JP2006188634A - Method for producing lubricant base oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a lubricant base oil, with which a lubricant base oil having low viscosity, a high viscosity index and low evaporation property is efficiently and inexpensively obtained. <P>SOLUTION: The method for producing a lubricant base oil comprises a process for preparing a hydrocracking catalyst obtained by supporting at least one kind of a metal of the group VIa of the periodic table and at least one kind of a metal of the group VIII on a carrier having ≤80% fraction of desorption amount at 300-800°C based on the total desorption amount of NH<SB>3</SB>in NH<SB>3</SB>desorption temperature-dependency evaluation, a process for hydrocracking a raw material oil containing ≥50 vol.% of slack-wax in the presence of the hydrocracking catalyst under 0.1-14 MPa hydrogen partial pressure at 230-430°C average reaction temperature at 0.3-3.0hr<SP>-1</SP>LHSV at 50-14,000 scf/b ratio of hydrogen to oil, a process for distilling and separating the obtained hydrocracked oil to give a lubricating oil fraction and a process for dewaxing the lubricating oil fraction. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a lubricating base oil.

  Conventionally, the production of lubricating base oil from crude oil has been carried out as follows. First, crude oil is distilled at atmospheric pressure, and the residual oil is further distilled under reduced pressure, and separated into various lubricating oil fractions and vacuum distillation residual oil ranging from low viscosity to high viscosity. In order to obtain a heavy lubricating oil fraction (bright stock) from the vacuum distillation residual oil, the vacuum distillation residual oil is treated by a solvent removal method to remove asphalt. Further, a lubricating base oil is produced by subjecting various viscosity grade lubricating oil fractions including bright stock to purification treatments such as solvent refining, hydrorefining and dewaxing.

A hydrocracking method is known as a method for producing a high viscosity index lubricating base oil. This is a method for producing a high-viscosity index base oil from the resulting oil by hydrocracking a vacuum distillation distillate, bright stock, various waxes or a mixture thereof using a catalyst at high temperature and high pressure. For example, Patent Document 1 discloses a hydrocracking method using an alumina catalyst with a wax as a raw material oil, and Patent Documents 2 and 3 disclose a high viscosity index lubricating base oil based on a catalytic isomerization method using a slack wax as a raw material oil. Each manufacturing method is disclosed. Further, Patent Document 4 discloses that a mixture of crude heavy crude distillation oil and / or vacuum distillation oil and slack wax is hydrocracked in the presence of a hydrocracking catalyst to reduce the high viscosity index. A method for producing a viscosity lubricant base oil is disclosed.
Japanese Patent Publication No.57-17037 JP-A-1-223196 JP-A-1-301790 JP-A-6-116572

By the way, in recent years, in the fields of automobiles and industrial machinery, higher performance and energy saving have progressed, and there has been a strong demand for improving the performance of lubricating oils used in these devices. And since the performance of the lubricating oil depends largely on the quality of the lubricating base oil, improvement in the characteristics of the lubricating base oil is required, particularly in the fields of automotive lubricating oil such as engine oil and transmission oil and hydraulic oil for construction machinery. It has been. For example, as a lubricating base oil used for engine oil, both the kinematic viscosity at 100 ° C. and the CCS viscosity at −35 ° C. are low from the viewpoint of improving fuel economy and reducing CO ₂ emissions. There is a strong demand for low-viscosity base oils having a small NOACK value, which is an indicator of evaporation.

  However, even with the above conventional production method, there is room for improvement in the following points in order to obtain a lubricating base oil having a low viscosity, a high viscosity index and a low evaporation property.

  For example, in the case of a conventional production method using a solvent refining method, a lubricating base oil having a high viscosity index is limited to a lubricating oil fraction produced from a specific high-quality crude oil, and in the solvent refining process, Must be extremely high, and is not practical in terms of production efficiency and production cost.

Moreover, the conventional manufacturing method using hydrocracking method uses heavy oil such as vacuum distillation distillate, bright stock, various waxes, or a mixture thereof as a raw material oil, and has a relatively high viscosity. Although a high viscosity index can be achieved for the fraction, a relatively low viscosity fraction (a fraction having a kinematic viscosity at 100 ° C. of 2.5 to 7.5 mm ² / s or a kinematic viscosity at 40 ° C. Viscosity index at a fraction of 25 to 40 mm ² / s) is not so high. That is, the conventional hydrocracking method is mainly intended for the production of a relatively high viscosity lubricating base oil, and is suitable for the production of a low viscosity, high viscosity index and low evaporating lubricating base oil. I can't say that.

