JP5759409B2 - 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 is a product in which fluidity at low temperatures is regarded as important. Therefore, the base oils used in these products are converted to those other than wax components from which wax components such as normal paraffin and slightly-branched isoparaffin that cause low temperature fluidity reduction are sufficiently removed. It is desirable that In recent years, hydrocarbons obtained by the Fischer-Tropsch synthesis method (hereinafter abbreviated as “FT synthetic oil”) do not contain environmentally hazardous substances such as sulfur compounds. Although attracting attention, these hydrocarbons also contain many wax components.

  As a dewaxing technique for converting a wax component in a hydrocarbon oil into a non-wax component, for example, a so-called dual function in which a hydrocarbon oil has hydrogenation-dehydrogenation ability and isomerization ability in the presence of hydrogen. Catalytic dewaxing is known in which a normal paraffin in a hydrocarbon is isomerized into an isoparaffin by contacting with a catalyst (see, for example, Patent Document 1).

JP-T-2006-502297

  When the feed oil to be contact dewaxed becomes heavy, the cloud point may not satisfy the target value even when the pour point of the product oil satisfies a predetermined value. Such a phenomenon becomes a problem in the production of heavy lubricating base oil such as bright stock. A trace amount of very long chain hydrocarbon is considered as a causative substance. Although there are means such as solvent dewaxing, centrifugation, and adsorption separation as methods for removing the causative substances, none of them is an efficient method and is not practical in terms of cost.

  An object of the present invention is to provide a method for producing a lubricating base oil that can efficiently obtain a heavy lubricating base oil having a sufficiently low pour point and cloud point.

  One aspect of the present invention includes a step of bringing a feedstock containing hydrocarbons having 21 or more carbon atoms into contact with a first catalyst and a second catalyst in this order in the presence of hydrogen. Contains a zeolite having a 10-membered ring one-dimensional pore structure and a support containing a binder, and platinum and / or palladium supported on the support, and the micropore volume per unit mass of the catalyst is A hydroisomerization catalyst 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, ammonium ions and / or Alternatively, it is derived from an ion exchange zeolite obtained by ion exchange in a solution containing protons, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.04 to 0.12. c / g, and the second catalyst has a support containing a zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support, Alternatively, the catalyst is a catalyst in which the total supported amount of palladium is 0.05 to 0.4 parts by mass with respect to 100 parts by mass of the carrier in terms of metal atoms, and the volume V1 of the first catalyst and the volume V2 of the second catalyst Provided is a method for producing a lubricating base oil, wherein the ratio V1 / V2 is 70/30 to 90/10.

  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).

  According to the method for producing a lubricating base oil of the present invention, a heavy lubricating base oil having a sufficiently low pour point and cloud point can be obtained efficiently.

  The present inventors infer the reason why the above effect is obtained as follows. That is, the zeolite contained in the first catalyst and the second catalyst has a 10-membered one-dimensional pore structure, so that it is considered to be a causative substance that deteriorates the cloud point. Can be selectively adsorbed in the pores, the hydroisomerization is efficiently performed by the first catalyst having the specific micropore volume, and the ultralong remaining after the hydroisomerization. Chain paraffin is decomposed by the second catalyst having the above-mentioned specific active metal in the above-mentioned specific ratio, so that both the pour point and cloud point can be improved while maintaining the yield of the lubricating base oil. It is thought that it became.

Another aspect of the present invention includes a step of bringing a feedstock containing a hydrocarbon having 21 or more carbon atoms into contact with a first catalyst and a second catalyst in this order in the presence of hydrogen, An ion-exchanged zeolite obtained by ion-exchange of an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure in a solution containing ammonium ions and / or protons, and a binder When a mixture that contains, N ₂ atmosphere, a first step of obtaining a heated carrier precursor at a temperature of 250 to 350 ° C., the catalyst precursor was contained platinum salts and / or palladium salt on a carrier precursor And a second step of obtaining a hydroisomerization catalyst in which platinum and / or palladium is supported on a carrier containing zeolite by calcining the body at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen. The hydroisomerization catalyst obtained in the method for producing a hydroisomerization catalyst, wherein the second catalyst comprises a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum supported on the support And / or palladium, and the total supported amount of platinum and / or palladium is 0.05 to 0.4 parts by mass with respect to 100 parts by mass in terms of metal atoms, the first catalyst The ratio V1 / V2 of the volume V1 of the second catalyst and the volume V2 of the second catalyst is 70/30 to 90/10.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the lubricating base oil which can obtain the heavy lubricating base oil with a sufficiently low pour point and a cloud point efficiently can be provided.

