JP5342206B2 - Method for producing hydrocarbon composition, hydrocarbon composition, lubricating base oil, lubricating oil composition - Google Patents

Description

  The present invention relates to a method for producing a hydrocarbon composition, a hydrocarbon composition, a lubricating base oil, and a lubricating oil composition.

  Conventionally, in the fields of fuels such as light oil and heavy oil, and lubricating oils, improvement of low-temperature characteristics of hydrocarbon base materials has been attempted.

  For example, in the field of lubricating oils, the low temperature viscosity characteristics of lubricating oils are improved by blending additives such as pour point depressants with lubricating base oils such as highly refined mineral oils (for example, patent documents). 1-3). Further, as a method for producing a high viscosity index base oil, a method of refining a lubricating base oil by hydrocracking / hydroisomerization is known for a raw material oil containing natural or synthetic normal paraffin (for example, (See Patent Documents 4 to 6).

In order to obtain a lubricating base oil and lubricating oil composition having a high viscosity index and excellent low-temperature characteristics, a highly refined treatment method by a hydrocracking method or a hydroisomerization method and a dewaxing method are important. As the dewaxing method, a solvent dewaxing method using a dewaxing solvent such as MEK or a hydrodewaxing method has become the mainstream.
JP-A-4-36391 Japanese Patent Laid-Open No. 4-68082 Japanese Patent Laid-Open No. 4-120193 JP 2005-154760 A JP-T-2006-502298 JP-T-2002-503754

  However, recently, demands for improving the low-temperature characteristics of hydrocarbon-based substrates have become increasingly severe, and it has become difficult to sufficiently satisfy such demands. In particular, in the case of a lubricating base oil, a high viscosity index is required in addition to the low-temperature viscosity characteristics, but it is difficult to say that these two requirements are sufficiently compatible in the conventional lubricating base oil.

  Therefore, the present inventors have examined that the conventional hydrocarbon base material has insufficient low-temperature characteristics because the conventional paraffin solvent precipitated by MEK and the like is precipitated at a temperature lower than the dewaxing temperature. And low-branched paraffin was not sufficiently removed.

  Although it is possible to improve the low temperature characteristics by greatly reducing the dewaxing temperature, this method not only consumes a lot of energy, but also limits the dewaxing device capability and the yield. Is concerned. In addition, in the hydrodewaxing method, it is necessary to carry out excessive treatment such as setting up a higher reaction temperature and decomposition rate in order to improve the low-temperature characteristics because the initial capital investment is very expensive. Thus, there is room for further improvement in terms of energy consumption and yield deterioration. On the other hand, if it is found that a product containing a hydrocarbon base material or additive produced by these methods does not meet the specified quality standards after production, remanufacturing and reviewing the production conditions Will be forced.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a hydrocarbon composition excellent in low-temperature characteristics and a method for producing the same. Another object of the present invention is to provide a lubricating base oil and a lubricating oil composition that contain the hydrocarbon composition, have excellent low-temperature viscosity characteristics, and have a high viscosity index.

  In order to achieve the above-mentioned object, the present inventors firstly separated specific branched paraffins, which could not be removed by conventional dewaxing methods, and could hinder improvement in low-temperature characteristics. The method was examined. As a result, it was newly found that urea selectively includes (adducts) a branched paraffin having a branching group having 5 or less carbon atoms and having 6 or more carbon atoms from the end of the main chain to the branching position. It was. And, by utilizing the inclusion action of urea, it is possible to selectively and efficiently separate specific branched paraffins that may impede improvement of low temperature performance from hydrocarbon raw materials, and the resulting hydrocarbon composition The inventors have found that the low temperature characteristics of the product can be improved, and have completed the present invention.

That is, the present invention is a method for producing a hydrocarbon composition used in a lubricating base oil, which comprises contacting a hydrocarbon raw material containing a branched paraffin having a branched alkyl group having 5 or less carbon atoms with urea. A hydrocarbon composition comprising a step of separating a branched paraffin having 6 or more carbon atoms from at least one end to a branch position from the hydrocarbon raw material as a urea adduct to obtain a hydrocarbon composition. A manufacturing method is provided.

  In the present invention, the content of linear paraffin in the hydrocarbon raw material is preferably 5% by mass or less.

Moreover, this invention provides the hydrocarbon composition used for the lubricating base oil manufactured by the manufacturing method of the said invention.

  The present invention also provides a lubricating base oil containing the hydrocarbon composition of the present invention.

  The present invention also provides a lubricating oil composition containing the hydrocarbon composition of the present invention.

