JP6009197B2 - Method for producing lubricating base oil - Google Patents

Description

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

  Among petroleum products, for example, lubricating oil, light oil, jet fuel and the like are products in which fluidity at low temperatures is regarded as important. Therefore, the base oils used in these products have wax components such as normal paraffin and slightly branched isoparaffin that cause a decrease in low-temperature fluidity completely or partially removed, or wax. It is desirable to be converted to something other than ingredients.

  As a dewaxing technique for removing the wax component from the hydrocarbon oil, for example, a method of extracting the wax component with a solvent such as liquefied propane or MEK is known. However, this method has a high operating cost and a problem of a decrease in product yield due to removal of wax.

  When producing a lubricating base oil by solvent dewaxing, furfural, N-methyl-2-pyrrolidinone, tetrahydrofuran, etc. before and after solvent dewaxing for the purpose of improving the oxidation stability of the finally obtained lubricating base oil The aromatic component is extracted and removed by the above. This treatment further reduces the yield of the lubricating base oil.

  As a method that can increase the yield of lubricating base oil over solvent dewaxing, there is a method of converting a wax component in a hydrocarbon oil into a non-wax component by a catalyst. As this method, for example, hydrocarbon oil is brought into contact with a so-called bifunctional catalyst having hydrogenation-dehydrogenation ability and isomerization ability in the presence of hydrogen, and normal paraffin in the hydrocarbon is isomerized to isoparaffin. Isomerization dewaxing is known.

  As the bifunctional catalyst used for isomerization dewaxing, a catalyst containing a molecular sieve made of a solid acid, in particular, zeolite or the like, and a metal belonging to Group 8 to Group 10 or Group 6 of the periodic table, particularly on a molecular sieve, is described above. There is known a catalyst having a metal supported thereon (see, for example, Patent Document 1 below).

JP-T-2006-502297

  There are several types of products using the lubricating base oil depending on the purpose of use. Because the low-temperature performance and viscosity characteristics required for each product differ depending on the oil type, the raw material oil of each product that has been fractionated by distillation in advance during isomerization dewaxing is individually applied at the optimal reaction temperature for each oil type. It was common to perform an isomerization dewaxing treatment.

  In isomerization dewaxing, generally, the higher the reaction temperature in the reactor, the faster the isomerization reaction proceeds. On the other hand, the cracking reaction also proceeds to lighten the product oil and reduce the product yield. For this reason, it is desirable that the reaction temperature in the isomerization dewaxing is as low as possible within the range satisfying the performance and production required for the product oil. However, when obtaining a product oil excellent in low-temperature fluidity suitable for a base oil for lubricating oil, it is necessary to set the reaction temperature so that the conversion rate of normal paraffin is sufficiently high. difficult. In particular, since the reaction temperature of isomerization dewaxing of heavy hydrocarbon oil requires a higher temperature than light hydrocarbon oil, it is difficult to improve the yield of heavy lubricating base oil.

  An object of this invention is to provide the manufacturing method of the lubricating base oil which can manufacture a heavy lubricating base oil efficiently.

  The method for producing a lubricating base oil of the present invention comprises a heavy hydrocarbon oil containing normal paraffin having a boiling point of 470 ° C. or higher, a light hydrocarbon oil containing normal paraffin having a boiling point of 330 ° C. or higher and lower than 470 ° C., And a step of bringing a base oil feedstock obtained by mixing with a hydroisomerization catalyst in the presence of hydrogen.

  In this specification, the boiling point means a value at normal pressure (101.325 kPa).

  According to the method for producing a lubricating base oil of the present invention, heavy hydrocarbons are obtained by isomerizing and dewaxing a base oil feedstock obtained by mixing the specific light hydrocarbon oil with the specific heavy hydrocarbon oil. The reaction temperature required for the oil isomerization reaction can be lowered, and the yield of the lubricating base oil corresponding to the heavy hydrocarbon oil can be improved. Also, the reaction temperature required for the isomerization reaction of heavy hydrocarbon oil is the same as the reaction temperature required for isomerization dewaxing of heavy hydrocarbon oil alone, and light hydrocarbon oil is isomerized and dewaxed alone. Sometimes it can be lower than the arithmetic average with the required reaction temperature. For these reasons, the present inventors believe that the presence of light hydrocarbon oil in the feedstock improves the contact efficiency between the feedstock and the catalyst, and the isomerization reaction proceeds efficiently.

  Further, according to the method for producing a lubricating base oil of the present invention, the reaction temperature in the isomerization dewaxing of heavy hydrocarbon oil can be lowered. The adjustment time of the reaction temperature when performing low isomerization dewaxing can be shortened. Thereby, the manufacturing efficiency in manufacture of the lubricating base oil from which oil types differ can be improved.

  In the method for producing a lubricating base oil of the present invention, it is preferable that the heavy hydrocarbon oil has a boiling point of 470 ° C. or higher and the light hydrocarbon oil has a boiling point of less than 470 ° C.

  In the method for producing a lubricating base oil of the present invention, the content of the light hydrocarbon oil is preferably 10 parts by volume or more and 40 parts by volume or less when the total amount of the base oil feedstock is 100 parts by volume.

  In the method for producing a lubricating base oil of the present invention, the hydroisomerization catalyst includes a carrier containing molecular sieves, and a metal belonging to Groups 8, 9, and 10 of the periodic table carried on the carrier. It is preferable that the catalyst composition is obtained by firing a catalyst composition containing at least one metal selected from the group consisting of molybdenum and tungsten.

  In addition, the hydroisomerization catalyst has a high isomerization selectivity in that a support containing zeolite having a 10-membered one-dimensional pore structure, platinum and / or palladium supported on the support, The micropore volume per unit mass of the hydroisomerization catalyst is 0.02 to 0.11 cc / g, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.00. It is preferable that it is 04-0.12cc / g.

In addition, the hydroisomerization catalyst described above is an organic template-containing zeolite containing an organic template and having a 10-membered one-dimensional pore structure, ammonium ions and / or protons, in that high isomerization selectivity can be obtained. A first step of obtaining a carrier precursor by heating a mixture containing ion-exchanged zeolite obtained by ion exchange in a solution containing the binder and a binder at a temperature of 250 to 350 ° C. in an N ₂ atmosphere; A catalyst precursor in which a platinum salt and / or palladium salt is contained in the precursor is calcined at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen, and platinum and / or palladium is supported on a support containing zeolite. And a second step of obtaining a hydroisomerization catalyst that has been obtained.

  In the present specification, the micropore volume per unit mass of the hydroisomerization catalyst is calculated by a method called nitrogen adsorption measurement. That is, for the catalyst, the physical adsorption / desorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is analyzed. Specifically, the adsorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is expressed as t. By analyzing by the -plot method, the micropore volume per unit mass of the catalyst is calculated. The micropore volume per unit mass of zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

  In the present specification, the micropore refers to a “pore having a diameter of 2 nm or less” defined by the International Union of Pure and Applied Chemistry (IUPAC).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the lubricating base oil which can manufacture a heavy lubricating base oil efficiently can be provided.

It is a mimetic diagram showing one embodiment of a manufacturing system of hydrocarbon oil in which a manufacturing method of lubricating base oil concerning the present invention is carried out.