It is a flowchart which shows an example of the lubricating base oil manufacturing apparatus which enforces the manufacturing method of the lubricating base oil which concerns on this invention. It is a flowchart which shows the other example of the lubricating base oil manufacturing apparatus which enforces the manufacturing method of the lubricating base oil which concerns on this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a flowchart showing an example of a lubricating base oil production apparatus that implements a lubricating base oil production method according to the present invention. A lubricating base oil production apparatus 100 shown in FIG. 1 is an apparatus that produces a hydrocarbon oil containing components useful as a lubricating oil base oil from a raw material containing paraffinic hydrocarbons.

  A hydrocarbon oil production apparatus 100 shown in FIG. 1 includes a reaction tower 10 for hydrotreating a raw material (raw oil) containing paraffinic hydrocarbons, and a product oil obtained from the reaction tower 10 is fractionated into desired fractions. A first distillation column 15 and a second distillation column 20 are provided. And the supply line L1 for supplying raw material oil to the reaction tower 10 is connected to the tower top part of the reaction tower 10, Furthermore, the line L2 into which hydrogen is introduce | transduced is connected to this line L1. Feedstock and hydrogen are supplied to the reaction tower 10 through these lines. The bottom of the reaction tower 10 and the distillation tower 20 are connected by a transfer line L3, and the product oil obtained from the reaction tower 10 is sent to the first distillation tower 15 through this line L3. Connected to the first distillation column 15 are lines L4, L5 and L6 for taking out the naphtha fraction, kerosene fraction and lubricating oil fraction fractionated in the first distillation column 15. Line L <b> 6 is connected to the second distillation column 20, and the lubricating oil fraction can be supplied to the second distillation column 20. The second distillation column 20 is connected to lines L8, L9, and L10 for taking out various lubricating base oils fractionated in the second distillation column 20.

  In the present embodiment, the reaction tower 10 includes a first catalyst layer 12 containing a first catalyst and a high second catalyst layer 14 containing a second catalyst in this order from the tower top side. Have.

  The paraffinic hydrocarbon to be subjected to the hydrotreating is not particularly limited with respect to the carbon number thereof, and examples thereof include those containing hydrocarbons having 21 to 100 carbon atoms. In the present embodiment, a feedstock containing hydrocarbons having 30 or more carbon atoms, preferably a feedstock containing 50% by mass or more of hydrocarbon oils having 40 or more carbon atoms, is subjected to the hydrotreatment.

  As the raw material oil, a fraction obtained by fractionating FT synthetic oil, vacuum gas oil, vacuum gas oil hydrocracking bottom oil, and vacuum residue solvent degassed oil can be used.

As a first catalyst of the present embodiment, an ion obtained by ion exchange of an organic template-containing zeolite containing an organic template and having a 10-membered one-dimensional pore structure in a solution containing ammonium ions and / or protons A first step of heating a mixture containing an exchanged zeolite and a binder at a temperature of 250 to 350 ° C. in a N ₂ atmosphere to obtain a support precursor; and a platinum salt and / or a palladium salt in the support precursor. The catalyst precursor contained is calcined at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen to obtain a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite. The hydroisomerization catalyst obtained by the manufacturing method of a hydroisomerization catalyst provided with a process can be used.

The organic template-containing zeolite used in the present embodiment is a one-dimensional fine particle consisting of a 10-membered ring from the viewpoint of achieving both high isomerization activity and suppressed decomposition activity in normal paraffin hydroisomerization reaction at a high level. Has a pore structure. Examples of such zeolite include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, ^* MRE, and SSZ-32. The above three letters of the alphabet mean the skeletal structure codes given by the Structure Committee of The International Zeolite Association for each classified molecular sieve type structure. To do. In addition, zeolites having the same topology are collectively referred to by the same code.