  According to the method for producing a hydrocarbon composition of the present invention, a hydrocarbon raw material containing a branched paraffin has a branching group having 5 or less carbon atoms, and the number of carbons from the end of the main chain to the branching position is 6 or more. Certain branched paraffins can be selectively and efficiently removed. Further, when the hydrocarbon raw material contains linear paraffin, the linear paraffin can be separated and removed together with the specific branched paraffin. Therefore, the hydrocarbon composition of the present invention produced by the above production method has excellent low temperature characteristics. In particular, by using the hydrocarbon composition of the present invention as a base material for a lubricating base oil and lubricating oil composition, a lubricating base oil and lubricating oil composition having excellent low temperature viscosity characteristics and a high viscosity index can be realized. It becomes.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The method for producing a hydrocarbon composition according to this embodiment includes the following steps (1) to (3).
(1) A hydrocarbon raw material containing a branched paraffin having a branched alkyl group having 5 or less carbon atoms (hereinafter sometimes referred to as “specific branched paraffin (A)”) and urea or a urea solution are mixed and contacted. The process of
(2) A branched paraffin having 6 or more carbon atoms from at least one end to a branch position in the specific branched paraffin (A) from the mixture obtained in the step (1) (hereinafter referred to as “specific branched paraffin (B)”. Separating the water as a urea adduct (urea clathrate) to obtain a hydrocarbon-containing component, and
(3) A step of obtaining a hydrocarbon composition by separating and purifying excess urea or urea solution from the hydrocarbon-containing component obtained in step (2).

Moreover, it is preferable that the manufacturing method of the hydrocarbon composition which concerns on this embodiment is further equipped with the following process (4)-(6) (separation process or a reuse process) as needed.
(4) A step of separating the urea adduct obtained in step (2) into urea and inclusions,
(5) Reusing the urea obtained in step (4) for step (1), and
(6) A step of reusing the inclusions obtained in step (4) for the production process of hydrocarbon raw materials.

The hydrocarbon raw material is not particularly limited as long as it contains the above-mentioned specific branched paraffin (A), but it is obtained in a petroleum refining process such as a kerosene fraction, a light oil fraction, a heavy oil fraction, a solvent fraction, or a lubricating oil fraction. The distillate fraction is preferred, and among these, the lubricating oil fraction is particularly preferred. As a lubricating oil fraction here, the kinematic viscosity in 40 degreeC becomes like this. Preferably it is 1-1000 mm < ² > / s, More preferably, it is 2-500 mm < ² > / s, More preferably, it is 5-100 mm < ² > / s. For example, the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm ² / s, more preferably 1.5 to 50 mm ² / s, and still more preferably ^{2 to 20} mm ² / s.

  Lubricating oil fraction is selected from lubricating oil production raw materials, hydrocracking / isomerization process, solvent extraction process, dewaxing process (hydrodewaxing, solvent dewaxing, etc.), hydrofinishing process, and distillation process. A lubricating oil fraction obtained through one or more steps is preferred.

  Further, the lubricating oil fraction includes a solvent refining step, a lubricating oil fraction obtained through a solvent dewaxing step or a hydrodewaxing step, or a hydrocracking and / or hydroisomerization step, and a solvent. Lubricating oil fraction obtained through a dewaxing step or hydrodewaxing step is more preferred, obtained through a hydrocracking and / or hydroisomerization step and a solvent dewaxing step or hydrodewaxing step. A lubricating oil fraction is particularly preferred.

  The hydrocarbon raw material may contain straight-chain paraffin, which is also included by contact with urea. However, when the content of linear paraffin in the hydrocarbon raw material is large, the separation efficiency of the specific branched paraffin (B), which is the main purpose, may be deteriorated, and an excessive urea or urea solution is required. The linear paraffin content in the hydrocarbon raw material is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass. It is as follows.

  As the hydrocarbon raw material having a linear paraffin content of 5% by mass or less, a raw material dewaxed by a solvent dewaxing method using a dewaxing solvent such as MEK or a raw material dewaxed by a hydrodewaxing method is suitable. It is. In the present invention, these raw materials only have to remove linear paraffin to some extent, so that there is an advantage that excessive dewaxing conditions can be relaxed.

  Further, the viscosity index of the hydrocarbon raw material is preferably 80 or more, more preferably 100 or more, further preferably 120 or more, particularly preferably 135 or more, preferably 180 or less, more preferably 170. Hereinafter, it is more preferably 160 or less. By setting the viscosity index of the hydrocarbon raw material to 80 or more, an appropriate viscosity from a low temperature to a high temperature can be maintained. In addition, when a viscosity index exceeds 180, while there exists a possibility that the yield of the target hydrocarbon composition may deteriorate, it becomes difficult to obtain desired low-temperature characteristics.

  The pour point of the hydrocarbon raw material is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, further preferably −10 ° C. or lower, preferably −50 ° C. or higher, more preferably −40 ° C. or higher, and still more preferably − 30 ° C or higher. When the pour point of the hydrocarbon raw material exceeds 10 ° C, urea or urea solution is excessively required, and the efficiency of removing the specific branched paraffin (B) may be deteriorated. The pour point of the hydrocarbon raw material is -50 ° C. If it is less than 1, it does not meet the object of the present invention to further improve the low temperature characteristics.