  The present invention will be described below with reference to FIG. FIG. 1 shows an embodiment of a production system in which the method for producing a lubricating base oil according to this embodiment is implemented. The production system 100 includes a first fractionator 10, a light hydrocarbon oil storage tank 20, a first heavy hydrocarbon oil storage tank 30, a second heavy hydrocarbon oil storage tank 40, a hydroisomerization apparatus 50, a hydrogenation A processing device 60, a second rectifying column 65, and a third rectifying column 70 are provided. The first rectifying column 10 is connected to a line L1 for supplying the first rectifying column 10 with a wax fraction as a raw material for the lubricating base oil. In the first fractionator 10, the light hydrocarbon oil, the first heavy hydrocarbon oil, and the second heavy hydrocarbon oil fractionated in the first fractionator 10 are respectively mixed with the light hydrocarbon oil. Lines L2, L3 and L4 for transferring to the storage tank 20, the first heavy hydrocarbon oil storage tank 30 and the second heavy hydrocarbon oil storage tank 40 are connected. Lines L12, 13 and 14 for transferring the hydrocarbon oil stored in the light hydrocarbon oil storage tank 20, the first heavy hydrocarbon oil storage tank 30 and the second heavy hydrocarbon oil storage tank 40 to the subsequent stage. Are connected to each other. The lines L12, 13 and 14 are connected to the line 15, and a mixed oil obtained by mixing a predetermined hydrocarbon oil at a predetermined ratio can be supplied to the hydroisomerization apparatus 50 via the line 15. The hydroisomerization apparatus 50 is connected to a line L16 for transferring the product oil obtained by hydroisomerization to the hydroprocessing apparatus 60. The hydrotreating apparatus 60 is connected to a line L17 for transferring the product oil that has been subjected to hydrofinishing to the second rectifying column 65. Lines L18, L19 and L20 for taking out the naphtha fraction, kerosene oil fraction and lubricating oil fraction fractionated in the second rectification column 65 are connected to the second rectification column 65. The line L <b> 20 is connected to the third rectifying tower 70, and the lubricating oil fraction can be supplied to the third rectifying tower 70. The third rectifying tower 70 is connected to lines L22, L23, and L24 for taking out various lubricating base oils fractionated in the third rectifying tower 70. The “line” means a pipe for transferring a fluid.

  The manufacturing method of the lubricating base oil according to the present embodiment using the manufacturing system 100 will be described. The method according to this embodiment includes the following steps S1 to S5.

  In step S1, the wax fraction is fractionated into a heavy hydrocarbon oil and a light hydrocarbon oil in the first fractionator 10. In the present embodiment, the wax fraction is fractionated into a first heavy hydrocarbon oil, a second heavy hydrocarbon oil and a light hydrocarbon oil that are heavier than the first heavy hydrocarbon oil. Yes.

  In step S2, in the hydroisomerization apparatus 50, a heavy hydrocarbon oil containing normal paraffin having a boiling point of 470 ° C. or more, a light hydrocarbon oil containing normal paraffin having a boiling point of 330 ° C. or more and less than 470 ° C., Is mixed with a hydroisomerization catalyst in the presence of hydrogen.

  In step S3, the hydrofinishing apparatus 60 hydrofinishes the product oil obtained from the hydroisomerization apparatus 50.

  In step S4, in the second rectifying column 65, the product oil hydrofinished by the hydrotreating apparatus 60 is fractionated into a naphtha fraction, a kerosene oil fraction, and a lubricating oil fraction by atmospheric distillation.

    In step S5, in the third rectifying tower 70, the lubricating oil fraction obtained as the bottom oil in the second rectifying tower 65 is fractionated into various lubricating base oils.

  Hereinafter, steps S1 to S5 will be described in more detail.

(Process S1)
The heavy hydrocarbon oil and the light hydrocarbon oil can be obtained, for example, by fractionating a wax fraction having a boiling point of 330 ° C. or higher containing normal paraffin as a component.

  Examples of the raw material oil for obtaining a wax fraction having a boiling point of 330 ° C. or higher include heavy gas oil, vacuum gas oil, lubricating oil raffinate, bright stock, slack wax (crude wax), waxy oil, deoiled wax, and paraffin wax. , Microcrystalline wax, petrolatum, synthetic oil, FT synthetic oil, FT synthetic wax, high pour point polyolefin, and linear α-olefin wax. In particular, it is preferable to use atmospheric residue, vacuum gas oil, vacuum residue, slack wax, FT synthetic oil, or FT synthetic wax. These can be used individually by 1 type or in combination of 2 or more types. Furthermore, it is preferable that these oils have been subjected to hydrotreatment or mild hydrocracking. By these treatments, substances that reduce the activity of hydroisomerization catalysts such as sulfur-containing compounds and nitrogen-containing compounds, and substances that lower the viscosity index of lubricating base oils such as aromatic hydrocarbons and naphthenic hydrocarbons It can be reduced or eliminated.

  When the raw material oil contains 20% by volume or more of a light fraction having a boiling point of 330 ° C. or lower, it is preferably subjected to an atmospheric distillation column to remove the light fraction having a boiling point of 330 ° C. or lower.

  In the present embodiment, a light hydrocarbon oil composed of a fraction of 330 ° C. or more and less than 470 ° C. and a first heavy hydrocarbon oil composed of a fraction of 470 ° C. or more and less than 520 ° C. are obtained from the middle of the rectification column by vacuum distillation. Three fractions are obtained by extracting the second heavy hydrocarbon oil consisting of a fraction at 520 ° C. or higher from the bottom of the column. In the next step S2, these fractions are obtained from the first heavy hydrocarbon oil and light hydrocarbon oil, the second heavy hydrocarbon oil and light hydrocarbon oil, or the first heavy hydrocarbon oil. And a second heavy hydrocarbon oil and a light hydrocarbon oil, respectively, are mixed and subjected to hydroisomerization treatment.

  However, the combination of the heavy hydrocarbon and the light hydrocarbon oil used in the present invention is not limited to the above, and can be appropriately changed according to the target lubricating base oil.

(Process S2)
In this embodiment, it is obtained by mixing a heavy hydrocarbon oil containing normal paraffin having a boiling point of 470 ° C. or higher and a light hydrocarbon oil containing normal paraffin having a boiling point of 330 ° C. or higher and lower than 470 ° C. As the base oil feedstock, the above-mentioned first heavy hydrocarbon oil and light hydrocarbon oil, second heavy hydrocarbon oil and light hydrocarbon oil, or first heavy hydrocarbon oil and second oil A combination of heavy and light hydrocarbon oils can be used.

  As a means for mixing heavy hydrocarbons and light hydrocarbon oils, a method of mixing the respective raw materials in a pipe for supplying the raw materials from the tank to the reactor, or a tank installed in the preceding stage of the reactor. The method of mixing by is mentioned.

  In the heavy hydrocarbon oil, T5 is preferably 480 ° C. or higher, and more preferably 490 ° C. or higher, from the viewpoint of preventing the low boiling point component from significantly overlapping the base oil as the final product.

  In the light hydrocarbon oil, T95 is preferably 460 ° C. or lower, more preferably 450 ° C. or lower, from the viewpoint of improving the efficiency of distillation by reducing the overlap component with the heavy fraction.

  The mixing ratio of the heavy hydrocarbon and the light hydrocarbon oil is such that the content of the light hydrocarbon oil is 10 parts by volume or more and 40 parts by volume or less when the total amount of the base oil feedstock is 100 parts by volume. Preferably, it is 20 to 40 parts by volume. By mixing the light hydrocarbon oil with the heavy hydrocarbon within these ranges, the effect of reducing the isomerization reaction temperature by mixing the light hydrocarbon oil with the heavy hydrocarbon oil can be sufficiently exerted, and the main The heavy base oil that is the target product fraction can be produced efficiently.

  The hydroisomerization catalyst used in this embodiment is composed of a carrier containing molecular sieves, a metal belonging to Groups 8, 9, and 10 of the periodic table, molybdenum and tungsten supported on the carrier. And a catalyst containing at least one metal selected from the group.

  From the viewpoint of further improving the production efficiency of the lubricating base oil, the hydroisomerization catalyst comprises an ion exchange molecular sieve obtained by ion exchange of a molecular sieve containing an organic template in a solution, and the ion exchange molecular sieve. Calcining a catalyst composition comprising a metal belonging to Groups 8, 9 and 10 of the periodic table, and at least one metal selected from the group consisting of molybdenum and tungsten, It is preferable to be obtained.