  In the case of the catalytic isomerization method of slack wax, the isomerization catalyst is likely to deteriorate due to the nitrogen compound or sulfur compound contained in the slack wax. Therefore, an increase in the number of steps, an increase in production efficiency, and an increase in production cost are inevitable, for example, it is necessary to provide a hydrorefining step before the isomerization step to sufficiently remove nitrogen and sulfur.

  The present invention has been made in view of such circumstances, and a method for producing a lubricating base oil capable of efficiently and inexpensively obtaining a low-viscosity, high-viscosity index, and low-evaporating lubricating base oil. The purpose is to provide.

In order to solve the above problems, a manufacturing method of the lubricating base oil of the present invention, NH ₃ desorption amount of the fraction of NH ₃ at 300 to 800 ° C. relative to the total desorption of NH ₃ in the desorption temperature dependence evaluation A first step of preparing a hydrocracking catalyst in which at least one of group VIa metals in the periodic table and at least one group VIII metal are supported on a carrier that is 80% or less; In the presence of a chemical cracking catalyst, a raw material oil containing 50% by volume or more of slack wax, hydrogen partial pressure 0.1-14 MPa, average reaction temperature 230-430 ° C., LHSV 0.3-3.0 hr ⁻¹ , hydrogen oil ratio 50 A second step of hydrocracking at ˜14000 scf / b, a third step of distilling and separating the cracked product oil obtained in the second step to obtain a lubricating oil fraction, and a lubricating oil fraction obtained in the third step 4th step of dewaxing Characterized in that it comprises a.

In the method for producing a lubricating base oil of the invention, as described above, Group VIa metals to the amount of desorption meet certain criteria carriers NH ₃ in NH ₃ desorption temperature dependence evaluation as hydrocracking catalyst and VIII, Slack in the feedstock by hydrocracking a feedstock containing 50% by volume or more of slack wax in the presence of the hydrocracking catalyst under the above specified conditions using a catalyst supporting both of the group metals. Isoparaffins can be efficiently and reliably produced by decomposing and isolating high molecular weight n-paraffins derived from wax or the like, and excessive decomposition of the produced isoparaffin compounds can be sufficiently suppressed. . Accordingly, the cracked product oil obtained by hydrocracking can be given a sufficient amount of molecules having a moderately branched chemical structure and a high viscosity index in a suitable molecular weight range. Through the dewaxing treatment of the fraction, a lubricating base oil having a low viscosity, a high viscosity index and a low evaporation property can be obtained efficiently and inexpensively.

  Furthermore, according to the production method of the present invention, when the obtained lubricating base oil is blended with the above-mentioned viscosity-temperature characteristics, excellent thermal / oxidative stability, and additives, the additives are added. The characteristic which improves the effect of can be provided. For example, when preparing a lubricating oil composition by adding an antioxidant to the lubricating oil obtained by the production method of the present invention, the characteristics that improve the thermal and oxidation stability of the lubricating base oil itself and the effectiveness of the antioxidant As a result of the synergistic action, a lubricating oil composition having a high level of thermal and oxidation stability can be obtained even if the amount of the antioxidant is small.

In this invention, it is preferable that the kinematic viscosity in 100 degreeC of slack wax is 3.0-25 mm < ² > / s. By using such a slack wax, it is possible to effectively realize all of the reduction in the viscosity, the increase in the viscosity index, and the reduction in the evaporation amount of the obtained lubricating base oil.

  Further, the carrier of the hydrocracking catalyst used in the present invention is an amorphous composite oxide, and is Al, B, Ba, Bi, Cd, Ga, La, Mg, Si, Ti, W, Y, Zn, and Zr. It is preferable to contain a binary oxide having an acid property of a composite of two kinds of oxides of elements selected from: In addition, the acid property binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder.

  Further, the carrier is amorphous silica / alumina, amorphous silica / zirconia, amorphous silica / magnesia, amorphous silica / titania, amorphous silica / boria, amorphous alumina / zirconia, amorphous alumina / magnesia, amorphous At least one selected from alumina / titania, amorphous alumina / boria, amorphous zirconia / magnesia, amorphous zirconia / titania, amorphous zirconia / boria, amorphous magnesia / titania, amorphous magnesia / boria and amorphous titania / boria It is preferable to contain two kinds of acid nature binary oxides. The acidic binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder. As such a binder, silica, alumina, magnesia, titania, zirconia, clay, or a mixture thereof is preferable.

  Further, in the hydrocracking catalyst used in the present invention, the supported amount of Group VIa metal is 5 to 30% by mass per one type of metal, and the supported amount of Group VIII metal is 0.2 to It is preferable that it is 10 mass%.