  Further, the content of the branched paraffin in the hydrocarbon raw material (the total content of the specific branched paraffin (A) and the other branched paraffin) is preferably 40% by mass or more, more preferably 60% by mass or more, and still more preferably. It is preferably adjusted to 80% by mass or more, particularly preferably 90% by mass or more. When the content of branched paraffin in the hydrocarbon raw material is less than 40% by mass, it becomes difficult to obtain a lubricating base oil having a high viscosity index.

  Further, in the step (1), the ratio of the hydrocarbon mixed raw material and urea is not particularly limited, and it is sufficient that sufficient urea is present to include part or all of the specific paraffin. Preferably, 0.01 to 10 parts by weight of urea, more preferably 0.1 to 5 parts by weight, still more preferably 0.5 to 4 parts by weight, and particularly preferably 1 to 3 parts by weight with respect to 1 part by weight of the raw material. use. When the ratio of urea is less than 0.01 part by weight with respect to 1 part by weight of the hydrocarbon mixed raw material, the effect of reducing or removing the specific branched paraffin (B) tends to decrease. Not only is a large amount required, but there is a tendency that an effect commensurate with the proportion of urea cannot be obtained.

  Urea may be introduced separately into a mixing tank or piping to be mixed with the hydrocarbon mixed raw material, but since urea is a solid, it contacts with the hydrocarbon mixed raw material in a state dissolved in a solvent as a urea solution. It is preferable to make it.

  As the solvent used for the urea solution, it is preferable to use a urea-soluble solvent such as water, lower alcohols such as methanol and glycol, and mixtures thereof. In addition, from the viewpoint of good miscibility with hydrocarbon raw materials and the ability to increase contact efficiency even at room temperature, hydrocarbon solvents such as aromatic solvents such as benzene, toluene and xylene can be used together as necessary. good. The urea solution is preferably a mixture of urea and a water-soluble solvent or a water-soluble solvent and a hydrocarbon solvent, more preferably a mixture of urea and methanol and / or water and a hydrocarbon solvent, urea, methanol and an aromatic solvent. And a mixture thereof is more preferable. A surfactant may be added to the urea solution.

  The mixing ratio of urea and the solvent in the urea solution is not particularly limited, but is preferably 10 to 1000 g of urea, more preferably 200 to 800 g of urea, and further preferably 300 to 700 g with respect to 1 L of solvent.

  The ratio of the urea-soluble solvent in the solvent, preferably methanol and / or water, more preferably methanol, is preferably 1 to 100% by volume, more preferably 5 to 50% by volume. The proportion of the hydrocarbon solvent, preferably an aromatic solvent, more preferably toluene, is preferably 0 to 99% by volume, more preferably 50 to 95% by volume.

  The contact between the hydrocarbon raw material and urea or urea solution in the step (1) can be performed at room temperature, and the contact temperature is, for example, 0 to 90 ° C, preferably 10 to 50 ° C, more preferably 20 to 40. C. can be exemplified. In addition, when using water as a solvent, it is 5-90 degreeC, for example, Preferably it is 60-80 degreeC. If the contact temperature exceeds the upper limit, urea may decompose or the solvent may volatilize. If the contact temperature is lower than the lower limit, a wax component may precipitate from the hydrocarbon raw material, or water in the solvent may freeze. Etc., and the efficiency tends to decrease.

  The contact time between the hydrocarbon raw material and urea in the step (1) is not particularly limited. In order to obtain low temperature characteristics necessary for the obtained hydrocarbon composition, a part or all of the specific branched paraffin (B) is added. In order to isolate | separate, it can adjust arbitrarily according to industrial manufacture efficiency. The preferable contact time may be instantaneous as long as the contact can be made efficiently, but is more preferably 1 minute or more, more preferably 10 minutes or more, and further preferably 30 minutes or more. Even if the contact time is too long, the effect of increasing the contact time is reduced and the production efficiency is lowered. Therefore, it is preferably 10 hours or less, more preferably 8 hours or less.

  When the hydrocarbon raw material and urea or urea solution are mixed and brought into contact in the step (1), the specific branched paraffin component is included (adducted), and white granular crystals are generated in the mixture. Therefore, in step (2), crystals (urea adducts) are separated from the mixture to obtain hydrocarbon-containing components.

  The urea adduct separation method is not particularly limited as long as it is a method capable of separating a liquid and a solid. For example, a stationary method, a filtration method using a filter medium such as a paper filter, a filter cloth, a wire mesh, or a centrifugal separation. Law.