  The molecular sieve containing the organic template that is the raw material of the ion-exchange molecular sieve is not particularly limited as long as it is hydrothermally synthesized in the presence of the organic template (hereinafter sometimes referred to as “synthetic molecular sieve”). In the present embodiment, the synthetic molecular sieve is preferably zeolite.

The zeolite preferably has a pore structure consisting of a 10-membered ring or an 8-membered ring from the viewpoint of achieving a high level of both high isomerization activity and suppressed decomposition activity in the isomerization reaction of normal paraffin. . Specific examples of such zeolite include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, ^* MRE and SSZ-32 having a pore structure consisting of a 10-membered ring, and 8 Examples include ANA, CHA, ERI, GIS, KFI, LTA, NAT, PAU, YUG, and DDR having a pore structure consisting of member rings. The above three letters of the alphabet mean the framework structure code given by the Structure Committee of The International Zeolite Association for each classified structure of molecular sieve type zeolite. To do. In addition, zeolites having the same topology are collectively referred to by the same code.

Among the above zeolites, in terms of high isomerization activity and a low cracking activity, TON having a one-dimensional-like pore structure consisting of 10-membered rings, zeolite having the MTT structure, and a zeolite having a ^* MRE structure ZSM -48 zeolite and SSZ-32 zeolite are preferred. ZSM-22 zeolite is more preferable as the zeolite having the TON structure, and ZSM-23 zeolite is more preferable as the zeolite having the MTT structure.

  When the ZSM-22, ZSM-23, or ZSM-48 zeolite is used as the synthetic molecular sieve, the molar ratio of silicon to aluminum element ([Si] / [Al]) in these crystalline aluminosilicates (hereinafter, “ The “Si / Al ratio”) is preferably 10 to 400, and more preferably 20 to 300. When the Si / Al ratio is less than the lower limit, the activity for the conversion of normal paraffin increases, but the selectivity of isomerization to isoparaffin decreases, and the increase in the decomposition reaction accompanying the increase in the reaction temperature is rapid. This is not preferable. On the other hand, when the Si / Al ratio exceeds the upper limit, it is difficult to obtain the catalyst activity necessary for the conversion of normal paraffin, which is not preferable.

  The organic template used for hydrothermal synthesis of molecular sieves is selected according to the structure of the molecular sieve to be synthesized, but molecular sieves are usually synthesized under alkaline conditions. An amine derivative is preferable in that the influence on the properties of the raw material can be reduced.

  Further, the organic template may be at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetramine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof. preferable.

  In the present embodiment, it is preferable that the molecular sieve containing the organic template has substantially no organic template removed by firing. In other words, before the organic template is removed by ion exchange, the synthetic molecular sieve is not baked at all, or even if baked, the conditions under which the organic template is substantially completely burned and removed (particularly Is not required to be fired at a high temperature). When baking the synthetic molecular sieve in an atmosphere containing molecular oxygen, the baking temperature is preferably about 500 ° C. or less, more preferably 450 ° C. or less, and more preferably 400 ° C. so that substantially no organic template is burned and removed. The following are even more preferred: Most preferably in this embodiment, the synthetic molecular sieve is not baked at all before the organic template is removed by ion exchange.

  The ion exchange molecular sieve according to the present embodiment is obtained by ion exchange of a synthetic molecular sieve containing an organic template in a solution. The solution used at this time is a solution containing water as a main solvent. It is preferable.

  Here, “with water as the main solvent” means that the content of water contained in the solution is 50% by mass or more based on the total amount of the solvent in the solution. In this invention, it is preferable that content of this water is 70 mass% or more, and it is more preferable that it is 100 mass%.

  Moreover, when the said solution contains an organic solvent, it is preferable that the content is 50 mass% or less on the basis of the solvent whole quantity of a solution, and it is more preferable that it is 30 mass% or less. When the content of the organic solvent exceeds 50% by mass, for example, when a compound that supplies a cationic species for ion exchange is used, problems such as a decrease in solubility of the compound in the solvent tend to occur. Therefore, it is most preferable that the solution does not contain an organic solvent.

  In the present embodiment, the ion-exchange molecular sieve is preferably obtained by ion-exchange of the synthetic molecular sieve with a solution containing a cationic species and water as a main solvent.

  In the molecular sieve in a hydrothermally synthesized state, an alkali metal cation or an alkaline earth metal cation is generally present as a counter cation. In the above ion exchange, such counter cations are also ion-exchanged, and at the same time, the organic template is appropriately removed.

  The cationic species contained in the solution containing water as the main solvent is not particularly limited, and various cationic species can be used. From the viewpoint of forming Bronsted acid sites useful in the catalyst according to the present invention, ammonium ions Or a proton is preferable. When protons are used as the cationic species, mineral acids are usually used. In this case, however, the pH of the solution is lowered, and the molecular sieve structure may be destroyed. Therefore, the most preferred cationic species in the present invention is ammonium ion. The ammonium type molecular sieve obtained by ion exchange of the synthetic molecular sieve in the presence of ammonium ion releases ammonia during the subsequent calcination of the catalyst composition, and the counter cation becomes a proton to produce Bronsted acid. It becomes a point. Examples of the compound that supplies ammonium ions into the solution include various inorganic and organic ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, and ammonium acetate. The content of the cation species contained in the solution is preferably set to be 10 to 1000 equivalents relative to the total amount of the organic template and the counter cation contained in the molecular sieve to be used.

  The ion exchange is carried out by immersing a powdery synthetic molecular sieve, a molded article of synthetic molecular sieve, or a molded article of a mixture of a synthetic molecular sieve and a binder, containing a cationic species and containing water as a main solvent, preferably an aqueous solution. However, this is preferably carried out by a method of stirring or flowing.

  Moreover, it is preferable to perform said stirring or a flow under a heating in order to improve the efficiency of ion exchange. In the present embodiment, a method of heating an aqueous solution containing a cationic species and performing ion exchange under boiling and reflux is particularly preferable.

  The ion exchange time is preferably about 1 to 24 hours, although it depends on other conditions. In addition, from the viewpoint of ion exchange efficiency and economy, the amount of the solution brought into contact with the synthetic molecular sieve is preferably 0.01 L to 10 L per 1 g of the synthetic molecular sieve. Furthermore, in order to increase the efficiency of ion exchange, it is preferable to exchange the solution once or twice or more during the ion exchange of the synthetic molecular sieve with the solution, and the solution is refreshed once or twice. It is more preferable to exchange. When exchanging the solution once, for example, after immersing the synthetic molecular sieve in a solvent containing a cationic species and containing water as a main solvent, heating the mixture for 1 to 6 hours, and then exchanging the solution for a new one Further, the ion exchange efficiency can be increased by heating to reflux for 6 to 12 hours.

  The ion-exchanged molecular sieve is preferably collected by filtration or the like, then washed with deionized water or the like, and dried at a temperature of about 60 to 130 ° C. for about 10 to 48 hours.

  On the ion exchange molecular sieve, at least one metal selected from the group consisting of metals belonging to Groups 8, 9 and 10 of the periodic table, molybdenum and tungsten is supported. Examples of the metals belonging to Groups 8, 9 and 10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum. Among these, platinum and / or palladium are preferable and platinum is more preferable from the viewpoint of activity, selectivity, and activity persistence. The metals belonging to Groups 8, 9 and 10 of the periodic table, and molybdenum and tungsten can be used alone or in combination of two or more.

  Further, when the base oil feedstock contains a large amount of sulfur-containing compounds and / or nitrogen-containing compounds, from the viewpoint of sustaining catalytic activity, nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, Nickel-tungsten-cobalt or the like is preferable as a combination of metals to be supported on the ion-exchange molecular sieve.

  Examples of a method for supporting the metal on the ion exchange molecular sieve include known methods such as an impregnation method (equilibrium adsorption method, pore filling method, initial wetting method), and ion exchange method. Moreover, as a compound containing the said metal element component used in that case, the said metal hydrochloride, sulfate, nitrate, a complex compound, etc. are mentioned. In addition, examples of the compound containing platinum include chloroplatinic acid, tetraamminedinitroplatinum, dinitroaminoplatinum, and tetraamminedichloroplatinum.