  Furthermore, the hydrocracking catalyst is preferably a catalyst having molybdenum and nickel supported on a carrier.

  According to the method for producing a lubricant base oil of the present invention, a lubricant base oil having a low viscosity, a high viscosity index and a low evaporation property can be obtained easily and reliably.

Hereinafter, preferred embodiments of the present invention will be described in detail.
(Raw oil)
In the method for producing a lubricating base oil of the present invention, a raw material oil containing 50% by volume or more of slack wax is used. The “raw oil containing 50% by volume or more of slack wax” as used in the present invention is a mixed oil of a raw oil consisting only of slack wax, slack wax and other raw material oil, and 50 volumes of slack wax. % And both raw material oils containing at least% are included.

Slack wax is produced as a by-product in the solvent dewaxing process when producing a lubricating base oil from a paraffinic lubricating oil fraction. The main component of slack wax is n-paraffin and branched paraffin (isoparaffin) with few side chains. There is little naphthene and aromatics. The kinematic viscosity of the slack wax used in the preparation of the raw material oil can be appropriately selected according to the kinematic viscosity of the target lubricating base oil, but a low viscosity base oil is produced as the lubricating base oil of the present invention. For this, a relatively low viscosity slack wax having a kinematic viscosity at 100 ° C. of about ² to 25 mm ² / s, preferably about 2.5 to ²⁰ mm ² / s, more preferably about 3 to 15 mm ² / s is desirable. . Moreover, although the other property of slack wax is also arbitrary, melting | fusing point becomes like this. Preferably it is 35-80 degreeC, More preferably, it is 45-70 degreeC. The oil content of the slack wax is preferably 50% by mass or less, more preferably 25% by mass or less. The sulfur content of the slack wax is preferably 1% by mass or less, more preferably 0.5% by mass or less.

  When the raw material oil is a mixed oil of slack wax and other raw material oil, the other raw material oil is not particularly limited as long as the ratio of slack wax to the total amount of the mixed oil is 50% by volume or more. A heavy oil-distilled distillate and / or a mixed oil of vacuum-distilled distillate is preferably used.

  Further, when the raw material oil is a mixed oil of slack wax and another raw material oil, the ratio of slack wax in the mixed oil is more preferably 70% by volume or more from the viewpoint of producing a base oil having a high viscosity index. 75% by volume or more is even more preferable. When the ratio is less than 50% by volume, the oil base such as aromatics and naphthenes in the obtained lubricating base oil tends to increase and the viscosity index of the lubricating base oil tends to decrease.

On the other hand, the heavy atmospheric distillation distillate and / or vacuum distillation distillate of crude oil used in combination with slack wax has a distillation temperature of 300 to 570 ° C. in order to keep the viscosity index of the lubricating base oil produced high. A fraction having a distillate component of 60% by volume or more in the range is preferable.
(Hydrocracking catalyst)
In the present invention, the NH ₃ desorption amount of the fraction of NH ₃ at 300 to 800 ° C. relative to the total desorption of NH ₃ in the desorption temperature dependence evaluation is less than 80% carrier, the periodic table of the Group VIa metals A hydrocracking catalyst in which at least one of them and at least one of Group VIII metals is supported is used.

Here, “NH ₃ desorption temperature dependency evaluation” refers to literature (Sawa M., Niwa M., Murakami Y., Zeolites 1990, 10, 532, Karge HG, Dondur V., J. Phys. Chem. 1990, 94, 765, etc.) and is performed as follows. First, the catalyst carrier is pretreated at a temperature of 400 ° C. or higher for 30 minutes or more under a nitrogen stream to remove adsorbed molecules, and then adsorbs NH ₃ at 100 ° C. until saturation. Then, the catalyst support to 100 to 800 ° C. 10 ° C. / min was heated by the following heating rate desorbed NH _3, to monitor the NH ₃ separated at every predetermined temperature by desorption. Then, the fraction of the NH ₃ desorption amount at 300 ° C. to 800 ° C. with respect to the total NH ₃ desorption amount (desorption amount at 100 to 800 ° C.) is obtained.

The catalyst support used in the present invention are those desorption of the fraction of NH ₃ at 300 to 800 ° C. relative to the total desorption of NH ₃ in the NH ₃ desorption temperature dependence evaluation of the following 80%, preferably Is 70% or less, more preferably 60% or less. By constituting a hydrocracking catalyst using such a carrier, the acid properties that govern the cracking activity are sufficiently suppressed, so that the high molecular weight n-paraffin derived from slack wax or the like in the raw oil by hydrocracking. The production of isoparaffin by decomposition isomerization can be performed efficiently and reliably, and excessive decomposition of the produced isoparaffin compound can be sufficiently suppressed. As a result, a sufficient amount of molecules having a moderately branched chemical structure and a high viscosity index can be provided in an appropriate molecular weight range.