  In step (3), the urea-containing component obtained in step (2) is subjected to separation / purification of excess urea or urea solution. For example, by adding excess water to the hydrocarbon-containing component, excess urea and a water-soluble solvent can be transferred to the water phase and separated from the oil phase. When a light hydrocarbon solvent such as toluene is present in the oil phase, it can be distilled off by distillation under reduced pressure. Through such separation and purification, a hydrocarbon composition in which the specific branched paraffin (B) is sufficiently reduced or removed is obtained.

  Further, with respect to the steps (4) to (6), the urea adducts separated as described above are purified through a washing step, a separation step of urea and inclusions, and a recovery step, whereby urea and inclusions are obtained. Can be reused. The separated urea is reused as a contact material with a hydrocarbon raw material, and the separated inclusion is recycled as a hydrocracking or hydroisomerization raw material, or as paraffin wax, isoparaffin, or a raw material thereof. Also good. Further, the solvent can be separated and reused by distillation or the like.

  The hydrocarbon composition of the present invention is a hydrocarbon composition produced by the above production method. The hydrocarbon composition is not particularly limited, but is preferably kerosene, light oil, heavy oil, solvent, or a lubricating base oil or lubricating oil composition, among which a lubricating base oil or lubricating oil composition is particularly preferable. .

  The pour point of the hydrocarbon composition in the present invention, preferably the lubricating base oil, is preferably 1 point (2.5 ° C.) or higher, more preferably 2 points (5 ° C.) or lower than the hydrocarbon feedstock. Specifically, it is preferably 0 ° C. or lower, more preferably −15 ° C. or lower, further preferably −20 ° C. or lower, preferably −60 ° C. or higher, preferably −40 ° C. or higher, more preferably − 35 ° C or higher. The lower the pour point, the more excellent the low-temperature properties can be obtained, but the pour point is preferably in the above range from the balance between the yield of the hydrocarbon composition and the low-temperature properties.

  The freezing point of the hydrocarbon composition of the present invention, preferably the lubricating base oil, is preferably 1 point (1 ° C.) or higher, more preferably 3 points (3 ° C.), and even more preferably 5 points (5 C.) having a low freezing point, specifically, preferably 0 ° C. or lower, more preferably −15 ° C. or lower, further preferably −20 ° C. or lower, particularly preferably −25 ° C. or lower, preferably It is −60 ° C. or higher, preferably −40 ° C. or higher, more preferably −35 ° C. or higher. The lower the freezing point, the more excellent the low-temperature properties can be obtained. However, the freezing point is preferably within the above range from the balance between the yield of the hydrocarbon composition and the low-temperature properties.

  The BF viscosity at −25 ° C. of the hydrocarbon composition of the present invention, preferably the lubricating base oil, is preferably 500 mPa · s or more, more preferably 1000 mPa · s or more, and even more preferably 1500 mPa · s or more than the hydrocarbon raw material. In particular, it has a low BF viscosity of 10,000 mPa · s or more.

  The viscosity index of the hydrocarbon composition of the present invention, preferably a lubricating base oil, is preferably 80 or more, more preferably 95 or more, further preferably 115 or more, particularly preferably 135 or more, preferably 170 or less, more Preferably it is 165 or less, More preferably, it is 160 or less. As the viscosity index is higher, excellent lubricity can be maintained from low temperature to high temperature, but if it is too high, it becomes difficult to obtain desired low temperature characteristics.

The kinematic viscosity at 100 ° C. of the hydrocarbon composition of the present invention, preferably a lubricating base oil, is preferably 1 to 100 mm ² / s, more preferably 1.5 to 50 mm ² / s, and even more preferably ^{2 to 20} mm ^2. Although it is / s, it is preferable to fractionate the lubricating base oil in the following range.
(I) less than the kinematic viscosity at 100 ° C. is 1.5 mm ² / s or more 3.5 mm ² / s, more preferably kinematic viscosity at 2.0 to 3.0 mm ² / s lubricating base oils (II) 100 ° C. Is 3.5 mm ² / s or more and less than 5 mm ² / s, more preferably 3.7 to 4.5 mm ² / s of the lubricant base oil (III), the kinematic viscosity at 100 ° C. is 5 to 20 mm ² / s, more preferably Is a lubricant base oil of 5.5 to 11 mm ² / s, particularly preferably 6 to 8 mm ² / s.

Moreover, the kinematic viscosity at 40 ° C. of the hydrocarbon composition in the present invention, preferably the lubricating base oil, is preferably 1 to 1000 mm ² / s, more preferably ² to 500 mm ² / s, and still more preferably 5 to 100 mm ^2. Although it is / s, it is preferable to fractionate the lubricating base oil in the following range.
(IV) less than the kinematic viscosity at 40 ° C. is 6.0 mm ² / s or more 12 mm ² / s, more preferably 8.0~12mm ² / s lubricating base oil (V) kinematic viscosity at 40 ° C. is 12 mm ² / s or more and less than 30 mm ² / s, more preferably 14 to 29 mm ² / s of lubricating base oil (VI) having a kinematic viscosity at 40 ° C. of 30 to 80 mm ² / s, more preferably 32 to 50 mm ² / s, particularly preferably Is a lubricating base oil of 33 to 40 mm ² / s.

