Title of Invention

PROCESS OIL, PROCESS FOR PRODUCTION OF DEASPHALTED OIL, PROCESS FOR PRODUCTION OF EXTRACT, AND PROCESS FOR PRODUCTION OF PROCESS OIL

Abstract The present invention is related to a process oil using as a raw material a deasphalted oil obtained by deasphalting a vacuum residual oil of a crude oil and a manufacturing method of the process oil, the process oil having properties of: (a) a polycyclic aromatics (PCA) content of less man 3 mass%; (b) a viscosity (100°C) of 40 to 70 mm2/s; (c) an aniline point of 85 to 100°C; (d) a flash point of 250°C or higher; (e) an aromatic hydrocarbon content of 40 to 55 mass%; and (f) a polar substance content of 10 to 15 mass%. The present invention is also related to a process oil and a manufacturing method of the process oil, the process oil obtained by mixing: an extract obtained by deasphalting and solvent-extracting a vacuum residual oil of a crude oil; and a lubricant base oil having a polycyclic aromatics (PCA) content of less than 3 mass%, and having properties of: (a) a polycyclic aromatics (PCA) content of less than 3 mass%; (i) a viscosity (100°C) of 30 to 80 mm2/s; (j) an aniline point of 90°C or lower; (k) a flash point of 240°C or higher; (1) a benzo(a)pyrene content of 1 mass ppm or less; (m) a specified aromatic compound content of 10 mass ppm or less; and (n) a polar substance content of 10 to 30 mass%.
Full Text

DESCRIPTION
TECHNICAL FIELD
[0001]
The present invention is related to a process oil that is added to a natural rubber
or a synthetic rubber to manufacture a rubber composition, manufacturing methods of a
deasphalted oil and an extract as raw materials for manufacturing the process oil, and a
manufacturing method of the process oil.
BACKGROUND ART
[0002]
A process oil is typically added to a rubber material used for manufacturing a tire
in order to enhance mechanical performances and processability of the rubber material.
The process oil is used as: a constituent of a plasticizer for a thermoplastic resin; a
constituent of a printing ink; and a lubricant or a solvent component used for a softener or
the like for a recycled asphalt, as well as being used with rubber materials such as a
natural rubber and a synthetic rubber.
[0003]
For a process oil used as an additive for the rubber materials, there has been
conventionally employed an extract that is a by-product produced in manufacturing a
paraffinic base oil by solvent refining. However, due to a carcinogenicity problem,
noncarcinogenic aromatic oils for tires have been being manufactured by various
manufacturing methods.
[0004]
In manufacturing a rubber for a tire, since compatibility of the process oil and the
rubber material is regarded as important, an aromatic component of the process oil is an
important factor. However, since excessive dependency on the aromatic component leads
to increase of the carcinogenicity of the process oil, the aromatic oil as a source of the
carcinogenicity has to be removed while maintaining the compatibility of the process oil
and the rubber material in a proper state.

[0005]
Furthermore, a hazardous effect of polycyclic aromatics (PCA; same meaning as
PAH (PolyAromatic Hydrocarbon)) contained in the process oil has been acknowledged
as a problem in recent years. Especially, since the process oil used for an automobile tire
pollutes me environment via dusts of die tire, there has been a demand for reducing the
PCA contained in the process oil. In Europe or other areas, a mineral oil having a PCA
content of 3 mass% or more is restricted in handling. However, since an extracted oil with
high aromatics content obtained by conventional manufacturing methods contains high
contents of the polycyclic aromatics, it has been urgendy required to develop a process oil
with reduced PCA (specifically, less man 3 mass%) and a manufacturing method thereof.
[0006]
With such background, there has been studied a technology for manufacturing a
process oil wim reduced PCA content and capable of balancing the compatibility with a
rubber material and non-carcinogenicity. For example, a technology related to a
manufacturing method of a process oil for a tire rubber has been disclosed, in which a
naphthenic asphaltene and a solvent-extracted oil are combined (see, for instance, Patent
Document 1). As another technology, there has been disclosed a manufacturing method of
a process oil using an extract obtained by solvent-extracting a deasphalted oil (see, for
instance, Patent Document 2 and Patent Document 3).
[0007]
[Patent Document 1] JP-A-11-80434
[Patent Document 2] JP-A-2000-80208
[Patent Document 3] JP-A- 2002-3861
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0008]
However, while the process oil obtained by me technology disclosed in the Patent

Document 1 ensures safety, a rubber composition containing the process oil did not
exhibit performances equal to rubber compositions containing conventional aromatic oils.
In process oils obtained by the technologies disclosed in the Patent Documents 2 and 3,
since the deasphalted oil of a paraffinic residual oil is used as it is, the pour point thereof
is high, which undesirably causes a wax component to be separated out on a surface of a
rubber in a rubber composition using the process oil.
In addition, in the technologies disclosed in the Documents 2 and 3, the extract
obtained by solvent-extracting the deasphalted oil is used in manufacturing the process
oils. However, since the extract contains high content of an aromatic component, further
processing such as extraction and hydrogenation are required to control the content of the
aromatic component to be less than a regulation value, thus requiring many manufacturing
steps.
[0009]
An object of the present invention is to provide a process oil exhibiting
performances equal to conventional aromatic oils while being noncarcinogenic and
excellent in safety, as well as providing a simpler manufacturing method of the process oil.
Another object of the present invention is to provide manufacturing methods of a
deasphalted oil and an extract as raw materials that are favorably used in manufacturing
the process oil.
MEANS FOR SOLVING THE PROBLEMS
[0010]
In order to solve the problem described above, a process oil according to a first
aspect of the present invention uses as a raw material a deasphalted oil obtained by
deasphalting a vacuum residual oil of a crude oil, the process oil having properties of (a)
to (f) below:
(a) a polycyclic aromatics (PC A) content of less than 3 mass%;
(b) a viscosity (100 °C) of 40 to 70 mm2/s;
(c) an aniline point of 85 to 100 °C;

(d) a flash point of 250 °C or higher;
(e) an aromatic hydrocarbon content of 40 to 55 mass%; and
(f) a polar substance content of 10 to 15 mass%.
[0011]
According to the aspect of the present invention, the process oil uses as the raw
material the deasphalted oil obtained by deasphalting die vacuum residual oil of the crude
oil. With the PCA content being less man 3 mass%, the process oil is noncarcinogenic and
excellent in safety. In addition, with the properties of (b) to (f), the process oil can
maintain performances equal to conventional aromatic oils, so mat a rubber composition
made by adding the process oil to a natural rubber or a synthetic rubber will have
preferable rubber properties, while being capable of preventing bleeding wiui the oil
bleeding on a surface of a rubber and separation of a wax component.
Here, the process oil of the present invention uses me deasphalted oil as the raw
material, which may be: a deasphalted oil; any one of oil components made of a
deasphalted oil as a raw material such as a dewaxed oil (a dewaxed deasphalted oil)
obtained by dewaxing the deasphalted oil and an extract extracted from the dewaxed oil;
and a mixture of two or more of the oil components above.
[0012]
The process oil of the present invention preferably has (g) pour point of 40 °C or
lower. By setting the range of the pour point, the wax component is not separated out on
the surface of a rubber to be manufactured, thus improving appearance and commercial
value.
[0013]
The process oil according to the aspect of the present invention preferably shows
an ASTM color phase of 8.0 or lower when being diluted with a toluene of sixty times as
large volume as me process oil
Since the process oil of the present invention contains small content of an
asphaltene component, when used for manufacturing of a colored asphalt, the asphalt will
be finished with a good color.

[0014]
By adjusting the process oil of the present invention to have (h) aniline point of
85 to 95 °C, the PCA content becomes appropriate and the compatibility with a rubber
material is improved, resulting in exhibiting the above described effects more effectively.
[0015]
A process oil according to a second aspect of the present invention is obtained by
mixing: an extract obtained by deasphalting and solvent-extracting a vacuum residual oil
of a crude oil; and a lubricant base oil having a polycyclic aromatics (PCA) content of less
than 3 mass%, the process oil having properties of: (a) and (i) to (n) below:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(i) a viscosity (100 °C) of 30 to 80 mm2/s;
(j) an aniline point of 90 °C or lower;
(k) a flash point of 240 °C or higher;
(1) a benzo(a)pyrene content of 1 mass ppm or less;
(m) a specified aromatic compound content of 10 mass ppm or less; and
(n) a polar substance content of 10 to 30 mass%.
[0016]
According to the aspect of the present invention, the process oil is obtained by
mixing an extract obtained by deasphalting and solvent-extracting the vacuum residual oil
of the crude oil and a predetermined lubricant base oil, and the PCA content is less than 3
mass%, so that the process oil is noncarcinogenic and excellent in safety. In addition, with
the properties of (i) to (n), the process oil can maintain performances equal to
conventional aromatic oils, so that a rubber composition obtained by adding the process
oil to a natural rubber or a synthetic rubber will have preferable rubber properties, while
being capable of preventing bleeding with the oil bleeding on a surface of a rubber and
separation of a wax component.
[0017]
By adjusting the process oil of the present invention to have (o) aniline point of
60 to 90oC, the PCA content becomes appropriate and the compatibility with a rubber