  As such a support, a binary oxide which is amorphous and has an acid property is preferable. For example, it is exemplified in the literature ("Metal oxide and its catalytic action", Tetsuro Shimizu, Kodansha, 1978). And binary oxides.

Among them, an amorphous composite oxide which is an acid composed of two kinds of oxides of elements selected from Al, B, Ba, Bi, Cd, Ga, La, Mg, Si, Ti, W, Y, Zn and Zr. It is preferable to contain a property binary oxide. By adjusting the ratio of each oxide of these acid property binary oxides, a support having an acid property suitable for this purpose can be obtained in the NH ₃ adsorption / desorption evaluation. In addition, the acid property binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder.

  Further, the carrier is amorphous silica / alumina, amorphous silica / zirconia, amorphous silica / magnesia, amorphous silica / titania, amorphous silica / boria, amorphous alumina / zirconia, amorphous alumina / magnesia, amorphous At least one selected from alumina / titania, amorphous alumina / boria, amorphous zirconia / magnesia, amorphous zirconia / titania, amorphous zirconia / boria, amorphous magnesia / titania, amorphous magnesia / boria and amorphous titania / boria It is preferable to contain two kinds of acid nature binary oxides. The acidic binary oxide constituting the carrier may be one of the above or a mixture of two or more. Further, the carrier may be composed of the above-mentioned acid property binary oxide, or may be a carrier obtained by binding the acid property binary oxide with a binder. The binder is not particularly limited as long as it is generally used for catalyst preparation, but is preferably selected from silica, alumina, magnesia, titania, zirconia, clay, or a mixture thereof.

  In the present invention, the carrier includes at least one of group VIa metals (molybdenum, chromium, tungsten, etc.) and at least one of group VIII metals (nickel, cobalt, palladium, platinum, etc.). One type is supported to form a hydrocracking catalyst. These metals are responsible for hydrogenation ability, terminate the reaction in which the paraffinic compound is decomposed or branched by the acidic carrier, and play an important role in producing isoparaffin having an appropriate molecular weight and branched structure.

  As the amount of metal supported in the hydrocracking catalyst, the supported amount of Group VIa metal is 5 to 30% by mass per one type of metal, and the supported amount of Group VIII metal is 0.2 to 10% by mass per one type of metal. % Is preferred.

  Further, in the hydrocracking catalyst used in the present invention, molybdenum is included in the range of 5 to 30% by mass as one or more metals of Group VIa metal, and as one or more metals of Group VIII metal. More preferably, nickel is contained in the range of 0.2 to 10% by mass.

The hydrocracking catalyst composed of the above support and one or more metals of Group VIa metal and one or more metals of Group VIII metal is preferably used for hydrocracking in a sulfurized state. The sulfurization treatment can be performed by a known method.
(Hydrolysis process)
In the present invention, in the presence of the above-mentioned hydrocracking catalyst, a raw material oil containing 50% by volume or more of slack wax, a hydrogen partial pressure of 0.1 to 14 MPa (preferably 1 to 14 MPa, more preferably 2 to 7 MPa), Average reaction temperature 230-430 ° C. (preferably 330-400 ° C., more preferably 350-390 ° C.), LHSV 0.3-3.0 hr ⁻¹ (preferably 0.5-2.0 hr ⁻¹ ), hydrogen oil ratio Hydrogenolysis is performed at 50 to 14000 scf / b (preferably 100 to 5000 scf / b).

  In such a hydrocracking process, isomerization to isoparaffin progresses in the process of cracking n-paraffin derived from slack wax in the raw material oil, thereby producing an isoparaffin component having a low pour point and a high viscosity index. At the same time, it breaks down aromatic compounds, which are inhibitors of high viscosity index contained in the feedstock, into monocyclic aromatic compounds, naphthene compounds and paraffin compounds, and inhibits high viscosity index. The polycyclic naphthene compound as a factor can be decomposed into a monocyclic naphthene compound or a paraffin compound. From the viewpoint of increasing the viscosity index, it is preferable that the raw material oil contains fewer compounds having a high boiling point and a low viscosity index.