  If the kinematic viscosity at 100 ° C. or 40 ° C. is less than the lower limit, the lubricating performance and evaporation characteristics may be insufficient, and if it exceeds the upper limit, it becomes difficult to obtain desired low-temperature viscosity characteristics.

  In the present invention, it is particularly preferable to fractionate a lubricating base oil in the range of at least (II) and / or (V) among the above base oils.

  When the hydrocarbon composition of the present invention is used as a base material for a lubricating base oil, the lubricating base oil may consist only of the hydrocarbon composition of the present invention, or the hydrocarbon composition of the present invention. The lubricant base oil may be constituted by using the product in combination with one or more of other lubricant base oils. Similarly, the lubricating base oil contained in the lubricating oil composition of the present invention may consist only of the hydrocarbon composition of the present invention, and the hydrocarbon composition of the present invention may be replaced with other lubricating oils. You may comprise a lubricating base oil in combination with 1 type, or 2 or more types of base oil.

  When the hydrocarbon composition of the present invention and another lubricating base oil are used in combination, the proportion of the hydrocarbon composition of the present invention in the mixed base oil is preferably 30% by mass or more. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.

The other base oil used in combination with the lubricating base oil of the present invention is not particularly limited. For example, a mineral base oil, a synthetic base oil, and a natural fat / oil base having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s. Arbitrarily selected from base oils and the like. Examples of the mineral base oil include solvent refined mineral oil, hydrocracked mineral oil, hydrocracked mineral oil, solvent dewaxed base oil, and hydrodewaxed base oil having a kinematic viscosity at 100 ° C. of 1 to 100 mm ² / s. It is done.

Synthetic base oils include, for example, poly α-olefins having a kinematic viscosity of 1 to 100 mm ² / s at 100 ° C. or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl). Glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc., polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate) , Pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl diphenyl ether, polyphenyl ether, etc., among others, poly α-olefins Preferred. As the poly α-olefin, typically, an oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those. Of the hydrides.

  The hydrocarbon composition of the present invention preferably contains an additive that can further improve the low-temperature viscosity characteristics, such as a low-temperature fluidity improver, a pour point depressant, or a viscosity index improver.

  For example, when the hydrocarbon composition of the present invention is used as a base material for heavy oil such as light oil or A heavy oil, the low temperature fluidity improvement required for reducing the pour point and clogging point of the hydrocarbon composition of the present invention By blending the agent (CFI), a light oil composition or heavy oil composition excellent in low temperature performance can be obtained. The blending amount of the low-temperature fluidity improver is preferably 0.001 to 0.1% by mass based on the total amount of the light oil composition or heavy oil composition.

  In addition, when the hydrocarbon composition of the present invention is used as a base material for a lubricating oil composition, the hydrocarbon composition of the present invention is added to a pour point depressant (PPD) and / or viscosity index improver ( By adding VM), a lubricating oil composition having excellent low temperature viscosity characteristics and a high viscosity index can be obtained. The blending amount of the pour point depressant (PPD) is preferably 0.001 to 2% by mass, more preferably 0.1 to 1% by mass, based on the total amount of the lubricating oil composition. The blending amount of the viscosity index improver (VM) is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the lubricating oil composition. The weight average molecular weight of the pour point depressant is preferably 10,000 to 300,000, more preferably 50,000 to 200,000, and the pour point depressant is particularly preferably polymethacrylate. The weight average molecular weight of the viscosity index improver is preferably 10,000 to 1,000,000, more preferably 50,000 to 600,000, and still more preferably 200,000 to 400,000.

  When the hydrocarbon composition of the present invention is used as a base material for a lubricating oil composition, by including the pour point depressant and / or viscosity index improver, in particular, the lubricating oil composition has a temperature of −30 ° C. or lower (−30 MRV viscosity or BF viscosity at ℃, -35 ℃ and -40 ℃) can be improved. MRV viscosity or BF viscosity at −30 ° C. or lower (−30 ° C., −35 ° C. and −40 ° C.) of the lubricating oil composition contains the above pour point depressant and / or viscosity index improver in the hydrocarbon mixed raw material. The MRV viscosity or BF viscosity is preferably 500 mPa · s or higher, more preferably 1000 mPa · s or higher, even more preferably 2000 mPa · s or higher, and particularly preferably 3000 mPa · s or higher. In addition, MRV viscosity here refers to MRV viscosity measured based on ASTM D 4684, and BF viscosity refers to BF viscosity measured based on JPI-5S-26-99.

  The hydrocarbon composition of the present invention may further contain various additives, for example, petroleum product additives such as fuel additives and lubricating oil additives.