material is improved, resulting in exhibiting the above described effects more effectively.
[0018]
A manufacturing method of a process oil according to a third aspect of the
present invention includes: a deasphalting step for deasphalting a vacuum residual oil of a
crude oil to obtain a deasphalted oil; and a solvent-extraction step for solvent-extracting
the deasphalted oil to obtain an extract with a yield of 50 mass% or higher of the
deasphalted oil, the extract being provided as the process oil.
[0019]
According to the aspect of the present invention, since the manufacturing method
includes the deasphalting step for obtaining the deasphalted oil from the vacuum residual
oil of the crude oil and the solvent-extraction step for solvent-extracting the deasphalted
oil to obtain the extract as the process oil, the process oil having the properties of (a) to (f)
described above can be properly provided.
In the solvent-extraction step for solvent-extracting the deasphalted oil to obtain
the extract, the extract is obtained with the yield of 50 mass% or higher of the deasphalted
oil and the extract is provided as the process oil, so that the process oil with the PCA
content of less than 3 mass% can be securely obtained.
[0020]
A manufacturing method of a process oil according to a fourth aspect of the
present invention includes: a deasphalting step for deasphalting a vacuum residual oil of a
crude oil to obtain a deasphalted oil; and a solvent-extraction step for solvent-extracting
the deasphalted oil to obtain an extract, in which the extract obtained in the
solvent-extraction step and at least one member selected from the group consisting of the
deasphalted oil obtained in the deasphalting step and a mineral oil having a polycyclic
aromatics (PCA) content of less than 3 mass% are mixed to obtain a mixed oil, the mixed
oil being provided as the process oil.
The mixed oil of the extract and the deasphalted oil obtained in the deasphalting
step or the mineral oil with the polycyclic aromatics (PCA) content of less than 3 mass%
may be provided as the process oil. Even with the arrangement, the process oil having the

properties of (a) to (f) can also be provided properly.
In such case, it is not necessary to obtain the extract with the yield of 50 mass%
or higher of the deasphalted oil in the solvent-extraction step for obtaining the extract
from the deasphalted oil, but it is only necessary to mix the extract obtained with a desired
yield and at least one member selected from the group consisting of the deasphalted oil
obtained in the deasphalting step and the mineral oil with the PCA content of less than 3
mass% in order to obtain the process oil. However, there is also no problem in employing
the extract obtained with the yield of 50 mass% or higher of me deasphalted oil, of which
the PCA content is expected to be low.
[0021]
A manufacturing method of a process oil according to a fifth aspect of the present
invention includes: a deasphalting step for deasphalting a vacuum residual oil of a crude
oil to obtain a deasphalted oil; a dewaxing step for dewaxing the deasphalted oil to obtain
a dewaxed oil; and a solvent-extraction step for solvent-extracting me dewaxed oil to
obtain an extract with a yield of 50 mass% or higher of the deasphalted oil, me extract
being provided as the process oil.
[0022]
According to the aspect of the present invention, since the manufacturing memod
includes the deasphalting step for obtaining the deasphalted oil from the vacuum residual
oil of the crude oil, the dewaxing step for obtaining the dewaxed oil from the deasphalted
oil and the solvent-extraction step for solvent-extracting the dewaxed oil to obtain the
extract as the process oil, the process oil having me properties of (a) to (f) described above
can be properly provided.
Especially, dewaxing the deasphalted oil can provide proper fluidity to the
process oil, which accordingly facilitates handling of the oil, while preventing me wax
component from being separated out on the surface of a rubber to be manufactured.
In the solvent-extraction step for extracting the dewaxed oil to obtain the extract,
the extract is obtained with a yield of 50 mass% or higher of the deasphalted oil and the
extract is provided as the process oil, so that the process oil with the PCA content of less

and the deasphalted oil or the like is used as the process oils, the process oil having the
properties of (a) to (f) can be obtained effectively, thus enhancing properties of the rubber
composition.
[0025]
In the manufacturing method of the process oil according to the aspect of the
present invention, it is preferable that a yield of the deasphalted oil obtained in the
deasphalting step is 30 mass% or higher of the vacuum residual oil, and a viscosity at
100 °C of the deasphalted oil is 30 to 50 mm2/s.
According to the aspect of the present invention, since the yield of the
deasphalted oil obtained in the deasphalting step is 30 mass% or higher of the vacuum
residual oil in the manufacturing method of the process oil, the viscosity at 100 °C of the
deasphalted oil can be adjusted to 30 mm2/s or higher and foaming in the deasphalting
step can be prevented, thus achieving consistent production of the deasphalted oil.
By adjusting the viscosity at 100 °C of the deasphalted oil to be 30 to 50 mm2/s,
the viscosity at 100 °C of the resulting process oil can be easily adjusted to 40 to 70
mm /s.
[0026]
In the manufacturing method of the process oil according to the aspect of the
present invention, it is preferable that a pour point of the dewaxed oil obtained in the
dewaxing step is 0 to 25 °C, and a yield of the dewaxed oil is 90 mass% or higher of the
deasphalted oil.
According to the aspect of the present invention, since the pour point of the
dewaxed oil obtained in the dewaxing step is adjusted to be 0 to 25 °C in the
manufacturing method of the process oil, the pour point of the resulting process oil can be
easily adjusted to 40 °C or lower.
Since the yield of the dewaxed oil is set to 90 mass% or higher of the deasphalted
oil, when, for instance, a hydrodewaxing is employed in the dewaxing step, decrease in
yield due to decomposition can be prevented, and when a solvent dewaxing is employed
in the dewaxing step, generation of the wax component can be minimized, thereby

preferably preventing decrease in production efficiency.
[0027]
In the manufacturing method of the process oil according to the aspect of the
present invention, it is preferable that an extraction temperature in the solvent-extraction
step is 80 to 150oC, and a solvent ratio is 2.0 to 12.0.
According to the aspect of the present invention, since specific ranges are set for
the extraction temperature and the solvent ratio in the solvent-extraction step in the
manufacturing step of the process oil, the extract with the PCA content of less than 3
mass% can be obtained efficiently.
[0028]
According to a seventh aspect of the present invention, a manufacturing method
of a deasphalted oil using as a raw material a vacuum residual oil of a crude oil includes
deasphalting the vacuum residual oil using as a solvent a propane or a mixed solvent of a
butane and a propane under conditions of: a solvent ratio of 4.5 to 6; a column top
temperature of 85 to 100 °C; and a yield for the deasphalted oil of 30 to 40 vol%, the
deasphalted oil having properties of (a), (1) and (m) below:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic compound content of 10 mass ppm or less.
[0029]
According to the aspect of the present invention, since the deasphalted oil with
reduced content of the specified aromatic compound can be easily obtained, the superior
extract can be easily manufactured from the deasphalted oil as a crude material, the extract
being the raw material of the process oil having the properties of (a) and (i) to (n).
[0030]
According to an eighth aspect of the present invention, a manufacturing method
of an extract using as a raw material a deasphalted oil obtained by deasphalting a vacuum
residual oil of a crude oil includes: solvent-extracting the deasphalted oil under conditions
of: an extraction temperature of 80 to 150 °C; and a solvent ratio of 2.0 to 15.0, the extract

having properties of (1) and (m) below:
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic compound content of 10 mass ppm or less.
[0031]
According to the aspect of the present invention, since the extract with reduced
content of the specified aromatic compound can be easily obtained, the process oil being
excellent in safety with the properties of (a) and (i) to (n) can be easily manufactured from
the extract as the raw material.
[0032]
According to an ninth aspect of the present invention, a manufacturing method of
a process oil includes: a deasphalting step for deasphalting a vacuum residual oil of a
crude oil to obtain a deasphalted oil; and a solvent-extraction step for solvent-extracting
the deasphalted oil to obtain an extract; in which the extract obtained in the
solvent-extraction step and a lubricant base oil having a polycyclic aromatics (PCA)
content of less than 3 mass% are mixed to obtain a mixed oil, the mixed oil being
provided as the process oil.
With the manufacturing method of the process oil of the present invention, the
process oil having the properties of (a) and (i) to (n) described above can be provided
property.
[0033]
In the manufacturing method of the process oil according to the aspect of the
present invention, it is preferable that the lubricant base oil further has properties of (p) to
(r), (1) and (m) below.
(p) a viscosity (100 °C) of 5 to 40 mm2/s;
(q) an aniline point of 75 to 120 °C;
(r) a flash point of 200 °C or higher;
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic compound content of 10 mass ppm or less.
[0034]

With the lubricant base oil having such properties, it becomes even easier to
obtain the process oil having the properties of (a) and (i) to (n) by mixing the extract and
the lubricant base oil.
[0035]
According to the aspect of the present invention, in the manufacturing method of
the process oil, a volume mixing ratio of the extract and the lubricant base oil is preferably
set to 95/5 to 60/40.
By setting the mixing volume ratio of the extract and the lubricant base oil to the
range described above, it becomes even easier to obtain the process oil having the
properties of (a) and (i) to (n).
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
[0036]
Fig. 1 is a flow chart showing an example of a manufacturing method of a
process oil according to a first embodiment of the present invention;
Fig. 2 is a flow chart showing another example of a manufacturing method of a
process oil according to the first embodiment of the present invention; and
Fig. 3 is a flow chart showing an example of a manufacturing method of a
process oil according to a second embodiment of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0037]