Further, the decomposition rate for evaluating the progress of the reaction is expressed by the following formula:
(Decomposition rate (volume%)) = 100− (ratio of the fraction having a boiling point of 360 ° C. or more in the product (volume%))
In this way, the decomposition rate is preferably 3 to 90% by volume. When the decomposition rate is less than 3% by volume, isoparaffins are generated by decomposition and isomerization of high-molecular-weight n-paraffins having a high pour point contained in the feedstock, and hydrocracking of aromatics and polycyclic naphthenes with poor viscosity index. When the decomposition rate exceeds 90% by volume, the yield of the lubricating oil fraction decreases, which is not preferable.
(Distillation separation process)
Next, the lubricating oil fraction is distilled and separated from the cracked product oil obtained by the hydrocracking step. At this time, a fuel oil fraction may be obtained as a light component.

  The fuel oil fraction is a fraction obtained as a result of sufficient desulfurization and denitrogenation, and sufficient aromatic hydrogenation. Among these, the naphtha fraction has a high isoparaffin content, the kerosene fraction has a high smoke point, and the light oil fraction has a high cetane number.

  On the other hand, when hydrocracking in the lubricating oil fraction is insufficient, a part of it may be subjected to the hydrocracking process again. Further, in order to obtain a lubricating oil fraction having a desired kinematic viscosity, the lubricating oil fraction may be further distilled under reduced pressure. This vacuum distillation separation may be performed after the dewaxing treatment described below.

In the evaporative separation step, a lubricant base oil called 70 Pale, SAE10, or SAE20 can be suitably obtained by distilling the cracked product oil obtained in the hydrocracking step under reduced pressure. More specifically, in the present invention, a lubricating base oil having the following properties can be obtained as a lubricating base oil corresponding to 70 Pale, SAE 10 or SAE 20. In addition, the following various properties are final properties of the lubricating base oil obtained through treatments such as hydrocracking, distillation, and dewaxing. Further, the NOACK evaporation amount in the present invention means an evaporation loss amount measured in accordance with ASTM D 5800.
70 Pale: Kinematic viscosity at 100 ° C. is 2.5 to 3.0 mm ² / s, viscosity index is 110 or more, and pour point is −15 ° C. or less SAE 10: Kinematic viscosity at 100 ° C. is 3.0 to 5.5 mm ² / S, viscosity index is 130 or more, CCS viscosity at -30 ° C is 1600 or less, NOACK evaporation is 15% by mass or less, and pour point is -10 ° C or less SAE20: kinematic viscosity at 40 ° C is 25 to 40 mm ² / s, the viscosity index is 130 or more, and the pour point is -10 ° C or less.

A system using slack wax having a lower viscosity as a raw material oil is suitable for producing a large amount of 70 Pale and 10 SAE fractions, and a system using slack wax having a high viscosity within the scope of the present invention is used as a raw oil. Suitable for producing many. However, even if a high-viscosity slack wax is used, conditions for generating a considerable amount of 70 Pale and SAE 10 can be selected depending on the progress of the decomposition reaction.
(Dewaxing process)
In the above-described distillation separation step, since the lubricating oil fraction fractionated from the cracked product oil has a high pour point, it is dewaxed to obtain a lubricating base oil having a desired pour point. The dewaxing treatment can be performed by a usual method such as a solvent dewaxing method or a contact dewaxing method. Among these, the solvent dewaxing method generally uses a mixed solvent of MEK and toluene, but may use a solvent such as benzene, acetone, MIBK or the like. In order to set the pour point of the dewaxed oil to −10 ° C. or lower, it is preferable to carry out under the conditions of a solvent / oil ratio of 1 to 6 times and a filtration temperature of −5 to −45 ° C. (preferably −10 to −40 ° C.). The wax removed here can be used again as a slack wax in the hydrocracking step.

  In the present invention, a solvent purification treatment and / or a hydrorefining treatment may be added to the dewaxing treatment. These additional treatments are performed in order to improve the ultraviolet stability and oxidation stability of the lubricating base oil, and can be carried out by a method used in a normal lubricating oil refining process.

  In the solvent purification, furfural, phenol, N-methylpyrrolidone or the like is generally used as a solvent, and a small amount of aromatic compounds, particularly polycyclic aromatic compounds remaining in the lubricating oil fraction are removed.

In addition, hydrorefining is performed to hydrogenate olefin compounds and aromatic compounds, and the catalyst is not particularly limited. However, at least one of Group VIa metals such as molybdenum, cobalt, nickel, etc. Using an alumina catalyst supporting at least one of the Group VIII metals, the reaction pressure (hydrogen partial pressure) is 7 to 16 MPa, the average reaction temperature is 300 to 390 ° C., and the LHSV is 0.5 to 4.0 hr ⁻¹ . Can be done below.

  According to the method for producing a lubricating base oil of the present invention having the above-described configuration, a low-viscosity, high-viscosity index and low-evaporating lubricating base oil can be obtained efficiently and inexpensively. It is suitable for producing a lubricating base oil such as SAE10 or SAE20.