  When the hydrocarbon composition of the present invention is used as a base material for a lubricating oil composition, the additive used in combination is not particularly limited, and any additive conventionally used in the field of lubricating oil can be blended. it can. Specific examples of such lubricating oil additives include antioxidants, ashless dispersants, metallic detergents, extreme pressure agents, antiwear agents, viscosity index improvers, pour point depressants, friction modifiers, oiliness agents. , Corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, seal swelling agents, antifoaming agents, colorants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specifically, the use of the lubricating base oil or lubricating oil composition containing the hydrocarbon composition of the present invention (that is, the lubricating base oil or lubricating oil composition of the present invention) includes gasoline engines for passenger cars and motorcycles. Gasoline engines, diesel engines, gas engines, gas heat pump engines, marine engines, lubricating oils used for internal combustion engines such as power generation engines (lubricants for internal combustion engines), automatic transmissions, manual transmissions, continuously variable transmissions, Lubricating oil (drive transmission device oil) used in drive transmission devices such as final reduction gears, hydraulic hydraulic fluid, compressor oil, turbine oil, industrial gear oil, refrigerator oil used in hydraulic devices such as shock absorbers and construction machinery , Anti-corrosion oil, heat medium oil, gas holder seal oil, bearing oil, paper machine oil, machine tool oil, slip guide surface oil, electrical insulating oil, cutting oil, press oil, rolling oil, heat treatment oil Etc. can be mentioned, by the use of a lubricating base oil of the present invention in these applications, it is possible to achieve a high level and a low-temperature viscosity characteristic and high viscosity index of the lubricating oil.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Example 1]
(Manufacture of hydrocarbon raw material 1)
The fraction from which the crude oil atmospheric distillation bottom was separated by vacuum distillation was subjected to a hydrogenation treatment after solvent extraction with furfural, and then dewaxed with a methyl ethyl ketone-toluene mixed solvent. Solvent dewaxing was performed using a mixed solvent of MEK and toluene at a solvent / oil ratio of 1.5 times and a filtration temperature of -25 ° C. Hereinafter, the solvent refining / solvent dewaxing mineral oil base oil thus obtained is referred to as hydrocarbon raw material 1 (GpI base oil). Table 1 shows the properties of the hydrocarbon raw material 1. In addition, the linear paraffin content of the hydrocarbon raw material 1 was less than 0.5 mass%.
(Manufacture of lubricating base oil 1)
100 g of hydrocarbon raw material 1 was collected in a round bottom flask, 200 g of urea, 360 ml of toluene and 40 ml of methanol were added and stirred at room temperature (about 25 ° C.) for 6 hours. The reaction liquid was filtered through a 1 micron filter to separate the produced white granular crystals (urea adduct) from the liquid phase. The liquid phase is further mixed with a large amount of water, and the aqueous phase containing urea and methanol is separated from the oil phase. The oil phase is distilled under reduced pressure (evaporator) to distill off the toluene to obtain the desired hydrocarbon composition (hereinafter referred to as "Lubricant base oil 1") was obtained. The yield and properties of the lubricating base oil 1 relative to the hydrocarbon raw material 1 are shown in Table 1.
Moreover, about the crystal | crystallization (urea adduct thing) obtained by filtration, it wash | cleaned 6 times with 50 ml of toluene, the collect | recovered white crystal | crystallization was put into the flask, 300 ml of pure water and 300 ml of toluene were added, and it stirred at 80 degreeC for 1 hour. The aqueous phase was separated and removed with a separatory funnel, and the toluene phase was washed with 300 ml of pure water three times. A desiccant (sodium sulfate) was added to the toluene phase for dehydration, and then the toluene was distilled off to remove the urea adduct. The object to be adducted was obtained from the object. The ratio of the adduct to be obtained thus obtained to the raw material (amount of urea adduct: mass percentage) was determined. The obtained results are shown in Table 1. Furthermore, as a result of analyzing the adduct by gas chromatography and ¹³ C-NMR, the adduct has a branching group having 5 or less carbon atoms, and the number of carbons from the end of the main chain to the branching position is 6 or more. It was found that some branched paraffin was the main component and a small amount of linear paraffin. More specifically, 99% by mass or more in the adduct object is branched paraffin, and the average carbon number of the adduct object is 27.2.
The number of carbons having a branch per molecule of branched paraffin is 0.87 on average, and the ratio of the carbons within the fourth from the end of the carbons having the branch to other carbons is 1: 2.4. confirmed. On the other hand, the length of the carbon chain constituted by ε-methylene carbon having no branch (carbon corresponding to a 30 ppm peak in the range of 0 ppm to 50 ppm of ¹³ C-NMR spectrum) is also confirmed to be C10 or more. It was done.