A process oil and a manufacturing method of the process oil according to a first
embodiment of the present invention will be described below.
The process oil of the present embodiment uses as a raw material a deasphalted
oil obtained by deasphalting a vacuum residual oil of a crude oil, the process oil having
properties of (a) to (f) below:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(b) a viscosity (100 °C) of 40 to 70 mm2/s;
(c) an aniline point of 85 to 100 °C;

(d) a flash point of 250 °C or higher;
(e) an aromatic hydrocarbon content of 40 to 55 mass%; and
(f) a polar substance content of 10 to 15 mass%.
[0038]
(a) Content of Polycyclic Aromatics (PCA):
The PCA content in the process oil of the present embodiment should be less than
3 mass%, and preferably less than 2.5 mass%. Since a mineral oil having the PCA content
of 3 mass% or more is restricted in handling in Europe or other areas due to its
carcinogenicity, the PCA content in the process oil of the present embodiment is
accordingly set to less than 3 mass%. By setting the PCA content to less than 3 mass%,
the process oil being noncarcinogenic and excellent in safety can be provided.
The PCA content in the process oil may be measured in compliance with IP346
(92) standardized by The Institute of Petroleum.
[0039]
(b) Viscosity (100 °C):
The viscosity at 100 °C of the process oil of the present embodiment should be
40 to 70 mm2/s, and preferably 40 to 55 mm2/s. When the viscosity is lower than 40
mm2/s, normal state properties of a rubber to which the process oil is added will be
degraded. When the viscosity exceeds 70 mm2/s, the viscosity is too high, which adversely
affects molding-processability and operability in being added to the rubber as well as
degrading rubber properties.
Incidentally, the viscosity at 100 °C of the process oil may be measured in
compliance with ASTM D445.
[0040]
(c) Aniline Point:
The aniline point of the process oil of the present embodiment should be 85 to
100 °C, and preferably 85 to 95 °C (i.e., property (h)). When the aniline point is lower
man 85 °C, the PCA content increases and possibly exceeds 3 mass% as a regulation value.
On the other hand, when the aniline point exceeds 100 °C, compatibility wim the rubber

material is degraded, which might generate bleeding.
Aniline points of conventional process oils have been typically set to 80 °C or
lower because the lower aniline point has been considered to less likely generate the
bleeding in terms of the compatibility with the rubber material. However, by
manufacturing the process oil by, for instance, mixing the extract obtained by
solvent-extracting a dewaxed oil and a dewaxed oil by a desired mixing ratio to control (e)
content of aromatic hydrocarbon and (f) content of polar substance to be in the range from
40 to 55 mass% and 10 to 15 mass% respectively, the bleeding can be sufficiendy
prevented even with the aniline point of 80 °C or higher.
Incidentally, the aniline point of the process oil may be measured in compliance
with ASTM D611.
[0041]
(d) Flash Point:
The flash point of the process oil of the present embodiment should be 250 °C or
higher, and preferably 280 °C or higher. When the flash point is lower than 250 °C, the
process oil is easy to vaporize, which causes a problem in safety and adversely affects the
environment.
Incidentally, the flash point of the process oil may be measured in compliance
with ASTM D92.
[0042]
(e) Content of Aromatic Hydrocarbon:
The aromatic hydrocarbon content in the process oil of the present embodiment
should be 40 to 55 mass%, and preferably 45 to 55 mass%. When the aromatic
hydrocarbon content is less than 40 mass%, the compatibility with the rubber material is
degraded, which makes it difficult to add the process oil to manufacture a rubber, and
adversely affect the properties of the rubber. On the other hand, when the aromatic
hydrocarbon content exceeds 55 mass%, the PCA content increases and possibly exceeds
3 mass% as the regulation value.
Incidentally, the aromatic hydrocarbon content in the process oil may be

measured in compliance with ASTM D2007.
[0043]
(f) Content of Polar Substance:
The polar substance content in the process oil of the present embodiment should
be 10 to 15 mass%, and preferably 12 to 15 mass%. When the polar substance content is
less than 10 mass%, the compatibility with the rubber material is degraded. On the other
hand, when the polar substance content exceeds 15 mass%, it adversely affects the
properties of the rubber when added to the rubber, and further, the PCA content increases
and possibly exceeds 3 mass% as the regulation value.
Incidentally, the content of the polar substance of the process oil may be
measured in compliance with ASTM D2007.
[0044]
(g) Pour Point:
The pour point of the process oil of the present embodiment is preferably 40 °C
or lower, and more preferably 20 °C or lower. When the pour point is higher than 40 °C, a
wax component is separated out on a surface of the rubber to be manufactured, which
degrades the appearance and a commercial value of the rubber to be manufactured.
Incidentally, the pour point of the process oil may be measured in compliance
with ASTM D97.
[0045]
Note mat the process oil of the present embodiment preferably exhibits ASTM
color phase of 8.0 or lower when being diluted by a toluene of 60 times as large volume as
the process oil, and more preferably 6.0 or lower. By adjusting the ASTM color phase to
be 8.0 or lower, content of an asphaltene component becomes small, and thus when used
for manufacturing of a colored asphalt, the asphalt will be finished with a good color.
[0046]
Now, examples of a procedure to manufacture the process oil of the present
embodiment will be described below.
A first procedure of the manufacturing method of the process oil of the present

embodiment includes: a deasphalting step for deasphalting a vacuum residual oil of a
crude oil to obtain a deasphalted oil; and a solvent-extraction step for solvent-extracting
the deasphalted oil to obtain an extract with a yield of 55 mass% or higher of the
deasphalted oil to provide the extract oil as the process oil. With the procedure of the
manufacturing method, the process oil having the properties of (a) to (f) described above
can be obtained efficiently.
[0047]
Note that in the first procedure that includes the deasphalting step for
deasphalting the vacuum residual oil of the crude oil to obtain the deasphalted oil and the
solvent-extraction step for solvent-extracting the deasphalted oil to obtain the extract, a
mixed oil obtained by mixing the extract obtained in the solvent-extraction step and at
least one member selected from the group consisting of the deasphalted oil obtained in the
deasphalting step and a mineral oil with the polycyclic aromatics (PCA) content of less
than 3 mass% may be provided as the process oil (first procedure-b). With such
arrangement, the process oil having the properties of (a) to (f) described above can be
properly provided.
[0048]
A second procedure of the manufacturing method of the process oil of the present
embodiment includes: a deasphalting step for deasphalting a vacuum residual oil of a
crude oil to obtain a deasphalted oil; a dewaxing step for dewaxing the deasphalted oil to
obtain a dewaxed oil; and a solvent-extraction step for solvent-extracting the dewaxed oil
to obtain an extract with a yield of 50 mass% or higher of the deasphalted oil to provide
the extract as the process oil. With the procedure of the manufacturing method also, the
process oil having the properties of (a) to (f) described above can be obtained efficiently.
Especially, as compared to the first procedure, dewaxing the deasphalted oil can
provide proper fluidity to the process oil, which accordingly facilitates handling of the oil
and prevents the wax component from being separated out on the surface of the rubber.
[0049]
Note that also in the second procedure that includes the deasphalting step for

deasphalting the vacuum residual oil of the crude oil to obtain the deasphalted oil, the
dewaxing step for dewaxing the deasphalted oil to obtain the dewaxed oil and the
solvent-extraction step for solvent-extracting the dewaxed oil to obtain the extract, a
mixed oil obtained by mixing the extract obtained in the solvent-extraction step and at
least one member selected from the group consisting of the deasphalted oil obtained in the
deasphalting step or the dewaxed oil obtained in the dewaxing step and a mineral oil with
the polycyclic aromatics (PCA) content of less than 3 mass% may be provided as the
process oil (second procedure-b). With such arrangement, the process oil having the
properties of (a) to (f) described above can be properly provided.
[0050]
Now, (I) deasphalting step and (III) solvent-extraction step included in the first
procedure and (II) dewaxing step included in the second procedure between the steps (I)
and (III) will be described in detail below.
[0051]
(I) Deasphalting Step:
In the deasphalting step, the vacuum residual oil, which has been obtained by
performing atmospheric distillation and vacuum distillation on the crude oil, is
deasphalted to obtain the deasphalted oil.
Here, in order to perform the atmospheric distillation on the crude oil, a
conventional atmospheric distillation device and a conventional distillation condition can
be used. Specifically, for instance, the crude oil such as a paraffinic crude oil or a
naphthenic crude oil, which is an object to be refined, is heated to about 350 °C in a
heating furnace or the like and sent out to an atmospheric distillation column, which is
then turned to be a petroleum vapor in the atmospheric distillation column. After cooling,
the petroleum vapor is sequentially fractionated into fractions in the ascending order of
boiling points. Since the vacuum residual oil is obtained by the atmospheric distillation
and the vacuum distillation in the present embodiment, it may be so arranged to obtain an
atmospheric residual oil having boiling point of 350 °C or higher.
[0052]