  Further, the lubricating base oil obtained by the production method of the present invention itself has excellent thermal / oxidative stability, and when an additive is added to the lubricating base oil, The additive function can be expressed at a higher level while the additive is sufficiently stably dissolved and retained in the lubricating base oil. Therefore, in a lubricating oil composition in which an antioxidant is blended with the lubricating base oil, a high level of thermal / oxidative stability can be achieved. For example, when the obtained lubricating base oil corresponds to 70 Pale, the RBOT life can be 290 min or longer. Further, when the obtained lubricating base oil corresponds to SAE10, the RBOT life can be 350 min or longer. Further, when the obtained lubricating base oil corresponds to SAE 20, the RBOT life can be 400 min or longer. The RBOT life as used herein refers to a composition in which 0.2% by mass of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) is added to a lubricating base oil. It means the RBOT value measured according to JIS K 2514.

  Furthermore, according to the lubricating base oil obtained by the production method of the present invention, the lubricating base oil itself has excellent viscosity-temperature characteristics and frictional characteristics, so that an improvement in friction reduction effect and, in turn, an improvement in energy saving is achieved. can do. Furthermore, since the lubricating base oil is also excellent in terms of the effectiveness of the additive, when a friction reducing agent is blended with the lubricating base oil, a high level of friction reducing effect and energy saving can be achieved. it can.

  Since the lubricating base oil obtained by the production method of the present invention has excellent characteristics as described above, it can be suitably used as a base oil for various lubricating oils. Specifically, the lubricant base oil is used for lubricating oils used in internal combustion engines such as gasoline engines for passenger cars, gasoline engines for motorcycles, diesel engines, gas engines, gas heat pump engines, marine engines, and power generation engines. (Lubricating oil for internal combustion engines), automatic transmissions, manual transmissions, continuously variable transmissions, final reduction gears, etc. Lubricating oils (drive transmission device oils), shock absorbers, hydraulic equipment for construction machinery, etc. Hydraulic oil, compressor oil, turbine oil, gear oil, refrigerating machine oil, metalworking oil used in the above, and the like. By using the lubricating base oil of the present invention for these applications, the viscosity of each lubricating oil Improvements in temperature characteristics, thermal / oxidation stability, energy savings, fuel savings, etc., as well as extending the life of each lubricant and reducing environmentally hazardous substances at a high level Kill as to become.

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]
First, amorphous silica-alumina (silica: alumina = 50: 50 (mass ratio)) was prepared, and NH ₃ desorption temperature dependency was evaluated. NH ₃ at 300 to 800 ° C. with respect to the total desorption amount of NH ₃ The fraction of the desorption amount of ₃ was 53%. The relationship between the temperature and the NH ₃ desorption amount in the NH ₃ desorption temperature dependency evaluation is shown in FIG. The amorphous silica / alumina was loaded with 3% by mass of nickel and 15% by mass of molybdenum to obtain a hydrocracking catalyst.

Next, the obtained hydrocracking catalyst was used in a sulfided state, and slack wax having the properties shown in Table 1 (hereinafter referred to as slack wax A) was used as a raw material oil, with a hydrogen partial pressure of 10 MPa, an average reaction temperature of 330 ° C., Hydrocracking was performed at LHSV 1.0 hr ⁻¹ and a hydrogen oil ratio of 1000 scf / b. Furthermore, gas, naphtha and middle distillate were distilled off from the obtained cracked product oil, and 70 Pale fraction, SAE10 fraction and SAE20 fraction were fractionated from the residue, respectively. The decomposition rate of hydrocracking was 30% by volume.

次に、分留したＳＡＥ１０留分について、メチルエチルケトンとトルエンとの混合溶剤を用いて、溶剤／油比３／１で溶剤脱ろうを行い、ＳＡＥ１０に相当する潤滑油基油を得た。得られた潤滑油基油の１００℃における動粘度は４．０５ｍｍ^２／ｓ、粘度指数は１４０、流動点は−２０℃、−３０℃におけるＣＣＳ粘度は１３９０ｍＰａ・ｓであった。また、実施例１の潤滑油基油について、ＡＳＴＭ Ｄ ５８００に準拠して、２５０℃、１時間の条件でＮＯＡＣＫ蒸発量を測定した。その結果、ＮＯＡＣＫ蒸発量は１４質量％であった。更に、ＳＡＥ１０相当の潤滑油基油にフェノール系酸化防止剤（２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール；ＤＢＰＣ）を０．２質量％添加した組成物について、ＪＩＳ Ｋ ２５１４に準拠して、１５０℃でのＲＢＯＴ残存寿命を測定した。その結果、ＲＢＯＴ残存寿命は３３０ｍｉｎであった。