[Example 2]
(Manufacture of hydrocarbon raw material 2)
A fraction obtained by separating a crude oil atmospheric distillation bottom by vacuum distillation is used as a hydrocracking raw material after destillation, and this is hydrocracked using a metal-supported catalyst mainly composed of a Group VIII transition metal, and then methyl ethyl ketone. -Solvent dewaxing with toluene mixed solvent. Solvent dewaxing was performed using a mixed solvent of MEK and toluene at a solvent / oil ratio of 1.5 times and a filtration temperature of -30 ° C. Hereinafter, the hydrocracking / solvent dewaxing mineral oil base oil thus obtained is referred to as hydrocarbon feedstock 2 (GpIII base oil). Table 1 shows the properties of the hydrocarbon raw material 2. In addition, the linear paraffin content of the hydrocarbon raw material 2 was less than 0.5 mass%.
(Manufacture of lubricating base oil 2)
A desired hydrocarbon composition (hereinafter referred to as “lubricant base oil 2”) was obtained in the same manner as the production of the lubricating base oil 1 except that the hydrocarbon raw material 2 was used instead of the hydrocarbon raw material 1. . Table 1 shows the yield and properties of the lubricant base oil 2 with respect to the hydrocarbon raw material 2.
Further, the crystals obtained by filtration were treated in the same manner as in Example 1, and the ratio of the obtained adduct to the raw material (urea adduct amount: mass percentage) was determined. The obtained results are shown in Table 1. Furthermore, as a result of analyzing the adduct by gas chromatography and ¹³ C-NMR, the adduct has a branching group having 5 or less carbon atoms, and the number of carbons from the end of the main chain to the branching position is 6 or more. It was found that some branched paraffin was the main component and a small amount of linear paraffin. More specifically, 99% by mass or more in the adduct was branched paraffin, and the average carbon number of the branched paraffin was 27.2. The number of carbons having a branch per molecule of branched paraffin is 1.2 on average, and it is confirmed that the ratio of the carbon within the fourth from the end of the carbon having the branch to the other carbon is 1: 3.6. It was done. On the other hand, the length of a carbon chain constituted by ε-methylene carbon (carbon corresponding to a 30 ppm peak in the range of 0 ppm to 50 ppm of ¹³ C-NMR spectrum) having no branched paraffins is C10 or more. It was also confirmed.

[Example 3]
(Manufacture of hydrocarbon raw material 3)
The solvent dewaxing extract (slack wax) obtained in the process of producing the GpI base oil was hydrocracked / isomerized using a metal-supported catalyst mainly composed of a Group VIII transition metal, and then noble metal content 0 The hydrodewaxing was performed at a temperature range of 315 ° C. to 325 ° C. using a zeolite hydrodewaxing catalyst adjusted to 1 to 5% by weight. Hereinafter, the wax decomposition / isomerization / solvent dewaxing mineral oil base oil thus obtained is referred to as hydrocarbon raw material 3 (GpIII + base oil). Properties of the hydrocarbon raw material 3 are shown in Table 1. In addition, the linear paraffin content of the hydrocarbon raw material 3 was less than 0.5 mass%.
(Manufacture of lubricating base oil 3)
A desired hydrocarbon composition (hereinafter referred to as “lubricating oil base oil 3”) was obtained in the same manner as in the production of the lubricating oil base oil 1 except that the hydrocarbon raw material 3 was used in place of the hydrocarbon raw material 1. . Table 1 shows the yield and properties of the lubricant base oil 3 with respect to the hydrocarbon raw material 3.
Further, the crystals obtained by filtration were treated in the same manner as in Example 1, and the ratio of the obtained adduct to the raw material (urea adduct amount: mass percentage) was determined. The obtained results are shown in Table 1. Furthermore, as a result of analyzing the adduct by gas chromatography and ¹³ C-NMR, the adduct has a branching group having 5 or less carbon atoms, and the number of carbons from the end of the main chain to the branching position is 6 or more. It was found that some branched paraffin was the main component and a small amount of linear paraffin. More specifically, 99% by mass or more of the adducts are branched paraffin, and the average number of carbons of the adducts is 1.3.
The number of carbons having a branch per molecule of the branched paraffin is 28.4 on average, and the ratio of the carbon within the fourth from the end of the carbons having the branch to the other carbon is 1: 1.15. confirmed. On the other hand, the length of the carbon chain constituted by ε-methylene carbon having no branch (carbon corresponding to a 30 ppm peak in the range of 0 ppm to 50 ppm of ¹³ C-NMR spectrum) is also confirmed to be C11 or more. It was done.