Next, further distillation (vacuum distillation) under reduced pressure is
performed on the obtained atmospheric residual oil. The vacuum distillation may be
performed using a conventional vacuum distillation device and a conventional operating
condition, and the vacuum distillation fractionates the atmospheric residual oil into
fractions such as a vacuum naphtha, a vacuum light gas oil and a vacuum residual oil,
from which the vacuum residual oil is obtained.
[0053]
Then, the vacuum residual oil is separated into an oil component (deasphalted oil)
and an asphalt component using a solvent such as a liquefied propane. Deasphalting using
the liquefied propane is performed by, for instance, adding the liquefied propane to the
vacuum residual oil by an amount of 4 to 8 times as large volume as that of the vacuum
residual oil, while setting temperature to 40-80 °C in order to extract the deasphalted oil.
[0054]
Here, the yield of the obtained deasphalted oil in the deasphalting step is
preferably 30 mass% or higher of the vacuum residual oil, more preferably, 35 mass% or
higher. With the yield of the obtained deasphalted oil being 30 mass% or higher of the
vacuum residual oil, the viscosity at 100°C of the deasphalted oil can be adjusted to 30
mm /s or higher and foaming in the deasphalting step can be prevented, thus achieving
consistent production of the deasphalted oil.
By adjusting the viscosity at 100 °C of the deasphalted oil to be 30 to 50 mm2/s,
the viscosity at 100 °C of the resulting process oil can be easily adjusted to 40 to 70
mm2/s.
[0055]
The viscosity at 100 °C of the obtained deasphalted oil is preferably 30 to 50
mm /s, and more preferably 35 to 45 mm2/s. By adjusting the viscosity at 100 °C of the
deasphalted oil to 30 to 50 mm2/s, the viscosity at 100 °C of the resulting process oil to be
obtained can be easily adjusted to 40 to 70 mm2/s.
[0056]
(II) Dewaxing Step:

In the dewaxing step required in the second procedure, a paraffin wax component
of the above-described deasphalted oil is separated to obtain the dewaxed oil. Performing
the dewaxing step gives proper fluidity to the resulting process oil, which allows handling
thereof to be facilitated and prevents the wax component from being separated out on the
surface of the rubber to be manufactured.
[0057]
In the dewaxing step, the dewaxing should preferably be performed so that the
pour point of the obtained dewaxed oil is 0 to 25 °C, and more preferably 10 to 20 °C. By
adjusting the pour point of the dewaxed oil to 0 to 25 °C, particularly 10 to 20 °C, the pour
point of the resulting process oil to be manufactured can be easily adjusted to 40 °C or
lower.
[0058]
Examples of dewaxing method for dewaxing the deasphalted oil so mat the
dewaxed oil to be obtained has the pour point of the above-described range may include
hydrodewaxing and solvent dewaxing.
As the hydrodewaxing, for instance, dewaxing using ZSM-5 catalyst (Exxon
Mobil Corporation) is preferably performed.
[0059]
The hydrodewaxing is preferably performed under the following conditions:
pressure = 1 to 16 mPa; LHSV (liquid hourly space velocity) = 0.1 to 5.0/hour; and
hydrogen/oil ratio = 100 to 800 Nm3/kL so that the pour point of the dewaxed oil to be
obtained is within the range of 0 to 25 °C.
[0060]
Examples of solvents used in the solvent dewaxing may include, a methyl ethyl
ketone, a toluene, a benzene and the like, and a mixed solvent thereof, particularly a
mixed solvent of the methyl ethyl ketone and the toluene, may be preferable for use.
When using the mixed solvent of the methyl ethyl ketone and the toluene, mixing ratio
thereof may be around 40/60 to 60/40. In the solvent dewaxing, the solvent as described
above is added to the deasphalted oil, which is then cooled. Then, precipitated wax crystal

is filtered and separated.
[0061]
The yield of the dewaxed oil is preferably 90 mass% or higher of the deasphalted
oil, and more preferably 95 mass% or higher. With the yield of the dewaxed oil being 90
mass% or higher of the deasphalted oil, when, for instance, hydrodewaxing is employed as
the dewaxing method, decrease in the yield due to decomposition can be prevented, and
when solvent dewaxing is employed as the dewaxing method, generation of the wax
component can be saved to be small, thereby preferably preventing decrease in production
efficiency from decreasing.
[0062]
(HI) Solvent Extraction Step:
In the solvent-extraction step, the deasphalted oil obtained in the above-described
deasphalting step (in the first procedure) or the dewaxed oil obtained in the
above-described dewaxing step (in the second procedure) is solvent-extracted using a
polar solvent to obtain the extract. By solvent-extracting the deasphalted oil or the
dewaxed oil to obtain the extract, the PCA content of the process oil can be easily
maintained to be less than 3 mass%, and the aniline point can be appropriately adjusted,
thereby preventing generation of the bleeding.
[0063]
Here, examples of available polar solvents may include a furfural, a
N-methyl-2-pyrrolidone (NMP), a phenol, a cresol, a sulfolane, a dimethylsulfoxide, a
formylmorpholine and the like, especially the furfural and me N-methyl-2-pyrrolidone
(NMP) may be preferable for use.
[0064]
In the solvent-extraction step, the solvent ratio (volume ratio of solvent/dewaxed
oil or deasphalted oil) is preferably 2.0 to 12.0, and more preferably 5.0 to 10.0. In this
case, the extraction temperature is preferably 80 to 150 °C, and more preferably 90 to
130 °C. By performing the solvent-extraction under the conditions above, me extract with
the PCA content of less man 3 mass% can be efficiently obtained.

[0065]
The yield of the extract obtained in the solvent-extraction step should be 50
mass% or higher of the deasphalted oil, and preferably 60 mass% or higher. As long as the
yield of the extract is 50 mass% or higher of the deasphalted oil, the process oil with the
PCA content of less than 3 mass% can be properly obtained.
Incidentally, in order to obtain the extract with the yield of 50 mass% or higher of
the deasphalted oil, for instance, when the furfural is used as the solvent, the solvent ratio
may be around 10 to 12 and the extraction temperature may be around 120 to 150°C,
whereas, when the NMP is used as the solvent, the solvent ratio may be around 5 to 8 and
the extraction temperature may be around 100 to 120 °C.
[0066]
Meanwhile, as in the first procedure-b and the second procedure-b, when the
mixed oil obtained by mixing the extract from the deasphalted oil (or the dewaxed oil)
with at least one member selected from the group consisting of the deasphalted oil (or the
dewaxed oil) and the mineral oil having the PCA content of less man 3 mass% is provided
as the process oil, the yield of the extract in the solvent-extraction step for obtaining the
extract from the deasphalted oil (or the dewaxed oil) is not necessarily to be 50 mass% or
higher of the deasphalted oil. It is only necessary to mix the extract obtained with a
desired yield with at least one member selected from the group consisting of the
deasphalted oil obtained by the deasphalting step (or the dewaxed oil obtained in the
dewaxing step) and the mineral oil having the PCA content of less than 3 mass%. With the
arrangement, when the yield of the used extract is lower than 50 mass% or higher of the
deasphalted oil, the PCA content of the extract can be 3 mass% or more, but by mixing
this extract with the mineral oil or the deasphalted oil (or the dewaxed oil), the PCA
content can be controlled to be less than 3 mass%, so that requirements of the properties
of (b) to (f) described above can be achieved.
Incidentally, there is no problem in using the extract obtained with the yield of 50
mass% or higher of the deasphalted oil, of which the PCA content is expected to be small.
[0067]


Here, the obtained extract can be used as it is as the process oil with 100 mass%
content of the extract.
On the other hand, the mixed oil obtained by mixing the extract and at least one
member selected from the group consisting of the deasphalted oil obtained in the
deasphalting step and the mineral oil with the polycyclic aromatics (PCA) content of less
than 3 mass% may be provided as the process oil in the first procedure, while the mixed
oil obtained by mixing the extract and at least one member selected from the group
consisting of the dewaxed oil obtained in the dewaxing step and the mineral oil with the
polycyclic aromatics (PCA) content of less than 3 mass% may be provided as the process
oil in the second procedure. As described above, when the mixed oil is provided as the
process oil, the extract content is preferably in the range from 40 mass% to below 100
mass%, and more preferably in the range from 50 mass% to below 100 mass%. While the
process oil consisting of 100 mass% of the extract can properly achieve the properties of
(a) to (f) described above, the process oil consisting of the mixed oil of the extract and the
deasphalted oil and me like, in which the extract content is in the range from 40 mass% to
below 100 mass%, can also properly achieve the properties of (a) to (f) described above.
[0068]
Now, the first procedure of the manufacturing method of the process oil of the
present embodiment will be described referring to the flowchart in Fig. 1. First, the
atmospheric distillation is performed on the crude oil to obtain the atmospheric residual
oil and the vacuum distillation is performed on the atmospheric residual oil to obtain the
vacuum residual oil (S1, S21, S22 and S2). Then, the obtained vacuum residual oil is
deasphalted in the deasphalting step to obtain the deasphalted oil (S31, S3). The obtained
deasphalted oil is men solvent-extracted in the solvent-extraction step to obtain the extract
(S51, S5).
Here, when the extract is not mixed with the deasphalted oil and/or the mineral
oil with me polycyclic aromatics (PCA) content of less than 3 mass%, me extract obtained
with the yield of 50 mass% or higher of the deasphalted oil should be employed.
[0069]

rubber component.
[0076]