Next, the fractioned SAE10 fraction was subjected to solvent dewaxing using a mixed solvent of methyl ethyl ketone and toluene at a solvent / oil ratio of 3/1 to obtain a lubricating base oil corresponding to SAE10. The obtained lubricating base oil had a kinematic viscosity at 100 ° C. of 4.05 mm ² / s, a viscosity index of 140, a pour point of −20 ° C., and a CCS viscosity at −30 ° C. of 1390 mPa · s. Moreover, about the lubricating base oil of Example 1, NOACK evaporation was measured on condition of 250 degreeC and 1 hour based on ASTMD5800. As a result, the NOACK evaporation amount was 14% by mass. Furthermore, a composition obtained by adding 0.2% by mass of a phenol-based antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) to a lubricating base oil equivalent to SAE10 conforms to JIS K 2514. The RBOT remaining life at 150 ° C. was measured. As a result, the RBOT remaining life was 330 min.

  As described above, the lubricant base oil equivalent to SAE10 obtained in Example 1 is a lubricant base oil that is low in viscosity and has an extremely high viscosity index and can provide an engine oil excellent in fuel economy. there were. Further, since this lubricating base oil has excellent low-temperature characteristics, low evaporability, and excellent antioxidant properties, it was a very high-performance lubricating base oil from a comprehensive point of view.

Moreover, about 70 Pale fraction, solvent dewaxing was performed like the case of SAE 10 fraction, and lubricating base oil corresponding to 70 Pale was obtained. The resulting lubricant base oil has a kinematic viscosity at 100 ° C. of 2.8 mm ² / s, a viscosity index of 114, a pour point of −22.5 ° C. It was a lubricating base oil.

Further, the SAE 20 fraction was subjected to solvent dewaxing in the same manner as in the SAE 10 fraction, and a lubricating base oil corresponding to SAE 20 was obtained. The obtained lubricating base oil has a kinematic viscosity at 40 ° C. of 38.2 mm ² / s, a viscosity index of 143, a RBOT remaining life of 400 min, a low viscosity, an extremely high viscosity index, and an antioxidant property. Excellent lubricating base oil from a comprehensive point of view.
[Example 2]
First, a support was prepared using 50 parts by mass of amorphous silica / zirconia (silica: zirconia = 50: 50 (mass ratio)) and 50 parts by mass of alumina as a binder. This was subjected to a NH ₃ desorption temperature dependence evaluation of carrier, desorption of the fraction of NH ₃ at 300 to 800 ° C. relative to the total desorption of NH ₃ was 24%. FIG. 2 shows the relationship between the temperature and the NH ₃ desorption amount in the NH ₃ desorption temperature dependency evaluation. This support was loaded with 3% by weight of nickel and 15% by weight of molybdenum to obtain a hydrocracking catalyst.

  A lubricating oil base corresponding to 70 Pale, SAE 10 and SAE 20 was obtained in the same manner as in Example 1 except that the hydrogenation catalyst thus obtained was used, and hydrocracking, distillation separation, and solvent dewaxing were sequentially performed. Got oil.

The kinematic viscosity at 100 ° C. of the lubricating base oil corresponding to SAE10 was 3.95 mm ² / s, the viscosity index was 145, the pour point was −20 ° C., and the CCS viscosity at −30 ° C. was 1600 mPa · s. Moreover, about the lubricating base oil of Example 2, NOACK evaporation was measured on condition of 250 degreeC and 1 hour based on ASTMD5800. As a result, the NOACK evaporation amount was 13% by mass. Furthermore, a composition obtained by adding 0.2% by mass of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) to a lubricating base oil equivalent to SAE is based on JIS K 2514. The RBOT remaining life at 150 ° C. was measured. As a result, the RBOT remaining life was 350 min.

  As described above, the SAE10 lubricating base oil obtained in Example 2 was a lubricating base oil that has an extremely high viscosity index and can provide an engine oil excellent in fuel efficiency while having a low viscosity. . Further, since this lubricating base oil has excellent low-temperature characteristics, low evaporability, and excellent antioxidant properties, it was a very high-performance lubricating base oil from a comprehensive point of view.

The lubricating base oil corresponding to 70 Pale has a kinematic viscosity at 100 ° C. of 3.0 mm ² / s, a viscosity index of 116, and a pour point of −25 ° C. It was a lubricating base oil.