  The amount of the metal supported on the ion exchange molecular sieve is preferably 0.001 to 20% by mass with respect to the mass of the ion exchange molecular sieve. When the supported amount is less than the lower limit value, it becomes difficult to provide a predetermined hydrogenation / dehydrogenation function. On the other hand, when the supported amount exceeds the upper limit value, lightening by decomposition of hydrocarbons on the metal is performed. Tends to proceed, the yield of the target fraction tends to decrease, and the catalyst cost tends to increase.

  The conditions for calcining the catalyst composition containing the ion exchange molecular sieve and the metal supported on the ion exchange molecular sieve are preferably 250 ° C. to 600 ° C. in an atmosphere containing molecular oxygen. 300 to 500 ° C. is more preferable. Examples of the atmosphere containing molecular oxygen include oxygen gas diluted with an inert gas such as oxygen gas and nitrogen, air, and the like. The firing time is usually about 0.5 to 20 hours. Through such a calcination treatment, the compound containing the above metal element supported on the ion exchange molecular sieve is converted into a simple metal, its oxide or a similar species, and the obtained catalyst contains normal paraffin. Isomerization activity is imparted. If the calcination temperature is outside the above range, the catalyst activity and selectivity tend to be insufficient.

  Further, according to the above baking treatment, when the ion-exchange molecular sieve is an ammonium type molecular sieve, the ammonium counter cation releases ammonia in the course of the above baking treatment to become protons, and a Brested acid point is formed. .

  The hydroisomerization catalyst according to the present embodiment is preferably 250 to 500 ° C., more preferably 300 to 400 ° C., for 0.5 to 5 hours in an atmosphere containing molecular hydrogen following the above-described calcination treatment. It is preferable that a reduction treatment of a certain degree is performed. By performing such a process, the high activity with respect to dewaxing of base oil feedstock can be more reliably imparted to the catalyst.

  In the hydroisomerization catalyst according to the present embodiment, the catalyst composition is preferably molded into a predetermined shape. Examples of the shape include a cylindrical shape, a pellet shape, a spherical shape, and a modified cylindrical shape having a three-leaf / four-leaf cross section. By molding the catalyst composition into such a shape, the mechanical strength of the catalyst obtained by calcination is increased, the handling of the catalyst is improved, and the pressure loss of the reaction fluid is reduced during the reaction. Is possible. A known method is used for forming the catalyst composition.

  The content of the ion-exchange molecular sieve on which the metal is supported in the catalyst composition is preferably 1 to 90 mass%, more preferably 10 to 80 mass%, based on the total amount of the catalyst composition.

  The catalyst composition preferably contains at least one porous oxide selected from the group consisting of alumina, silica, titania, boria, magnesia, and zirconia. In this case, the content ratio of the ion-exchange molecular sieve carrying the metal and the porous oxide in the catalyst composition is preferably 1 to 90 parts by mass and 99 to 10 parts by mass, and 10 to 80 parts by mass. And more preferably 90 to 20 parts by mass.

  When the catalyst composition contains the porous oxide, a carrier containing the ion exchange molecular sieve and the porous oxide may be formed before the metal is supported on the ion exchange molecular sieve. The supported ion exchange molecular sieve and the porous oxide may be mixed and molded. In the present embodiment, the former is preferable. That is, after ion exchange of the synthetic molecular sieve in solution, the ion exchange molecular sieve, the porous oxide, and, if necessary, other binder components are preferably mixed and molded. Further, the obtained molded body is preferably fired at a temperature of about 500 ° C. to 600 ° C. in an atmosphere containing molecular oxygen in order to bring out the solid acidity of the porous oxide.

  In the hydroisomerization catalyst according to the present embodiment, metals belonging to Groups 8, 9 and 10 of the periodic table, molybdenum and tungsten on the ion exchange molecular sieve as long as the effects of the present invention are not impaired. Other metals may be further supported. Further, when the catalyst composition contains a porous oxide, a metal other than the metals belonging to Group 8, Group 9 and Group 10 of the periodic table on the ion-exchange molecular sieve and / or the porous oxide, and metals other than molybdenum and tungsten May be carried.

  From the viewpoint of further improving the production efficiency of the lubricating base oil, it is more preferable to use a hydroisomerization catalyst obtained by the following production method.

In the method for producing a hydroisomerization catalyst according to the present embodiment, an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure is ion-exchanged in a solution containing ammonium ions and / or protons. A first step of obtaining a support precursor by heating a mixture containing an ion-exchanged zeolite and a binder obtained at a temperature of 250 to 350 ° C. under a N ₂ atmosphere, and a platinum salt and The catalyst precursor containing palladium salt is calcined at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen, and hydroisomerization in which platinum and / or palladium is supported on a support containing zeolite. A second step of obtaining a catalyst.

As the organic template-containing zeolite, zeolite having the above-mentioned 10-membered ring one-dimensional pore structure can be used. Among them, in terms of high isomerization activity and low decomposition activity, zeolite having TON, MTT structure, ^* ZSM-48 zeolite and SSZ-32 zeolite which are zeolites having MRE structure are preferred. ZSM-22 zeolite is more preferable as the zeolite having the TON structure, and ZSM-23 zeolite is more preferable as the zeolite having the MTT structure.

  The organic template-containing zeolite is hydrothermally synthesized by a known method from a silica source, an alumina source, and an organic template added to construct the predetermined pore structure.

  The organic template is an organic compound having an amino group, an ammonium group, etc., and is selected according to the structure of the zeolite to be synthesized, but is preferably an amine derivative. Specifically, at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetramine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof is more preferable.

  The molar ratio ([Si] / [Al]) between silicon and aluminum constituting the organic template-containing zeolite having a 10-membered ring one-dimensional pore structure (hereinafter referred to as “Si / Al ratio”) is 10. It is preferable that it is -400, and it is more preferable that it is 20-350. When the Si / Al ratio is less than 10, the activity for the conversion of normal paraffin increases, but the isomerization selectivity to isoparaffin tends to decrease, and the increase in decomposition reaction accompanying the increase in reaction temperature tends to become rapid. Therefore, it is not preferable. On the other hand, when the Si / Al ratio exceeds 400, it is difficult to obtain the catalyst activity necessary for the conversion of normal paraffin, which is not preferable.

  The organic template-containing zeolite synthesized, preferably washed and dried usually has an alkali metal cation as a counter cation, and the organic template is included in the pore structure. The zeolite containing an organic template used in producing the hydroisomerization catalyst according to the present invention is in such a synthesized state, that is, calcination for removing the organic template included in the zeolite. It is preferable that the treatment is not performed.

  The organic template-containing zeolite is then ion exchanged in a solution containing ammonium ions and / or protons. By the ion exchange treatment, the counter cation contained in the organic template-containing zeolite is exchanged with ammonium ions and / or protons. At the same time, a part of the organic template included in the organic template-containing zeolite is removed.

  The solution used for the ion exchange treatment is preferably a solution using a solvent containing at least 50% by volume of water, and more preferably an aqueous solution. Examples of the compound that supplies ammonium ions into the solution include various inorganic and organic ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, and ammonium acetate. On the other hand, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are usually used as the compound for supplying protons into the solution. An ion-exchanged zeolite obtained by ion-exchange of an organic template-containing zeolite in the presence of ammonium ions (here, an ammonium-type zeolite) releases ammonia during subsequent calcination, and the counter cation serves as a proton as a brane. Stead acid point. As the cation species used for ion exchange, ammonium ions are preferred. The content of ammonium ions and / or protons contained in the solution is preferably set to be 10 to 1000 equivalents relative to the total amount of counter cation and organic template contained in the organic template-containing zeolite to be used. .