A process oil and a manufacturing method of the process oil according to a
second embodiment of the present invention will be described below.
The process oil of the present embodiment is obtained by mixing: an extract
solvent-extracted from a deasphalted oil that has been obtained by deasphalting a vacuum
residual oil of a crude oil; and a lubricant base oil with a polycyclic aromatics (PCA)
content of less than 3 mass%, the process oil having properties of (a) and (i) to (n) below:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(i) a viscosity (100 °C) of 30 to 80 mm2/s;
(j) an aniline point of 90 °C or lower;
(k) a flash point of 240 °C or higher;
(1) a benzo(a)pyrene content of 1 mass ppm or less;
(m) a specified aromatic compound content of 10 mass ppm or less; and
(n) a polar substance content of 10 to 30 mass%.
[0077]
(a) Content of Polycyclic Aromatics (PCA):
The PCA content in the process oil of the present embodiment should be less than
3 mass%, and preferably less than 2.5 mass%. Since a mineral oil with the PCA content of
3 mass% or more is restricted in handling in Europe or other areas due to its
carcinogenicity, the PCA content in the process oil of the present embodiment is
accordingly set to less than 3 mass%. By setting the PCA content to less than 3 mass%,
the process oil being noncarcinogenic and excellent in safety can be provided.
The PCA content in the process oil may be measured in compliance with IP346
(92) standardized by The Institute of Petroleum.
[0078]
(i) Viscosity (100 °C):
The viscosity at 100 °C of the process oil of the present embodiment should be

30 to 80 mm2/s, and preferably 40 to 60 mm2/s. When the viscosity is lower than 30
mm2/s, normal state properties of a rubber to which the process oil is added will be
degraded. When the viscosity exceeds 80 mm2/s, the viscosity is too high, which adversely
affects molding-processability and operability in being added to the rubber as well as
degrading rubber properties.
Incidentally, the viscosity at 100 °C of the process oil may be measured in
compliance with ASTM D445.
[0079]
(j) Aniline Point:
The aniline point of the process oil of the present embodiment should be 90 °C or
lower, and preferably 60 to 90 °C (i.e., property (o)). When the aniline point exceeds
90 °C, compatibility of the process oil and the rubber material is degraded, which might
cause the process oil to bleed on the surface of the rubber. Although lower limit of the
aniline point is not particularly specified, when the aniline point is lower than 60 °C, the
PCA content increases and possibly exceeds 3 mass% as a regulation value. The aniline
point of the process oil may be measured in compliance with ASTM D611.
[0080]
(k) Flash Point:
The flash point of the process oil of the present embodiment should be 240 °C or
higher, and preferably 260 °C or higher. When the flash point is lower than 240 °C, the
process oil is easy to vaporize, which causes a problem in safety and adversely affects the
environment.
Incidentally, the flash point of the process oil may be measured in compliance
with ASTM D92.
[0081]
(1) Content of Benzo(a)pyrene:
The content of the benzo(a)pyrene in the process oil of the present embodiment is
1 mass ppm or less.
Although the benzo(a)pyrene is a carcinogenic substance, since the contents

thereof is set to 1 mass ppm or less, there is no need to concern about its carcinogenicity,
thereby providing the process oil that is excellent in safety.
[0082]
(m) Content of Specified Aromatic Compound (Total Concentration)
The content of the specified aromatic compound (total concentration) in the
process oil of the present embodiment is 10 mass ppm or less. Here, the specified aromatic
compound refers to the following eight types of substances: a benzo(a)anthracene; a
chrysene and a triphenylene; a benzo(b)fluoranthene; a benzo(k)fluoranthene; a
benzo(j)fluoranthene; a benzo(e)pyrene; a benzo(a)pyrene; and a dibenzo(a,h)anthracene.
Although any of the above specified aromatic compounds is highly carcinogenic
substance, since the content (total concentration) thereof is set to be 10 mass ppm or less,
there is no need to concern about its carcinogenicity, thereby providing the process oil that
is excellent in safety. Incidentally, the concentration was measured by the following
method.
[0083]
(Measuring Method of Concentration of Specified Aromatic Compound)
1 g of a sample is dissolved into a hexane in a 50 ml flask to prepare a sample
solution of 2 mass%. 1 ml of the sample solution is added to 5 g of a hydrous silica gel of
5 mass%, which is rinsed with 20 ml of a hexane. Then, an object substance having
adsorbed is eluted using 50 ml of a hexane solution containing 5 vol% of an acetone. After
concentrating the eluate to 1 ml, 1 (ig of a chrysene d12 or a benzo(a)pyrene d12 is added as
an internal standard material, which is then analyzed by a gaschromatograph.
[0084]
(n) Content of Polar Substance:
The polar substance content in the process oil of the present embodiment should
be 10 to 30 mass%, preferably 12 to 20 mass%, and more preferably 12 to 15 mass%.
When the polar substance content is less than 10 mass%, the compatibility with the rubber
material is degraded. On the other hand, when the polar substance content exceeds 30
mass%, the PCA content increases and possibly exceeds 3 mass% as the regulation value,

Then, the vacuum residual oil is separated into an oil component (deasphalted oil)
and an asphalt component using a solvent such as a liquefied propane (or a mixed solvent
of the liquefied propane and a butane). Deasphalting using the liquefied propane is
performed by, for instance, adding the liquefied propane to the vacuum residual oil by an
amount of 4.5 to 6 times as large volume as that of the vacuum residual oil and setting
extraction temperature to 85 to 100 °C (column top)/60 to 75 °C (column bottom ) to
extract the deasphalted oil.
[0089]
Here, the yield of the deasphalted oil obtained in the deasphalting step is 30 to 40
vol% of the vacuum residual oil. The viscosity at 100 °C of the obtained deasphalted oil is
preferably 30 to 50 mm2/s, and more preferably 30 to 45 mm2/s.
[0090]
By the above-described step, the deasphalted oil having the properties of (a), (1)
and (m) below can be manufactured:
(a) a polycyclic aromatics (PCA) content of less man 3 mass%;
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic compound content of 10 mass ppm or less.
[0091]
[Manufacturing of Extract (Solvent-Extraction Step)]
In the solvent-extraction step, the deasphalted oil obtained in the above-described
deasphalting step is solvent-extracted using the polar solvent to obtain the extract. By
solvent-extracting the deasphalted oil to obtain the extract, the PCA content of the process
oil can be easily maintained to be less than 3 mass%, and the aniline point can be
appropriately adjusted, which results in preventing generation of the bleeding.
[0092]
Here, examples of available polar solvents may include a furfural, a
N-methyl-2-pyrrolidone (NMP), a phenol, a cresol, a sulfolane, a dimethylsulfoxide, a
formylmorpholine and the like, especially the furfural and the N-methyl-2-pyrrolidone
(NMP) may be preferable for use.

Since the process oil obtained in the second embodiment described above has the
properties of (a) and (i) to (n), the process oil exhibits various performances that the
conventional process oil has required, such as processability and anti-bleeding
performance of the rubber. In addition, since the content of the PCA that is hazardous to
human bothes is controlled to be less than 3 mass% and the contents of the
benzo(a)pyrene and the specified aromatic compound are respectively controlled to be 1
mass ppm or less and 10 mass ppm or less, the process oil is not carcinogenic and thus
excellent in safety.
[0100]
In manufacturing conventional oils substituting the aromatic oil for tires, since
two-stage extraction or facility (step) for further performing hydrotreatment on the extract
has been required in order to obtain such process oil, yield decreased in each treatment. In
contrast, the present embodiment requires only a simple method for mixing the extract and
the lubricant base oil, which is further superior manufacturing method of the process oil as
compared to the conventional method.
[0101]
Addition of the process oil to the natural rubber or the synthetic rubber can
properly provide various types of rubber compositions, and the obtained rubber
compositions can be used for various rubber products such as tires.
Further, the process oil can also be used as a plasticizer for the thermoplastic
resin, a constituent of a printing ink and a softener for a modified asphalt used in paving.
[0102]
When a rubber (rubber composition) is manufactured using the process oil of the
present embodiment, content of the process oil may be, for instance, 10 to 50 parts by
weight, and preferably 20 to 40 parts by weight relative to 100 parts by weight of a rubber
component.
Also, in order to manufacture the rubber composition, reinforcers such as a
carbon black and a silica, a vulcanizing agent, a vulcanization accelerator, a filler, an
antioxidant such as waxes, a softener other than the process oil of the present