Furthermore, the kinematic viscosity at 40 ° C. of the lubricating base oil corresponding to SAE20 is 39.1 mm ² / s, the viscosity index is 145, the RBOT remaining life is 420 min, and the viscosity index is extremely high despite being low viscosity. From a comprehensive point of view, it was a high-performance lubricating base oil with excellent antioxidant properties.
[Comparative Example 1]
First, amorphous silica-alumina (silica: alumina = 5: 95 (mass ratio)) was prepared, and when NH ₃ desorption temperature dependency was evaluated for this support, 300 to 800 ° C. with respect to the total desorption amount of NH _3. The fraction of NH ₃ desorption amount at 99% was 99%. The relationship between the temperature and the NH ₃ desorption amount in the NH ₃ desorption temperature dependency evaluation is shown in FIG. This support was loaded with 3% by weight of nickel and 15% by weight of molybdenum to obtain a hydrocracking catalyst.

  A lubricating oil base corresponding to 70 Pale, SAE 10 and SAE 20 was obtained in the same manner as in Example 1 except that the hydrogenation catalyst thus obtained was used, and hydrocracking, distillation separation, and solvent dewaxing were sequentially performed. Got oil.

The kinematic viscosity at 100 ° C. of the lubricating base oil corresponding to SAE10 was 4.5 mm ² / s, the viscosity index was 120, the pour point was −20 ° C., and the CCS viscosity at −30 ° C. was 2100 mPa · s. Moreover, about the lubricating base oil of the comparative example 1, NOACK evaporation was measured on condition of 250 degreeC and 1 hour based on ASTMD5800. As a result, the NOACK evaporation amount was 13% by mass. Furthermore, a composition in which 0.2% by mass of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) is added to a SAE-equivalent lubricating base oil conforms to JIS K 2514. The RBOT remaining life at 150 ° C. was measured. As a result, the RBOT remaining life was 270 min.

  As described above, the SAE10 lubricating base oil obtained in Comparative Example 1 did not sufficiently achieve low viscosity and high viscosity index, and had insufficient oxidation stability.

4 is a graph showing the results of evaluating the NH ₃ desorption temperature dependence of the catalyst carrier used in Example 1. 4 is a graph showing the evaluation results of NH ₃ desorption temperature dependence of the catalyst carrier used in Example 2. 6 is a graph showing the results of evaluating the NH ₃ desorption temperature dependence of the catalyst carrier used in Comparative Example 1.

Claims (6)

NH ₃ to the carrier desorption of the fraction of the NH ₃ is 80% or less at 300 to 800 ° C. relative to the total desorption of NH ₃ in the desorption temperature dependence evaluation, at least one of the periodic table Group VIa metals And a first step of preparing a hydrocracking catalyst on which at least one of the Group VIII metals is supported,
In the presence of the hydrocracking catalyst, a feed oil containing 50% by volume or more of slack wax, hydrogen partial pressure of 0.1-14 MPa, average reaction temperature of 230-430 ° C., LHSV 0.3-3.0 hr ⁻¹ , hydrogen oil A second step of hydrocracking at a ratio of 50-14000 scf / b;
A third step of distilling and separating the cracked product oil obtained in the second step to obtain a lubricating oil fraction;
And a fourth step of dewaxing the lubricating oil fraction obtained in the third step. The method for producing a lubricating base oil according to claim 1, wherein the slack wax has a kinematic viscosity at 100 ° C. of 3.0 to 25 mm ² / s.   The carrier is an amorphous composite oxide, and is a composite of two kinds of oxides of elements selected from Al, B, Ba, Bi, Cd, Ga, La, Mg, Si, Ti, W, Y, Zn, and Zr. The method for producing a lubricating base oil according to claim 1, comprising a binary oxide having an acid property.   The carrier is amorphous silica / alumina, amorphous silica / zirconia, amorphous silica / magnesia, amorphous silica / titania, amorphous silica / boria, amorphous alumina / zirconia, amorphous alumina / magnesia, amorphous alumina / At least one selected from titania, amorphous alumina / boria, amorphous zirconia / magnesia, amorphous zirconia / titania, amorphous zirconia / boria, amorphous magnesia / titania, amorphous magnesia / boria and amorphous titania / boria It contains, The manufacturing method of the lubricating base oil as described in any one of Claims 1-3 characterized by the above-mentioned.   In the hydrocracking catalyst, the supported amount of the Group VIa metal is 5 to 30% by mass per one type of metal, and the supported amount of the Group VIII metal is 0.2 to 10% by mass per one type of metal. The manufacturing method of the lubricating base oil as described in any one of Claims 1-4 characterized by the above-mentioned. The method for producing a lubricating base oil according to claim 1, wherein the hydrocracking catalyst is a catalyst in which molybdenum and nickel are supported on the carrier.

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