[Comparative Examples 1-3]
In Comparative Example 1, the hydrocarbon raw material 2 was used as a lubricating base oil (hereinafter referred to as “lubricating base oil 4”), and its properties were evaluated. Further, in Comparative Examples 2 and 3, the hydrocarbon composition (hereinafter referred to as “hereinafter referred to as“ hydrocarbon composition ”) was prepared in the same manner as in the production of the hydrocarbon raw material 2 except that the dewaxing temperature of the solvent dewaxing was −33 ° C. Lubricating base oil 5 ”and“ lubricating base oil 6 ”) were obtained. Properties of the lubricating base oils 4 to 6 are shown in Table 2.
Further, each of the lubricating base oils 4 to 6 is treated with urea in the same manner as in the production of the lubricating base oil 1, and the ratio of the obtained adduct to the raw material (urea adduct amount: mass percentage) is obtained. It was. The obtained results are shown in Table 2.

As is apparent from Table 1, the lubricating base oils 1 to 3 obtained in Examples 1 to 3 have a high viscosity index, while being excellent in low temperature characteristics such as pour point, freezing point, and BF viscosity. It was confirmed that Particularly, the BF viscosity at −25 ° C. is 20,000 mPa · s or more in Example 1, about 30000 mPa · s or more in Example 2, and 1500 mPa · s or more in Example 3 with respect to the hydrocarbon raw material. Thus, the specific branched paraffin (specific branched paraffin (B)), which may interfere with the improvement of the low-temperature characteristics by the urea treatment at room temperature, can be selectively separated and removed, and is excellent as described above. The ability to produce lubricating base oils with properties is very useful in terms of energy consumption and yield.
On the other hand, as shown in Table 2, in Comparative Example 2, the yield with respect to the hydrocarbon raw material 2 was equivalent to that in Example 2, but almost no decrease in pour point or freezing point was observed. It is worse than the yield of Example 2, and the improvement degree of the pour point and freezing point is also smaller than that of Example 2. Furthermore, in Comparative Examples 2 and 3, since the urea adduct amount is about 4% by mass or more, even if the dewaxing conditions are severe and the energy consumption and the yield are sacrificed, there is a risk that the low temperature characteristics may be improved. It can be seen that certain branched paraffin (specific branched paraffin (B)) is not sufficiently separated and removed. In Comparative Examples 2 and 3, the CCS viscosity at −35 ° C. can be improved to some extent, but in Example 2, it was less than 3000 mPa · s, but only at a level exceeding 3000 mPa · s.

[Examples 4-6, Comparative Examples 4-6]
In Examples 4 to 6, lubricating oil compositions having the compositions shown in Table 3 were prepared using the above lubricating base oils 1 to 3 and the following additives, respectively. Moreover, in Comparative Examples 4-6, the lubricating oil composition which has a composition shown in Table 3 was prepared using said hydrocarbon raw materials 1-3 and the following additive, respectively. About each lubricating oil composition, MRV viscosity in -30 degreeC or -40 degreeC or BF viscosity in -40 degreeC was measured, respectively. The obtained results are shown in Table 3. In Table 3, “YS” means that when the MRV viscosity is measured, if the measurement cannot be performed within a certain time, a weight is added.
(Additive)
Additive Package A: An additive package containing an antioxidant, an ashless dispersant, a metallic detergent, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a metal deactivator, and the like.
Additive Package B: An additive package containing an antioxidant, an ashless dispersant, a metallic detergent, an antiwear agent, a corrosion inhibitor, a rust inhibitor, a metal deactivator, and the like.
Additive Package C: An additive package containing an antioxidant, ashless dispersant, metallic detergent, antiwear agent, friction modifier, corrosion inhibitor, rust inhibitor, metal deactivator, and the like.
Viscosity index improver D1: Polymethacrylate viscosity index improver (weight average molecular weight: 100,000)
Viscosity index improver D2: polymethacrylate viscosity index improver (weight average molecular weight: 300,000)
Pour point depressant E: Polymethacrylate pour point depressant (weight average molecular weight: 60,000)

As shown in Table 3, in the lubricating oil compositions of Examples 4 to 6, the MRV viscosity and BF viscosity of −30 ° C. or lower can be drastically reduced as compared with Comparative Examples 4 to 6. A significant effect of improving the low temperature viscosity characteristics was observed.

Claims (5)

A method for producing a hydrocarbon composition used in a lubricating base oil,
A hydrocarbon raw material containing a branched paraffin having a branched alkyl group having 5 or less carbon atoms is brought into contact with urea, and the number of carbon atoms from the hydrocarbon raw material to at least one end of the branched paraffin to the branch position is 6 The manufacturing method of a hydrocarbon composition provided with the process of isolate | separating the branched paraffin which is the above as a urea adduct thing, and obtaining a hydrocarbon composition.   The manufacturing method of the hydrocarbon composition of Claim 1 whose content of the linear paraffin in the said hydrocarbon raw material is 5 mass% or less. A hydrocarbon composition used for a lubricating base oil produced by the production method according to claim 1.   A lubricating base oil containing the hydrocarbon composition according to claim 3.   A lubricating oil composition comprising the hydrocarbon composition according to claim 3.