embodiment, a plasticizer, etc., which are generally used in rubber industry, may
appropriately be added in addition to the process oil of the embodiment and the rubber
component.
[0103]
[Modification of Embodiments]
Incidentally, the embodiment described above is only an embodiment illustrating
the present invention, and the present invention is not limited to the embodiment but
includes modifications and improvements as long as the objects and the advantages of the
present invention can be achieved. Specific structure and shape of the components in
implementing the present invention may be designed in any manner as long as the objects
and the advantages of the present invention can be achieved.
For example, although the manufacturing method shown in Fig. 1 is exemplified
as the manufacturing method of the process oil of the present invention having the
properties of (a) to (f) in the first embodiment, and the manufacturing method shown in
Fig. 3 is exemplified as the manufacturing method of the process oil of the present
invention having the properties of (a) and (i) to (n) in the second embodiment,
manufacturing method for obtaining the process oil may be appropriately adjusted as long
as the process oil has the properties of (a) to (f) in the first embodiment or the properties
of (a) and (i) to (n) in the second embodiment.
[Example]
[0104]
Now, the first embodiment of the present invention will be described in more
detail with examples and comparisons, the description of which by no means limits the
present invention.
[0105]
[Example 1]
(Deasphalting Step)
A vacuum residual oil obtained by performing the atmospheric distillation on a
middle-east crude oil and further performing the vacuum distillation is deasphalted using a

propane as a solvent to obtain a deasphalted oil A. Yield of the deasphalted oil A was 38
mass% of the vacuum residual oil, and the viscosity at 100 °C of the deasphalted oil A
was 37.6 mm2/s.
[0106]
(Dewaxing Step)
The deasphalted oil A was solvent-dewaxed using a mixed solvent of a methyl
ethyl ketone and a toluene (mixing ratio: methyl ethyl ketone/toluene = 40/60) to obtain a
dewaxed oil A having pour point of 12.5 °C. Yield of the dewaxed oil A was 93 mass% of
the deasphalted oil.
[0107]
(Solvent-Extraction Step)
Then, the dewaxed oil A was solvent-extracted using a furfural as a solvent to
obtain an extract A with a yield of 62 mass% of the deasphalted oil. Here, solvent ratio
was 10 and extraction temperature was 145 °C. The extract A was provided as a process
oil of Example 1 of the first embodiment of the present invention.
[0108]
[Example 2]
(Deasphalting Step)
As in Example 1, the vacuum residual oil obtained by performing the
atmospheric distillation on the middle-east crude oil and further performing the vacuum
distillation is deasphalted using the propane as a solvent to obtain the deasphalted oil A.
[0109]
(Dewaxing Step)
The deasphalted oil A was dewaxed using Ni-ZSM5 catalyst under the
following conditions: pressure = 3MPa; LHSV = 0.5/hour; hydrogen/oil ratio = 450 Nm3;
and dewaxing temperature = 335 °C so that a dewaxed oil B having pour point of 20.0°C
was obtained. Yield of the dewaxed oil B was 94 mass% of the deasphalted oil.
[0110]
(Solvent-Extraction Step)

Then, the dewaxed oil B was solvent-extracted using a N-methyl-2-pyrrolidone
(NMP) as a solvent to obtain an extract B with a yield of 64 mass% of the deasphalted oil.
Here, the solvent ratio was 7 and the extraction temperature was 110 °C. The extract B
was provided as a process oil of Example 2 of the first embodiment of the present
invention.
[0111]
[Example 3]
The dewaxed oil B obtained in Example 2 was solvent-extracted using the NMP
as a solvent to obtain an extract D with a yield of 48 mass% of the deasphalted oil. Here,
solvent ratio was 5 and extraction temperature was 95 oC. The extract D and the dewaxed
oil B obtained in Example 2 were mixed with mixing ratio of extract D/dewaxed oil B =
50/50 to obtain a process oil of Example 3 of the first embodiment of the present
invention.
[0112]
[Example 4]
The dewaxed oil B obtained in Example 2 was solvent-extracted using the NMP
as a solvent to obtain the extract D with a yield of 48 mass% of the deasphalted oil. Here,
the solvent ratio was 5 and the extraction temperature was 95oC. The extract D and a
commercially-available mineral oil X with the polycyclic aromatics (PCA) content of 1.8
mass% were mixed with mixing ratio of extract D/mineral oil X = 50/50 to obtain a
process oil of Example 4 of the first embodiment of the present invention.
[0113]
[Example 5]
The deasphalted oil A obtained in Example 1 was solvent-extracted using the
furfural as a solvent to obtain an extract X with a yield of 53% of the deasphalted oil. Here,
the solvent ratio was 5 and the extraction temperature was 125 °C. The extract X was
provided as a process oil of Example 5 of the first embodiment of the present invention.
[0114]
[Example 6]

An extract E obtained in later-described Comparison 6 and the deasphalted oil A
obtained in Example 1 (which is also a process oil of later-described Comparison 3) were
mixed with mixing ratio of extract E/deasphalted oil A = 50/50 to obtain a process oil of
Example 6 of the first embodiment of the present invention.
[0115]
[Comparison 1]
The dewaxed oil A obtained in Example 1 was solvent-extracted using the
furfural as a solvent to obtain an extract C with a yield of 49 mass% of the deasphalted oil.
Here, the solvent ratio was 8 and the extraction temperature was 110 °C. The extract C
was provided as a process oil of Comparison 1.
[0116]
[Comparison 2]
As in Example 3, the dewaxed oil B obtained in Example 2 was solvent-extracted
using the NMP as a solvent to obtain the extract D with a yield of 48 mass% of the
deasphalted oil. Here, the solvent ratio was 5 and the extraction temperature was 95 °C.
The extract D was provided as a process oil of Comparison 2.
[0117]
[Comparison 3]
The deasphalted oil A of Example 1 was provided as a process oil of Comparison
3.
[0118]
[Comparison 4]
The dewaxed oil A of Example 1 was provided as a process oil of Comparison 4.
[0119]
[Comparison 5]
The dewaxed oil B of Example 2 was provided as a process oil of Comparison 5.
[0120]
[Comparison 6]
The deasphalted oil A obtained in Example 1 was solvent-extracted using the

furfural as a solvent to obtain the extract E with a yield of 40% of the deasphalted oil.
Here, the solvent ratio was 5 and the extraction temperature was 125 °C. The extract E
was provided as a process oil of Comparison 6.
[0121]
Properties of the process oils of Examples 1 to 6 are shown in Tables 1 and 2
with properties of a conventional aromatic oil as reference. Also, properties of the process
oils of Comparisons 1 to 6 are shown in Tables 3 and 4 with the properties of the
conventional aromatic oil as reference. Here, standards or the like for evaluation are in
compliance with those described above.












[0127]
For the obtained high styrene rubbers, generation of bleeding (a phenomenon in
which an oil bleeds on a surface of a rubber) and separation of a wax component were
visually observed. For the obtained general-purpose styrene rubbers, rubber properties
such as elongation, hardness, tensile strength and M 300 (elasticity of a rubber when the
rubber is elongated at elongation percentage of 300%) were measured in compliance with
JIS K6301. Based on the visual observation and measurement, the high styrene rubbers
and general-purpose rubbers were compared and evaluated. The results are shown in
Tables 7 and 8.
Note mat measurement values of the rubber properties of the general-purpose
styrene rubbers were compared with those of a general-purpose styrene rubber
manufactured using the conventional aromatic oil as the reference (refer to Tables 1 and 3
for its properties). The evaluations were made using relative values with the measurement
values of the aromatic oil being 100.
[0128]
(Result)




[0129]
As is clear from results in table 7, the high styrene rubbers using the process oils
of Examples 1 to 6 were free from generation of the bleeding and separation of the wax
component, so that they were verified to be high styrene rubbers having no problem in
use.
Especially, in Examples 4 and 6, even though the yields of the extracts used were
less than 50 mass% of the deasphalted oils, the process oils having the properties of (b) to
(f) could be made by mixing the extracts with the mineral oils or the asphalted oils by the
mixing ratio of 50/50, and the evaluation results also showed no problem.
In addition, the rubber properties of the general-purpose styrene rubbers using the
process oils of Examples 1 to 6 did not show a big difference from that using the
conventional aromatic process oil, so that they were verified to have rubber properties
egual to those of conventional process oils.
[0130]
On the other hand, as is clear from the results in Table 8, since the process oil of
Comparison 3 had high aniline point and pour point, bleeding and separation of the wax
component were observed.