  The ion exchange treatment may be performed on the powdery organic template-containing zeolite alone, and prior to the ion exchange treatment, the organic template-containing zeolite is blended with an inorganic oxide as a binder, molded, and obtained. You may perform with respect to the molded object obtained. However, if the molded body is subjected to an ion exchange treatment without firing, the molded body is likely to collapse and pulverize, so the powdered organic template-containing zeolite can be subjected to an ion exchange treatment. preferable.

  The ion exchange treatment is preferably performed by an ordinary method, that is, a method in which a zeolite containing an organic template is immersed in a solution containing ammonium ions and / or protons, preferably an aqueous solution, and this is stirred or fluidized. Moreover, it is preferable to perform said stirring or a flow under a heating in order to improve the efficiency of ion exchange. In the present invention, a method of heating the aqueous solution and performing ion exchange under boiling and reflux is particularly preferable.

  Furthermore, from the viewpoint of increasing the efficiency of ion exchange, it is preferable to exchange the solution once or twice or more during the ion exchange of the zeolite with the solution, and exchange the solution once or twice. It is more preferable. In the case of changing the solution once, for example, the organic template-containing zeolite is immersed in a solution containing ammonium ions and / or protons, heated to reflux for 1 to 6 hours, and then replaced with a new one. By heating to reflux for ˜12 hours, the ion exchange efficiency can be increased.

  By the ion exchange treatment, almost all counter cations such as alkali metals in the zeolite can be exchanged for ammonium ions and / or protons. On the other hand, a part of the organic template included in the zeolite is removed by the above ion exchange treatment. However, it is generally difficult to remove all of the organic template even if the treatment is repeated. Part remains inside the zeolite.

  In this embodiment, a support precursor is obtained by heating a mixture containing ion-exchanged zeolite and a binder at a temperature of 250 to 350 ° C. in a nitrogen atmosphere.

  The mixture containing the ion exchange zeolite and the binder is preferably a mixture of the ion exchange zeolite obtained by the above method and an inorganic oxide as a binder and molding the resulting composition. The purpose of blending the inorganic oxide with the ion-exchanged zeolite is to improve the mechanical strength of the carrier (particularly, the particulate carrier) obtained by firing the molded body to such an extent that it can be practically used. The inventor has found that the choice of the inorganic oxide species affects the isomerization selectivity of the hydroisomerization catalyst. From such a viewpoint, the inorganic oxide is at least one selected from a composite oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, phosphorus oxide, and combinations of two or more thereof. Inorganic oxides are used. Among these, silica and alumina are preferable and alumina is more preferable from the viewpoint of further improving the isomerization selectivity of the hydroisomerization catalyst. The “composite oxide composed of a combination of two or more of these” is composed of at least two components of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, and phosphorus oxide. The composite oxide is preferably a composite oxide mainly composed of alumina containing 50% by mass or more of an alumina component based on the composite oxide, and more preferably alumina-silica.

  The mixing ratio of the ion exchange zeolite and the inorganic oxide in the composition is preferably 10:90 to 90:10, more preferably 30:70 to 85, as a ratio of the mass of the ion exchange zeolite to the mass of the inorganic oxide. : 15. When this ratio is smaller than 10:90, it is not preferable because the activity of the hydroisomerization catalyst tends to be insufficient. On the other hand, when the ratio exceeds 90:10, the mechanical strength of the carrier obtained by molding and baking the composition tends to be insufficient, which is not preferable.

  The method of blending the above-mentioned inorganic oxide with the ion-exchanged zeolite is not particularly limited. For example, it is usual to add a suitable amount of liquid such as water to both powders to form a viscous fluid and knead this with a kneader or the like. The method performed can be adopted.

  A composition containing the ion-exchanged zeolite and the inorganic oxide or a viscous fluid containing the composition is molded by a method such as extrusion molding, and preferably dried to form a particulate molded body. The shape of the molded body is not particularly limited, and examples thereof include a cylindrical shape, a pellet shape, a spherical shape, and a modified cylindrical shape having a trefoil / four-leaf cross section. The size of the molded body is not particularly limited, but from the viewpoint of ease of handling, packing density into the reactor, and the like, for example, the major axis is preferably about 1 to 30 mm and the minor axis is about 1 to 20 mm.

In this embodiment, it is preferable to heat the molded body obtained as described above at a temperature of 250 to 350 ° C. in a N ₂ atmosphere to obtain a carrier precursor. About heating time, 0.5 to 10 hours are preferable and 1 to 5 hours are more preferable.

  In the present embodiment, when the heating temperature is lower than 250 ° C., a large amount of the organic template remains, and the zeolite pores are blocked by the remaining template. In this case, it is considered that the isomerization active site exists in the vicinity of the pore pore mouse, the reaction substrate cannot diffuse into the pore due to the pore clogging, the active site is covered and the isomerization reaction does not proceed easily, It tends to be difficult to obtain a normal paraffin conversion rate sufficiently. On the other hand, when the heating temperature exceeds 350 ° C., the isomerization selectivity of the resulting hydroisomerization catalyst is not sufficiently improved.

  The lower limit temperature when the molded body is heated to form a carrier precursor is preferably 280 ° C. or higher. The upper limit temperature is preferably 330 ° C. or lower.

  In this embodiment, it is preferable to heat the mixture so that a part of the organic template contained in the molded body remains. Specifically, the micropore volume per unit mass of the hydroisomerization catalyst obtained through calcination after metal support described later is 0.02 to 0.11 cc / g, and the zeolite contained in the catalyst It is preferable to set the heating conditions so that the micropore volume per unit mass is 0.04 to 0.12 cc / g.

  Next, a catalyst precursor in which a platinum salt and / or a palladium salt is contained in the carrier precursor is 350 to 400 ° C., preferably 380 to 400 ° C., more preferably 400 ° C. in an atmosphere containing molecular oxygen. By calcining at a temperature, a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite is obtained. Note that “under an atmosphere containing molecular oxygen” means that the gas is in contact with a gas containing oxygen gas, preferably air. The firing time is preferably 0.5 to 10 hours, and more preferably 1 to 5 hours.

  Examples of the platinum salt include chloroplatinic acid, tetraamminedinitroplatinum, dinitroaminoplatinum, and tetraamminedichloroplatinum. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminedinitroplatinum, which is a platinum salt in which platinum is highly dispersed other than the chloride salt, is preferable.

  Examples of the palladium salt include palladium chloride, tetraamminepalladium nitrate, and diaminopalladium nitrate. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminepalladium nitrate, which is a palladium salt in which palladium is highly dispersed other than the chloride salt, is preferable.

  The supported amount of the active metal in the support containing zeolite according to the present embodiment is preferably 0.001 to 20% by mass, and more preferably 0.01 to 5% by mass based on the mass of the support. When the supported amount is less than 0.001% by mass, it is difficult to provide a predetermined hydrogenation / dehydrogenation function. On the other hand, when the supported amount exceeds 20% by mass, lightening by decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the target fraction tends to decrease, This is not preferable because the catalyst cost tends to increase.

  In addition, when the hydroisomerization catalyst according to the present embodiment is used for hydroisomerization of a hydrocarbon oil containing a large amount of a sulfur-containing compound and / or a nitrogen-containing compound, from the viewpoint of sustainability of the catalyst activity, as an active metal , Nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt, and the like. The supported amount of these metals is preferably 0.001 to 50% by mass, and more preferably 0.01 to 30% by mass based on the mass of the carrier.

  In the present embodiment, the catalyst precursor is preferably calcined so that the organic template left on the support precursor remains. Specifically, the micropore volume per unit mass of the resulting hydroisomerization catalyst is 0.02 to 0.11 cc / g, and the micropore volume per unit mass of zeolite contained in the catalyst It is preferable to set the heating conditions so as to be 0.04 to 0.12 cc / g.

