same conditions as in step 3, and are shown in Table 2. Two extracts and a second raffinate were obtained. The second extract has a higher kinematic viscosity, a higher aromaticity, and a lower aniline point than the first extract. That is, the second extract is a component obtained by removing light components and components having low aromaticity without performing distillation by performing removal in two stages. Since the second extract is substantially free of a specific carcinogenic substance, it is useful as a rubber compounding oil or a highly aromatic base oil as a base material thereof.

  The first raffinate was subjected to solvent dewaxing treatment to obtain a dewaxed oil having a pour point of -10 ° C or lower. Then, the hydrofinishing process of the obtained dewaxed oil was performed and the lubricating base oil was obtained. The properties of the lubricating base oil thus obtained are shown in the column of step 6 in Table 2.

  The total content of benzo (a) pyrene and 8 kinds of specific aromatic compounds (PAH) was measured as follows. First, 1 g of aromatic-containing base oil was dissolved in hexane in a 50 ml flask to prepare a 2% by mass sample solution. This sample solution was loaded onto 5% by mass water-containing silica gel, washed with hexane, and then the target component was eluted with a 1% by volume acetone / hexane solution. After the eluate was concentrated, a sample to which an internal standard was added was prepared, and identified and quantified with a general gas chromatograph mass spectrometer (GC-MS).

  According to the production method of the present embodiment, two types of lubricating base oils can be produced which use reduced-pressure distillation residue oil as a raw material, have different kinematic viscosities without using a distillation apparatus, and have a flash point of 280 ° C. or higher. At the same time, an aromatic content and a flash point are high, and an extract suitable as a rubber compounding oil can be produced at the same time.

[Comparative example]
A reduced-pressure distillation fraction (500N equivalent fraction) of crude atmospheric distillation residue and a polar solvent furfural were brought into countercurrent contact under the conditions shown in Table 2 to obtain a raffinate and an extract. The obtained raffinate was subjected to solvent dewaxing treatment to obtain a dewaxed oil having a pour point of −10 ° C. or lower. The dewaxed oil was hydrofinished to obtain a lubricating base oil. The properties of the lubricating base oil thus obtained are shown in the column for the polar solvent extraction step in Table 2. As shown in Table 2, the flash point of the lubricating base oil of this comparative example was less than 280 ° C. Moreover, the obtained extract had a total content of the specific aromatic compound exceeding 10 mass ppm.

  DESCRIPTION OF SYMBOLS 10 ... 1st deburring tower, 20 ... 2nd deburring tower, 30 ... 1st extraction tower, 40 ... 2nd extraction tower, 50,51 ... Dewaxing apparatus, 60,61 ... Hydrofinishing apparatus .

Claims (6)

A first deburring step in which a reduced-pressure distillation residue oil of a crude oil atmospheric distillation residue and a desolvation solvent are brought into contact with each other to separate into a first deburred oil and a first impregnated oil;
A first polar solvent extraction step in which the first desorbed oil and the polar solvent are contacted to separate the first extract and the first raffinate;
Obtaining a highly aromatic base oil comprising the first extract;
A first productizing step for obtaining a lubricating base oil from the first raffinate and a second productizing step for obtaining asphalt from the first impregnated oil,
As a petroleum product, a highly aromatic base oil containing the first extract, and at least one of the lubricating base oil and the asphalt, a method for producing a petroleum product,
The high aromatic base oil containing the first extract has a kinematic viscosity at 40 ° C. of 600 mm ² / s or more, an aniline point of 65 ° C. or more and 90 ° C. or less, a flash point of 250 ° C. or more, and an asphaltene content of 3 mass. % or less, ASTM D3238 in accordance% _{C a} is 20 to 45,% _{C N} is 5 to 25, the content of benzo (a) pyrene less than 1 mass ppm, and the total content of the specific aromatic compound (PAH) 10 Mass ppm or less,
In the first degassing step, the ratio of the desolving solvent brought into contact with the vacuum distillation residue oil is 1.5 to 4 as a volume ratio based on the vacuum distillation residue oil,
The yield of the first debris oil is 1-30% by volume based on the vacuum distillation residue oil, and the kinematic viscosity at 100 ° C. of the first debris oil is 15-30 mm ² / s. Adjusting the solvent ratio and / or deflaking temperature,
In the first polar solvent extraction step, the ratio of the polar solvent brought into contact with the first desorbed oil is set to 1 to 5 as a volume ratio based on the first desorbed oil . Production method. The second debris oil and the second debris oil are separated by bringing the first debris oil and the desorbing solvent into contact with each other under a deburring condition different from that of the first deburring step. The process of taking off
A second polar solvent extraction step of contacting the second desorbed oil and the polar solvent to separate the second extract and the second raffinate;
A first productizing step for obtaining a lubricating base oil from the first raffinate and / or the second raffinate; and a second step for obtaining asphalt from the first impregnated oil and / or the second impregnated oil. And at least one of the commercialization processes,
In the second removal process, the ratio of the removal solvent to be contacted with the first removal oil is 1 to 10 as a volume ratio based on the first inclusion oil,
In the second polar solvent extraction step, the ratio of the polar solvent brought into contact with the second desorbed oil is 1 to 5 as a volume ratio based on the second desorbed oil ,
The high aromatic base oil containing the first extract and / or the second extract and at least one of the lubricating base oil and the asphalt are obtained as petroleum products. Production method of petroleum products. In the commercialization step, by subjecting the first raffinate to a purification treatment including a dewaxing treatment,
The kinematic viscosity at 40 ° C. is less than 400 mm ² / s,
The flash point is 280 ° C or higher,
Aniline point is 100 ° C or higher,
The method for producing a petroleum product according to claim 1 or 2, wherein the lubricating base oil having a pour point of -5 ° C or lower and a basic nitrogen content of 0.01 mass% or lower is obtained. In the second escape step,
The yield of the second degassed oil is 15 to 50% by volume based on the vacuum distillation residue oil;
The method for producing a petroleum product according to claim 2, wherein the solvent ratio and / or the defrosting temperature are adjusted such that the kinematic viscosity at 100 ° C of the second desorbed oil is 30 to 60 mm ² / s. In the commercialization step, by subjecting the second raffinate to a purification treatment including a dewaxing treatment,
The kinematic viscosity at 40 ° C. is 400 mm ² / s or more,
The flash point is 280 ° C or higher,
Aniline point is 100 ° C or higher,
The method for producing a petroleum product according to claim 2 or 4 , wherein the lubricating base oil having a pour point of -5 ° C or lower and a basic nitrogen content of 0.01 mass% or lower is obtained. In the second polar solvent extraction step,
The yield of the second extract is 15 to 50% by volume based on the second desorbed oil;
The kinematic viscosity at 40 ° C. of the second extract is 600 mm ² / s or more, the aniline point is 90 ° C. or less, the flash point is 250 ° C. or more, the asphaltene content is 3% by mass or less, and the content of benzo (a) pyrene is The manufacturing method of the petroleum product of Claim 2 or 4 whose total content of 1 mass ppm or less and a specific aromatic compound (PAH) is 10 mass ppm or less.

Images