Since the process oils of Comparisons 4 and 5 had high aniline point, bleeding
was observed.
[0131]
As for the process oils of Comparisons 1, 2 and 6, the high styrene rubbers
thereof showed no bleeding and separation of the wax component, and the
general-purpose styrene rubbers thereof showed no problem in their rubber properties.
However, since yields of the extracts in manufacturing were low, the contents of the
aromatic hydrocarbons and the polar substances in the process oils became large, which
caused the PCA content to exceed 3 mass%, so that the process oils had problems in
carcinogenicity and safety.
[0132]
Next, me second embodiment of the present invention will be described in more
detail with examples and comparisons, the description of which by no means limits the
present invention.
[0133]
[Example 7]
(Deasphalting Step)
By performing the atmospheric distillation on a middle-east crude oil to extract a
fuel oil such as a kerosene and a light gas oil and further performing the vacuum
distillation on an atmospheric residual oil outlet from a distillation column bottom to
obtain a vacuum light gas oil. A vacuum residual oil obtained after fractionating the
vacuum light gas oil was used as a raw material to be deasphalted. The vacuum residual
oil was deasphalted using a propane as a solvent with solvent ratio of 5.5 and at
predetermined extraction temperature (column top: 90°C, column bottom: 65 °C) to obtain
a deasphalted oil B with a yield of 35 vol% of the vacuum residual oil. The properties are
shown in Table 9.
[0134]
(Solvent-Extraction Step)
The deasphalted oil obtained in the deasphalting step was extracted using the

N-methyl-2-pyrrolidone (NMP) as a solvent with solvent ratio of 3.0 and at extraction
temperature of 120 °C to obtain an extract E1. The properties are shown in Table 9.
[0135]
(Mixing Step)
The extract E1 was mixed with 10 vol% of a lubricant base oil B1 having
properties shown in Table 10 to obtain a mixed oil having viscosity at 100°C being 60
mm2/s (volume mixing ratio: 90/10). The mixed oil was provided as a process oil of
Example 7 of the second embodiment of the present invention.
[0136]
[Example 8]
The extract E1 obtained in Example 7 was mixed with 30 vol% of a lubricant
base oil B2 having properties shown in Table 10 to obtain a mixed oil having viscosity at
100°C being 60 mm2/s (volume mixing ratio: 70/30). The mixed oil was provided as a
process oil of Example 8 of the second embodiment of the present invention.
[0137]
[Example 9]
The extract E1 obtained in Example 7 was mixed with 7 vol% of a lubricant base
oil B3 having properties shown in Table 10 to obtain a mixed oil having viscosity at
100°C being 60 mm2/s (volume mixing ratio: 93/7). The mixed oil was provided as a
process oil of Example 9 of the second embodiment of the present invention.
[0138]
[Comparison 7]
The vacuum residual oil obtained in Example 7 was deasphalted with solvent
ratio of 7.0 and at predetermined extraction temperature (column top: 75°C, column
bottom: 60 °C) to obtain a deasphalted oil C with a yield of 60 vol% of the vacuum
residual oil. The deasphalted oil C was solvent-extracted under the extraction condition
similar to Example 7 to obtain an extract E2 having properties shown in Table 9. The
extract E2 was mixed with 15 vol% of the lubricant base oil Bl to obtain a mixed oil
having viscosity at 100°C being 60 mm2/s (volume mixing ratio: 85/15). The obtained

mixed oil was provided as a process oil of Comparison 7.
[0139]
[Comparison 8]
The extract E2 was mixed with 80 vol% of the lubricant base oil B1 to obtain a
mixed oil (volume mixing ratio: 20/80). The obtained mixed oil was provided as a process
oil of Comparison 8.
[0140]
[Comparison 9]
The extract E2 was mixed with 35 vol% of the lubricant base oil B2 to obtain a
mixed oil (volume mixing ratio: 65/35). The obtained mixed oil was provided as a process
oil of Comparison 9.
[0141]
[Comparison 10]
The extract E2 was mixed with 80 vol% of the lubricant base oil B2 to obtain a
mixed oil (volume mixing ratio: 20/80). The obtained mixed oil was provided as a process
oil of Comparison 10.
[0142]
Properties of the process oils of Examples 7 to 9 are shown in Table 11 with the
properties of the conventional aromatic oil as reference. Also, properties of the process
oils of Comparisons 7 to 10 are shown in table 12. Here, standards or the like for
evaluation are in compliance with those described above.








[Test Example 1]
Using the process oils obtained in Examples 7 to 9 and Comparisons 7 to 10
described above, a high styrene rubber and a general-purpose styrene rubber were
manufactured with the formulations of Tables 5 and 6 of the first embodiment.
[0146]
For the obtained high styrene rubbers, generation of bleeding (a phenomenon in
which an oil bleeds on a surface of a rubber) and separation of a wax component were
visually observed. For the obtained general-purpose styrene rubbers, rubber properties
such as elongation, hardness, tensile strength and M 300 (elasticity of a rubber when the
rubber is elongated at elongation percentage of 300%) were measured in compliance with
JIS K6301. Based on the visual observation and measurement, the high styrene rubbers
and general-purpose rubbers were compared and evaluated. The results are shown in

Tables 13 and 14.
Note that measurement values of the rubber properties of the general-purpose
styrene rubbers were compared with those of a general-purpose styrene rubber
manufactured using the conventional aromatic oil (refer to Table 11 for its properties).
The evaluations were made using relative values with the measurement values of the
aromatic oil being 100.
[0147]

As is clear from the results in table 13, the high styrene rubbers using me process

oils of Examples 7 to 9 were free from generation of the bleeding and separation of the
wax component, so that they were verified to be high styrene rubbers having no problem
in use.
In addition, the rubber properties of the general-purpose styrene rubbers using the
process oils of Examples 7 to 9 were not inferior to that using the conventional aromatic
process oil, so that they were verified to have rubber properties equal to those of
conventional process oils.
[0149]
On the other hand, as is clear from the results in table 14, since the extracts used
as the raw materials of the process oils of Comparisons 7 and 9 had high contents of
specified aromatic compound and benzo(a)pyrene, the process oils obtained by mixing
such extracts and the lubricant base oils also had problems in carcinogenicity and safety.
Also, the viscosities at 100°C of the process oils were low, so that the rubber properties
thereof were inferior to the aromatic oil as reference.
As for the process oils of Comparisons 8 and 10, although the contents of the
benzo(a)pyrene and the specified aromatic compound were satisfactory, me aniline points
were high, and bleedings were observed in the high styrene rubbers. Especially, since the
aniline point was quite high in Comparison 10, all of the elongation, tensile strength and
M300 of the general-purpose styrene rubber were poor.
INDUSTRIAL APPLICABILITY
[0150]
The process oil of the present invention can be used with advantage as a process
oil and a flatting agent for a natural rubber or a synthetic rubber, and a plasticizer for a
thermoplastic resin, a constituent of a printing ink and a softener for a modified asphalt
used in paving.
[0150]
The applicant asserts that no biological material of Indian origin has been used in
the present invention.


WE CLAIM:
1. A process oil using as a raw material a deasphalted oil obtained by deasphalting a
vacuum residual oil of a crude oil, the process oil comprising properties of:
(a) a policyclic aromatics (PCA) content of less than 3 mass%;
(b) a viscosity (100°C) of 40 to 70 mm2/s;
(c) an aniline point of 85 to 100°C;
(d) a flash point of 250°C or higher;
(e) an aromatic hydrocarbon content of 40 to 55 mass%; and
(f) a polar substance content of 10 to 15 mass%.
2. The process oil as claimed in claim 1, comprising a property of:
(g) a pour point of 40°C or lower.
3. The process oil as claimed in claim 1 or 2, wherein the process oil shows an
ASTM color phase of 8.0 or lower when being diluted with a toluene of sixty times as
large volume as the process oil.
4. The process oil as claimed in any one of claims 1 to 3, comprising a property of:
(h) an aniline point of 85 to 95°C.
5. A process oil obtained by mixing:
an extract obtained by deasphalting and solvent-extracting a vacuum residual oil
of a crude oil; and
a lubricant base oil having a polycyclic aromatics (PCA) content of less than 3
mass%, the process oil comprising properties of:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(i) a viscosity (100 °C) of 30 to 80 mm2/s;
(j) an aniline point of 90°C or lower;

(k) a flash point of 240°C or higher;
(1) a benzo(a)pyrene content of 1 mass ppm or less;
(m) a specified aromatic compound content of 10 mass ppm or lower; and
(n) a polar substance content of 10 to 30 mass%.
6. The process oil as claimed in claim 5, comprising a property of:
(o) an aniline point of 60 to 90°C.
7. A manufacturing method of the process oil as claimed in any one of claims 1 to 4,
comprising:
a deasphalting step for deasphalting a vacuum residual oil of a crude oil to obtain
a deasphalted oil; and
a solvent-extraction step for solvent-extracting the deasphalted oil to obtain an
extract with a yield of 50 mass% or higher of the deasphalted oil, the extract being
provided as the process oil.
8. A manufacturing method of the process oil as claimed in any one of claims 1 to 4,
comprising:
a deasphalting step for deasphalting a vacuum residual oil of a crude oil to obtain
a deasphalted oil; and
a solvent-extraction step for solvent-extracting the deasphalted oil to obtain an
extract;
wherein the extract obtained in the solvent-extraction step and at least one
member selected from the group consisting of the deasphalted oil obtained in the
deasphalting step and a mineral oil having a polycyclic aromatics (PCA) content of less
than 3 mass% are mixed to obtain a mixed oil, the mixed oil being provided as the process
oil.

9. A manufacturing method of the process oil as claimed in any one of claims 1 to 4,
comprising:
a deasphalting step for deasphalting a vacuum residual oil of a crude oil to obtain
a deasphalted oil;
a dewaxing step for dewaxing the deasphalted oil to obtain a dewaxed oil; and
a solvent-extraction step for solvent-extracting the dewaxed oil to obtain an extract with a
yield of 50 mass% or higher of the deasphalted oil, the extract being provided as the
process oil.
10. A manufacturing method of the process oil as claimed in any one of claims 1 to 4,
comprising:
a deasphalting step for deasphalting a vacuum residual oil of a crude oil to obtain
a deasphalted oil;
a dewaxing step for dewaxing the deasphalted oil to obtain a dewaxed oil; and
a solvent-extraction step for solvent-extracting the dewaxed oil to obtain an extract,
wherein the extract obtained in the solvent-extraction step and at least one member
selected from the group consisting of the dewaxed oil obtained in the dewaxing step and a
mineral oil having a polycyclic aromatics (PCA) content of less than 3 mass% are mixed
to obtain a mixed oil, the mixed oil being provided as the process oil.
11. The manufacturing method as claimed in claim 8 or 10, wherein a content of the
extract in the mixed oil is in the range from 40 mass% to below 80 mass%.
12. The manufacturing method as claimed in any one of claims 7 to 11, wherein:
a yield of the deasphalted oil obtained in the deasphalting step is 30 mass% or
higher of the vacuum residual oil, and
a viscosity (100°C) of the deasphalted oil is 30 to 50 mm2/s.