  The micropore volume per unit mass of the hydroisomerization catalyst is calculated by a method called nitrogen adsorption measurement. That is, for the catalyst, the physical adsorption / desorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is analyzed. Specifically, the adsorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is expressed as t. By analyzing by the -plot method, the micropore volume of the catalyst is calculated. By dividing the calculated pore volume by the amount of catalyst used in the nitrogen adsorption measurement, the micropore volume per unit mass of the catalyst can be obtained. The micropore volume per unit mass of zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

Micropore volume V _Z per unit mass of zeolite contained in the catalyst, for example, if the binder does not have a micropore volume, the value of the micropore volume per unit mass of the hydroisomerization catalyst It can be calculated according to the following formula from V _c and the content ratio M _z (mass%) of zeolite contained in the catalyst.
V _Z = V _c / M _z × 100

  The hydroisomerization catalyst according to the present embodiment is preferably a catalyst that has been subjected to a reduction treatment after being charged in a reactor that preferably performs a hydroisomerization reaction following the above-described calcination treatment. Specifically, reduction treatment is performed for about 0.5 to 5 hours in an atmosphere containing molecular hydrogen, preferably in a hydrogen gas flow, preferably at 250 to 500 ° C., more preferably at 300 to 400 ° C. It is preferable that By such a process, the high activity with respect to dewaxing of hydrocarbon oil can be more reliably imparted to the catalyst.

  Other embodiments of the hydroisomerization catalyst used in the present invention include a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support. The micropore volume per unit mass of the hydroisomerization catalyst is 0.02 to 0.11 ml / g, and the micropore volume per unit mass of the zeolite contained in the hydroisomerization catalyst is 0. What is 0.04-0.12 ml / g is preferable.

  More preferably, it contains a zeolite having a 10-membered ring one-dimensional pore structure, a support containing a binder, and platinum and / or palladium supported on the support, and the micropores per unit mass of the catalyst A hydroisomerization catalyst having a volume of 0.02 to 0.11 cc / g, wherein the zeolite contains an organic template and an organic template-containing zeolite having a 10-membered ring one-dimensional pore structure. And / or derived from ion-exchanged zeolite obtained by ion exchange in a solution containing protons, and the micropore volume per unit mass of zeolite contained in the catalyst is 0.04 to 0.12 cc / g. It is.

Said hydroisomerization catalyst can be manufactured by the method mentioned above. The micropore volume per unit mass of the catalyst and the micropore volume per unit mass of the zeolite contained in the catalyst are the compounding amount of the ion exchange zeolite in the mixture containing the ion exchange zeolite and the binder, and N of the mixture. The heating conditions under the _two atmospheres and the heating conditions under the atmosphere containing the molecular oxygen of the catalyst precursor can be appropriately adjusted to be within the above range.

  The reaction conditions for hydroisomerization include the following conditions.

  The temperature of the hydroisomerization reaction is preferably 200 to 450 ° C, more preferably 220 to 400 ° C. When the reaction temperature is lower than 200 ° C., the isomerization of normal paraffin contained in the hydrocarbon oil as a raw material becomes difficult to proceed, and the reduction and removal of the wax component tend to be insufficient. On the other hand, when the reaction temperature exceeds 450 ° C., decomposition of the hydrocarbon oil becomes prominent, and the yield of the target hydrocarbon tends to decrease.

  The pressure for the hydroisomerization reaction is preferably from 0.1 to 20 MPa, more preferably from 0.5 to 15 MPa. When the reaction pressure is less than 0.1 MPa, the deterioration of the catalyst due to coke generation tends to be accelerated. On the other hand, when the reaction pressure exceeds 20 MPa, the cost for constructing the apparatus tends to be high, and it tends to be difficult to realize an economical process.

Liquid hourly space velocity relative to the catalyst of the hydrocarbon oil is preferably 0.01~100hr ^-1, 0.1~50hr ^-1 are more preferred. When the liquid space velocity is less than 0.01 hr ⁻¹ , the decomposition of the hydrocarbon oil tends to proceed excessively and the production efficiency of the target hydrocarbon tends to decrease. On the other hand, when the liquid space velocity exceeds 100 hr ⁻¹ , the isomerization of normal paraffin contained in the hydrocarbon oil becomes difficult to proceed, and the reduction and removal of the wax component tend to be insufficient.

Hydrogen supply ratio of the hydrocarbon oil is preferably from 100 to 1000 nm ³ / ^{m 3,} more preferably 200~800Nm ³ / ^{m 3.} When the supply ratio is less than 100 Nm ³ / m ³ , for example, when the raw material oil contains sulfur and nitrogen compounds, desulfurization that occurs concurrently with the isomerization reaction, hydrogen sulfide generated by the denitrogenation reaction, and ammonia gas are the active metals on the catalyst. Adsorption poisoning tends to make it difficult to obtain a predetermined catalyst performance. On the other hand, when the supply ratio exceeds 1000 Nm ³ / m ³ , a hydrogen supply facility with a large capacity is required, so that it is difficult to realize an economical process.

  The conversion rate of normal paraffin in the hydroisomerization reaction in step S2 is appropriately adjusted according to the use of the obtained hydrocarbon oil.

  According to the method for producing a lubricating base oil according to the present invention, a base oil containing a large number of isomers having a branched chain structure can be obtained. In particular, for a high-quality lubricating base oil, the normal paraffin content is required to be 0.1% by mass or less, but according to the method for producing a lubricating base oil according to the present invention, this requirement is required. A lubricating base oil satisfying the level can be obtained in a high yield.

  The reaction apparatus may be any of a continuous flow type, a batch type, and a semi-batch type, but a continuous flow type is preferable from the viewpoint of productivity and efficiency. The catalyst layer may be a fixed bed, a fluidized bed, or a stirring bed, but is preferably a fixed bed from the viewpoint of equipment costs. The reaction phase is preferably a gas-liquid mixed phase.

  In general, isomerization refers to a reaction that changes only the molecular structure without changing the carbon number (molecular weight), and decomposition refers to a reaction that involves a decrease in carbon number (molecular weight). In the isomerization dewaxing reaction using the isomerization reaction, the carbon number (molecular weight) of the product should constitute the target base oil even if the hydrocarbon oil and the product oil are decomposed to some extent. Is within the predetermined allowable range, and the decomposition product may be a constituent of the base oil.

  In step S3, the product oil obtained through step S2 is further processed by hydrofinishing. Hydrofinishing can generally be carried out by bringing the finished product into contact with a supported metal hydrogenation catalyst (for example, platinum supported on alumina) in the presence of hydrogen. By performing such hydrofinishing, the hue, oxidation stability, etc. of the product oil obtained in step S2 can be improved, and the quality of the product can be improved.

  In this embodiment, a hydrotreating apparatus that performs hydrofinishing is provided on the downstream side of the hydroisomerization apparatus, but can be omitted.

  In step S4, the product oil hydrotreated through step S3 is subjected to atmospheric distillation and fractionated into a naphtha fraction, a kerosene oil fraction and a lubricating oil fraction. The naphtha fraction can be recovered from the line L18 as a fraction of less than 150 ° C., for example. A kerosene oil fraction can be recovered from the line L19 as a fraction of 150 ° C. or higher and lower than 330 ° C., for example. The lubricating oil fraction is supplied to the third rectifying tower 70 from the line 20 connected to the tower bottom, for example, as a fraction of 330 ° C. or higher.

  In step S5, the lubricating oil fraction obtained in step S4 is distilled into various lubricating base oils by distillation under reduced pressure. For example, the same fractionation conditions as in step S1 can be set. In this case, a lubricant base oil composed of a fraction of 330 ° C. or more and less than 470 ° C., a lubricant base oil composed of a fraction of 470 ° C. or more and less than 520 ° C., 520 It can be fractionated into a lubricating base oil consisting of fractions at or above. Various lubricating base oils can be obtained from lines L22, 23 and 24, respectively.

  In this embodiment, a fraction of 330 ° C. or more and less than 470 ° C., a fraction of 470 ° C. or more and less than 520 ° C., and a fraction of 520 ° C. or more are lubricated with 70 pale and SAE-10, SAE-20, SAE-30 +, respectively. It can be obtained as an oil base oil.