13. The manufacturing method as claimed in any one of claims 9 to 12, wherein a
pour point of the dewaxed oil obtained in the dewaxing step is 0 to 25oC, and a yield of
the dewaxed oil is 90 mass% or higher of the deasphalted oil.
14. The manufacturing method as claimed in any one of claims 7 to 13, wherein an
extraction temperature in the solvent-extraction step is 80 to 150°C, and a solvent ratio is
2.0 to 12.0.
15. A manufacturing method of the process oil as claimed in claim 5, comprising:
a deasphalting step for deasphalting a vacuum residual oil of a crude oil to obtain
a deasphalted oil; and
a solvent-extraction step for solvent-extracting the deasphalted oil to obtain an
extract, wherein the extract obtained in the solvent-extraction step and a lubricant base oil
having a polycyclic aromatics (PCA) content of less than 3 mass% are mixed to obtain a
mixed oil, the mixed oil being provided as the process oil.
16. The manufacturing method according to claim 15, wherein the lubricant base oil
has properties of:
(p) a viscosity (100°C) of 5 to 40 mm2/s;
(q) an aniline point of 75 to 120°C;
(r) a flash point of 200°C or higher;
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic compound content of 10 mass ppm or less.
17. The manufacturing method as claimed in claim 15 or 16, wherein a volume
mixing ratio of the extract and the lubricant base oil is 95/5 to 60/40.

18. The manufacturing method as claimed in any one of claims 15 to 17, wherein the
deasphalted oil uses as a raw material a vacuum residual oil of a crude oil, the deasphalted
oil having properties of (a), (1) and (m) below, and the method comprises:
deasphalting the vacuum residual oil using as a solvent a propane or a mixed
solvent of a butane and a propane under conditions of: a solvent ratio of 4.5 to 6;
a column top temperature of 85 to 100°C; and
a yield for the deasphalted oil of 30 to 40 vol%, the properties being:
(a) a polycyclic aromatics (PCA) content of less than 3 mass%;
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic hydrocarbon content of 10 mass ppm or less.
19. The manufacturing method as claimed in any one of claims 15 to 17, wherein the
extract uses as a raw material a deasphalted oil obtained by deasphalting a vacuum
residual oil of a crude oil, the extract having properties of (1) and (m) below, and the
method comprises:
solvent-extracting the deasphalted oil under conditions of:
an extraction temperature of 80 to 150°C; and
a solvent ratio of 2.0 to 15.0, the properties being:
(1) a benzo(a)pyrene content of 1 mass ppm or less; and
(m) a specified aromatic hydrocarbon content of 10 mass ppm or less.


ABSTRACT

PROCESS OIL, PROCESS FOR PRODUCTION OF DEASPHALTED OIL,
PROCESS FOR PRODUCTION OF EXTRACT, AND PROCESS
FOR PRODUCTION OF PROCESS OIL
The present invention is related to a process oil using as a raw material a
deasphalted oil obtained by deasphalting a vacuum residual oil of a crude oil and a
manufacturing method of the process oil, the process oil having properties of: (a) a
polycyclic aromatics (PCA) content of less man 3 mass%; (b) a viscosity (100°C) of 40 to
70 mm2/s; (c) an aniline point of 85 to 100°C; (d) a flash point of 250°C or higher; (e) an
aromatic hydrocarbon content of 40 to 55 mass%; and (f) a polar substance content of 10
to 15 mass%. The present invention is also related to a process oil and a manufacturing
method of the process oil, the process oil obtained by mixing: an extract obtained by
deasphalting and solvent-extracting a vacuum residual oil of a crude oil; and a lubricant
base oil having a polycyclic aromatics (PCA) content of less than 3 mass%, and having
properties of: (a) a polycyclic aromatics (PCA) content of less than 3 mass%; (i) a
viscosity (100°C) of 30 to 80 mm2/s; (j) an aniline point of 90°C or lower; (k) a flash point
of 240°C or higher; (1) a benzo(a)pyrene content of 1 mass ppm or less; (m) a specified
aromatic compound content of 10 mass ppm or less; and (n) a polar substance content of
10 to 30 mass%.

Documents:

04191-kolnp-2007-abstract.pdf

04191-kolnp-2007-claims.pdf

04191-kolnp-2007-correspondence others.pdf

04191-kolnp-2007-description complete.pdf

04191-kolnp-2007-drawings.pdf

04191-kolnp-2007-form 1.pdf

04191-kolnp-2007-form 3.pdf

04191-kolnp-2007-form 5.pdf

04191-kolnp-2007-international publication.pdf

04191-kolnp-2007-international search report.pdf

04191-kolnp-2007-others.pdf

04191-kolnp-2007-pct priority document notification.pdf

04191-kolnp-2007-pct request form.pdf

04191-kolnp-2007-translated copy of priority document.pdf

4191-KOLNP-2007-(11-07-2012)-ANNEXURE TO FORM 3.pdf

4191-KOLNP-2007-(11-07-2012)-ENGLISH TRANSLATION OF PRIORITY DOCUMENT.pdf

4191-KOLNP-2007-(11-07-2012)-EXAMINATION REPORT REPLY RECIEVED.pdf

4191-KOLNP-2007-(24-08-2012)-ABSTRACT.pdf

4191-KOLNP-2007-(24-08-2012)-AMANDED CLAIMS.pdf

4191-KOLNP-2007-(24-08-2012)-CORRESPONDENCE.pdf

4191-KOLNP-2007-(24-08-2012)-DESCRIPTION (COMPLETE).pdf

4191-KOLNP-2007-(24-08-2012)-FORM-1.pdf

4191-KOLNP-2007-(24-08-2012)-FORM-2.pdf

4191-KOLNP-2007-(24-08-2012)-FORM-3.pdf

4191-KOLNP-2007-(24-08-2012)-OTHERS.pdf

4191-KOLNP-2007-(24-08-2012)-PA.pdf

4191-KOLNP-2007-(24-08-2012)-PETITION UNDER RULE 137.pdf

4191-KOLNP-2007-ASSIGNMENT.pdf

4191-KOLNP-2007-CORRESPONDENCE OTHERS 1.1.pdf

4191-KOLNP-2007-CORRESPONDENCE.pdf

4191-KOLNP-2007-EXAMINATION REPORT.pdf

4191-KOLNP-2007-FORM 18 1.1.pdf

4191-kolnp-2007-form 18.pdf

4191-KOLNP-2007-FORM 3-1.1.pdf

4191-KOLNP-2007-FORM 3.pdf

4191-KOLNP-2007-FORM 5.pdf

4191-KOLNP-2007-GRANTED-ABSTRACT.pdf

4191-KOLNP-2007-GRANTED-CLAIMS.pdf

4191-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

4191-KOLNP-2007-GRANTED-DRAWINGS.pdf

4191-KOLNP-2007-GRANTED-FORM 1.pdf

4191-KOLNP-2007-GRANTED-FORM 2.pdf

4191-KOLNP-2007-GRANTED-SPECIFICATION.pdf

4191-KOLNP-2007-INTERNATIONAL SEARCH REPORT & OTHERS.pdf

4191-KOLNP-2007-OTHERS.pdf

4191-KOLNP-2007-PA.pdf

4191-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

abstract-04191-kolnp-2007.jpg


Patent Number 255021
Indian Patent Application Number 4191/KOLNP/2007
PG Journal Number 03/2013
Publication Date 18-Jan-2013
Grant Date 15-Jan-2013
Date of Filing 01-Nov-2007
Name of Patentee IDEMITSU KOSAN CO. LTD.
Applicant Address 1-1, MARUNOUCHI 3-CHOME, CHIYODA-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 TANAKA MEISHI 24-4, ANESAKIKAIGAN, ICHIHARA-SHI, CHIBA 299-0107
2 TESHIMA KAZUHIRO 24-4, ANESAKIKAIGAN, ICHIHARA-SHI, CHIBA 299-0107
3 TAKASAKI MASAMI 1280, KAMIIZUMI, SODEGAURA-SHI, CHIBA 299-0293
4 ABE AKIHITO 24-4, ANESAKIKAIGAN, ICHIHARA-SHI, CHIBA 299-0107
5 NAKAMURA MASASHI 24-4, ANESAKIKAIGAN, ICHIHARA-SHI, CHIBA 299-0107
PCT International Classification Number C08L 21/00
PCT International Application Number PCT/JP2006/310692
PCT International Filing date 2006-05-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2005-160582 2005-05-31 Japan
2 2005-274689 2005-09-21 Japan