  The lubricating base oil for gasoline engines preferably has a viscosity index defined by JIS K 2283 of 135 or more, and more preferably 140 or more. Moreover, it is preferable that the pour point prescribed | regulated by JISK2269 is -20 degrees C or less, and it is more preferable that it is -25 degrees C or less.

  The lubricating base oil for a diesel engine preferably has a viscosity index defined by JIS K 2283 of 145 or more, and more preferably 150 or more. Moreover, it is preferable that the pour point prescribed | regulated by JISK2269 is -12.5 degrees C or less, and it is more preferable that it is -15 degrees C or less.

  The industrial lubricating base oil preferably has a viscosity index defined by JIS K 2283 of 150 or more, and more preferably 155 or more. Moreover, it is preferable that the pour point prescribed | regulated by JISK2269 is -10 degrees C or less, and it is more preferable that it is -12.5 degrees C or less.

  The manufacturing method of the lubricating base oil described above can be changed as appropriate according to the type of the lubricating base oil. For example, in step S1, the wax fraction is fractionated into fractions corresponding to 70 Pale, SAE10, SAE20, and SAE30 + and stored in the respective storage tanks, and these are mixed in the combinations shown in Table 1 in step S2 and hydroisomerized. Can be

  In step S5, a lubricating base oil corresponding to the above combination can be obtained by fractional distillation.

  In this embodiment, since the reaction temperature in the isomerization dewaxing of heavy hydrocarbon oil can be lowered, the reaction when the isomerization dewaxing with the next lowest reaction temperature is performed using the same isomerization dewaxing reactor. The temperature adjustment time can be shortened, whereby the production efficiency in the production of lubricating base oils of different oil types can be improved.

[Production of hydroisomerization catalyst]
(Production Example 1)
<Production of ZSM-22 zeolite>
A ZSM-22 zeolite composed of crystalline aluminosilicate having a Si / Al ratio of 45 (hereinafter sometimes referred to as “ZSM-22”) was produced by hydrothermal synthesis according to the following procedure.

First, the following four types of aqueous solutions were prepared.
Solution A: 1.94 g of potassium hydroxide dissolved in 6.75 mL of ion exchange water.
Solution B: A solution obtained by dissolving 1.33 g of aluminum sulfate 18-hydrate in 5 mL of ion-exchanged water.
Solution C: A solution obtained by diluting 4.18 g of 1,6-hexanediamine (organic template) with 32.5 mL of ion-exchanged water.
Solution D: 18 g of colloidal silica (Ludox AS-40 manufactured by Grace Davison) diluted with 31 mL of ion-exchanged water.

Next, solution A was added to solution B and stirred until the aluminum component was completely dissolved.
After adding the solution C to this mixed solution, the mixture of the solutions A, B and C was poured into the solution D with vigorous stirring at room temperature. Further, 0.25 g of ZSM-22 powder synthesized separately and not subjected to any special treatment after synthesis was added as a “seed crystal” for promoting crystallization, thereby obtaining a gel-like product.

  The gel obtained by the above operation is transferred to a stainless steel autoclave reactor having an internal volume of 120 mL, and the autoclave reactor is rotated on a tumbling apparatus at a rotation speed of about 60 rpm in an oven at 150 ° C. for 60 hours. The hydrothermal synthesis reaction was performed. After completion of the reaction, the reactor was cooled and opened, and dried overnight in a dryer at 60 ° C. to obtain ZSM-22 having a Si / Al ratio of 45.

<Ion exchange of ZSM-22 containing organic template>
ZSM-22 obtained above was subjected to ion exchange treatment with an aqueous solution containing ammonium ions by the following operation.

  ZSM-22 obtained above was placed in a flask, 100 mL of 0.5N ammonium chloride aqueous solution was added to 1 g of ZSM-22 zeolite, and heated to reflux for 6 hours. After cooling this to room temperature, the supernatant was removed and the crystalline aluminosilicate was washed with ion-exchanged water. The same amount of 0.5N-ammonium chloride aqueous solution as above was added again, and the mixture was refluxed with heating for 12 hours.

Thereafter, the solid content was collected by filtration, washed with ion-exchanged water, and dried overnight in a dryer at 60 ° C. to obtain ion-exchanged NH ₄ type ZSM-22. This ZSM-22 is ion-exchanged in a state containing an organic template.

<Binder formulation, molding, firing>
NH ₄ type ZSM-22 obtained above and alumina as a binder were mixed at a mass ratio of 7: 3, and a small amount of ion-exchanged water was added thereto and kneaded. The obtained viscous fluid was filled into an extrusion molding machine and molded to obtain a cylindrical molded body having a diameter of about 1.6 mm and a length of about 10 mm. This molded body was heated at 300 ° C. for 3 hours under an N ₂ atmosphere to obtain a carrier precursor.

<Platinum support, firing>
Tetraamminedinitroplatinum [Pt (NH ₃ ) ₄ ] (NO ₃ ) ₂ was dissolved in ion-exchanged water corresponding to the previously measured water absorption of the carrier precursor to obtain an impregnation solution. This solution was impregnated with the above carrier precursor by an initial wetting method, and supported so that the amount of platinum was 0.3% by mass with respect to the mass of the ZSM-22 type zeolite. Next, the obtained impregnated product (catalyst precursor) was dried overnight at 60 ° C. and then calcined at 400 ° C. for 3 hours under air flow to obtain a hydroisomerization catalyst 1.

  Furthermore, the micropore volume of the obtained hydroisomerization catalyst was calculated by the following method. First, in order to remove water adsorbed on the hydroisomerization catalyst, pretreatment was performed to evacuate at 150 ° C. for 5 hours. About the hydroisomerization catalyst after this pre-processing, nitrogen adsorption measurement was performed at liquid nitrogen temperature (-196 degreeC) using BELSORP-max by Nippon Bell Co., Ltd. company. The measured nitrogen adsorption isotherm was analyzed by the t-plot method, and the micropore volume (cc / g) of the hydroisomerization catalyst was calculated.

Moreover, to calculate the micropore volume V _Z per unit mass of zeolite contained in the catalyst according to the following formula. In addition, when nitrogen adsorption measurement was performed similarly to the above about the alumina used as a binder, it was confirmed that an alumina does not have a micropore.
V _Z = V _c / M _z × 100
In the formula, V _c represents the micropore volume per mass unit of the hydroisomerization catalyst, and M _z represents the content ratio (mass%) of zeolite in the catalyst.

  The micropore volume per mass unit of the hydroisomerization catalyst and the micropore volume per unit mass of zeolite contained in the catalyst were 0.055 cc / g and 0.079 cc / g, respectively.

Example 1
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

Through the reaction tube, base oil feedstock mixed with 60 parts by volume of FT wax having a boiling point range of 520 ° C. + which is the main target fraction and 40 parts by volume of FT wax having a boiling point range of 330 ° C. or more and less than 470 ° C. is passed. Then, isomerization dewaxing was performed at a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L, and a liquid space velocity of 1.5 h ⁻¹ . The reaction temperature at this time was 325 degreeC.

  The yield of the product oil boiling range 520 ° C. + was 35% by volume.

(Example 2)
The same procedure as in Example 1 was conducted except that 90 parts by volume of FT wax having a boiling point range of 520 ° C. + and 10 parts by volume of FT wax having a boiling point range of 330 ° C. to less than 470 ° C. were mixed. The isomerization dewaxing was performed. The reaction temperature at this time was 335 degreeC.

  The yield of the product oil in the boiling range of 520 ° C. + was 48% by volume.

Example 3
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

A base oil feedstock in which 60 parts by volume of FT wax having a boiling range of 470 ° C. or more and less than 520 ° C. and 40 parts by volume of FT wax having a boiling point range of 330 ° C. or more and less than 470 ° C., which are main target fractions, is passed through the reaction tube. Oil was isomerized and dewaxed at a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L, and a liquid space velocity of 1.5 h ⁻¹ . The reaction temperature at this time was 322 ° C.

  The yield of the product oil in the boiling range of 470 ° C. or higher and lower than 520 ° C. was 34% by volume.

Example 4
Example 3 except that 90 parts by volume of FT wax having a boiling range of 470 ° C. or more and less than 520 ° C. and 10 parts by volume of FT wax having a boiling range of 330 ° C. or more and less than 470 ° C. were mixed. In the same manner as above, isomerization dewaxing was performed. The reaction temperature at this time was 327 degreeC.

  The yield of the product oil in the boiling range of 470 ° C. or more and less than 520 ° C. was 43% by volume.

(Comparative Example 1)
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

FT wax having a boiling point range of 520 ° C. +, which is the main target fraction, is passed through the reaction tube as a base oil feedstock, and the hydrogen pressure is 15 MPa, the hydrogen / oil ratio is 500 NL / L, and the liquid space velocity is 1.5 h ^−1. Isomerization and dewaxing. The reaction temperature at this time was 340 degreeC.

  The yield of the product oil in the boiling range of 520 ° C. + was 50% by volume.

(Comparative Example 2)
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

An FT wax having a boiling point range of 470 ° C. or more and less than 520 ° C., which is a main target fraction, is passed through the reaction tube as a base oil feedstock, a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L, a liquid space velocity of 1. Isomerized dewaxing at 5 h- ¹ . The reaction temperature at this time was 330 degreeC.

  The yield of the product oil in the boiling range of 470 ° C. or more and less than 520 ° C. was 45% by volume.

(Comparative Example 3)
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

An FT wax having a boiling point range of 330 ° C. or higher and lower than 470 ° C. was passed through the reaction tube as a base oil feedstock, and isomerized at a hydrogen pressure of 15 MPa, a hydrogen / oil ratio of 500 NL / L and a liquid space velocity of 1.5 h ⁻¹ Dewaxing. The reaction temperature at this time was 320 degreeC.

(Comparative Example 4)
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 100 ml of the hydroisomerization catalyst 1 and subjected to reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (hydrogen partial pressure of 3 MPa).

A base oil feedstock in which 60 parts by volume of FT wax having a boiling point range of 520 ° C. and 40 parts by volume of FT wax having a boiling point range of 470 ° C. or more and less than 520 ° C. was passed through the reaction tube, and a hydrogen pressure of 15 MPa, hydrogen / Isomerization dewaxing was performed at an oil ratio of 500 NL / L and a liquid space velocity of 1.5 h- ¹ . The reaction temperature at this time was 336 degreeC.

  The yield of the product oil in the boiling range of 520 ° C. + and the yield in the boiling range of 470 ° C. to less than 520 ° C. were 30% by volume and 18% by volume, respectively.

(Comparative Example 5)
In the same manner as in Comparative Example 4, except that 90 parts by volume of FT wax having a boiling point range of 520 ° C. and 10 parts by volume of FT wax having a boiling point range of 470 ° C. or more and less than 520 ° C. were passed, Chemical dewaxing was performed. The reaction temperature at this time was 339 degreeC.

  The yield of the product oil in the boiling range of 520 ° C. + and the yield in the boiling range of 470 ° C. to less than 520 ° C. were 45% by volume and 5% by volume, respectively.

[Evaluation of product / raw material ratio]
The ratio of the content of the target fraction in the produced oil to the content of the target fraction in the base oil feedstock was calculated as “product / raw material”. In addition, it means that decomposition | disassembly of the heavy fraction in an isomerization dewaxing process is suppressed, so that this value is large. The results are shown in Table 2.

[Evaluation of Viscosity Index (VI) and Pour Point (PP)]
About the obtained target fraction, the viscosity index (VI) and the pour point (PP) were measured according to the following method.
The viscosity index (VI) was determined based on the viscosity index calculation method of JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”. The pour point (PP) was determined based on the pour point test method of JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

The arithmetic average reaction temperature shown in Table 2 is a weighted arithmetic average value obtained by the following equation when the reaction temperatures of Comparative Examples 1 to 3 are T1, T2, and T3, respectively.
Example 1: arithmetic average reaction temperature = (0.6 × T1 + 0.4 × T3) / (0.6 + 0.4)
Example 2: arithmetic average reaction temperature = (0.9 × T1 + 0.1 × T3) / (0.9 + 0.1)
Example 3: arithmetic average reaction temperature = (0.6 × T2 + 0.4 × T3) / (0.6 + 0.4)
Example 4: arithmetic mean reaction temperature = (0.9 × T2 + 0.1 × T3) / (0.9 + 0.1)

  According to the example in which the base oil feedstock obtained by mixing the light hydrocarbon oil with the heavy hydrocarbon oil is isomerized and dewaxed, the reaction temperature required for the isomerization reaction of the heavy hydrocarbon oil can be lowered, The yield of the lubricant base oil product with respect to the raw material corresponding to the quality hydrocarbon oil can be improved.

  DESCRIPTION OF SYMBOLS 10 ... 1st fractionator, 20 ... Light hydrocarbon oil storage tank, 30 ... 1st heavy hydrocarbon oil storage tank, 40 ... 2nd heavy hydrocarbon oil storage tank, 50 ... Hydroisomerization apparatus, 60 ... Hydrotreating apparatus, 65 ... second rectifying tower 65, 70 ... third rectifying tower, 100 ... production system.

Claims (5)

A method for producing a lubricant base oil to obtain a lubricant base oil of SAE-20 or a lubricant base oil of SAE-30 +,
A wax fraction containing normal paraffin and having a boiling point of 330 ° C. or more, a light hydrocarbon oil fraction having a boiling range of 330 ° C. or more and less than 470 ° C. , a fraction corresponding to SAE 20 having a boiling range of 470 ° C. or more and less than 520 ° C. and a boiling range Fractionating into a fraction corresponding to SAE30 + at 520 ° C. or higher ;
A base oil feedstock obtained by mixing the fraction corresponding to SAE20 and the light hydrocarbon oil fraction, or the fraction corresponding to SAE30 + and the light hydrocarbon oil fraction , in the presence of hydrogen. And a step of bringing into contact with a hydroisomerization catalyst. The content of the light hydrocarbon oil fraction in the base oil feedstock is 10 parts by volume or more and 40 parts by volume or less when the total amount of the base oil feedstock is 100 parts by volume. The manufacturing method of the lubricating base oil of description.   The hydroisomerization catalyst is at least selected from the group consisting of a carrier containing molecular sieves, a metal belonging to Groups 8, 9 and 10 of the periodic table, molybdenum and tungsten supported on the carrier. The method for producing a lubricant base oil according to claim 1, wherein the lubricant composition is obtained by firing a catalyst composition containing one kind of metal. The hydroisomerization catalyst contains a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support,
The micropore volume per unit mass of the hydroisomerization catalyst is 0.02 to 0.11 ml / g,
The lubricating base oil according to claim 1 or 2, wherein a micropore volume per unit mass of the zeolite contained in the hydroisomerization catalyst is 0.04 to 0.12 ml / g. Manufacturing method. The hydroisomerization catalyst,
An ion exchange zeolite obtained by ion exchange of an organic template-containing zeolite having an organic template and a 10-membered ring one-dimensional pore structure in a solution containing ammonium ions and / or protons, and a binder are included. A first step of obtaining a support precursor by heating the mixture at a temperature of 250 to 350 ° C. in an N ₂ atmosphere, and a catalyst precursor containing a platinum salt and / or a palladium salt in the support precursor, And a second step of obtaining a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite by firing at a temperature of 350 to 400 ° C. in an atmosphere containing gaseous oxygen It is obtained by the manufacturing method of a catalyst, The manufacturing method of the lubricating base oil of Claim 1 or 2 characterized by the above-mentioned.

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