As the above-mentioned organic template-containing zeolite, among the zeolites having the above-mentioned 10-membered ring one-dimensional pore structure, zeolites having a TON or MTT structure, and ^* MRE structures in terms of high isomerization activity and low decomposition activity ZSM-48 zeolite and SSZ-32 zeolite which are zeolites 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. It is considered that the isomerization active site is present near the pore pore mouse. In the above case, the reaction substrate cannot diffuse into the pore due to the clogging of the pore, and the active site is covered and the isomerization reaction does not proceed easily. The conversion rate of normal paraffin tends to be insufficient. 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.

  Further, when the hydroisomerization catalyst according to the present embodiment is used for hydroisomerization of a hydrocarbon oil containing a large amount of sulfur-containing compounds and / or nitrogen-containing compounds, 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 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.

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 the zeolite in the catalyst.
V _Z = V _c / M _z × 100

  The hydroisomerization catalyst according to the present invention is preferably a catalyst that has been subjected to a reduction treatment after being charged into 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.

  Further, in the present embodiment, the first catalyst 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, A hydroisomerization catalyst having a micropore volume per unit mass of 0.02 to 0.11 cc / g, wherein the zeolite contains an organic template and has a 10-membered ring one-dimensional pore structure. The template-containing zeolite is derived from an ion-exchanged zeolite obtained by ion exchange in a solution containing ammonium ions and / or protons, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.00. A hydroisomerization catalyst of 04 to 0.12 cc / g can be used.

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 blending amount of the ion exchange zeolite in the mixture containing the ion exchange zeolite and the binder, and the 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 second catalyst of the present embodiment includes a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support, and platinum and / or palladium. A catalyst having a total supported amount of 0.05 to 0.4 parts by mass in terms of metal atoms with respect to 100 parts by mass of the support is used.

  In the present embodiment, platinum and / or palladium is used for the purpose of preventing the stabilization of the unstable substance generated during the reaction by hydrogenation and preventing the catalyst deactivation by increasing the coke generation rate. The total supported amount is 0.05 parts by mass or more, preferably 0.08 parts by mass or more with respect to 100 parts by mass of the carrier in terms of metal atoms. On the other hand, for the purpose of preventing the cloudy substance removal reaction from being suppressed, the total supported amount of platinum and / or palladium is 0.4 parts by mass or less, preferably 0.00. 2 parts by mass or less.

  The zeolite constituting the catalyst can be obtained by calcining the zeolite after hydrothermal synthesis, for example, at a temperature of about 550 ° C. or higher in an atmosphere containing molecular oxygen. This temperature is selected to sufficiently burn and remove the organic template. Then, after the calcination, the second catalyst can be obtained by performing ion exchange, loading of a metal component, and activation by calcination.

  The support of the second catalyst can contain a binder. Examples of the binder include inorganic oxides, and specifically, selected from composite oxides composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, phosphorus oxide, and combinations of two or more thereof. At least one inorganic oxide can be used. Among these, silica and alumina are preferable and alumina is more preferable from the viewpoint of suppressing paraffin decomposition activity. Further, from the viewpoint of maintaining the crushing strength of the catalyst, a composite oxide mainly composed of alumina containing 50% by mass or more of an alumina component based on the composite oxide is preferable, and alumina-silica is more preferable.

  The mixing ratio of the zeolite and the inorganic oxide in the carrier of the second catalyst according to the present embodiment is preferably 10:90 to 90:10, more preferably 30 as the ratio of the mass of the zeolite to the mass of the inorganic oxide. : 70 to 85:15. When this ratio is smaller than 10:90, the catalyst activity tends to be insufficient, which is not preferable. On the other hand, when the ratio exceeds 90:10, the mechanical strength of the carrier tends to be insufficient, which is not preferable.

  In the present embodiment, the ratio V1 / V2 between the volume V1 of the first catalyst constituting the first catalyst layer and the volume V2 of the second catalyst constituting the second catalyst layer is 70/30 to 90. / 10. If the ratio is smaller than 70/30, that is, if the volume V1 of the first catalyst is too small, the pour point of the lubricating oil cannot be sufficiently lowered, while the ratio is larger than 90/10. That is, if the volume V2 of the second catalyst is too small, removal of the cloud point deteriorating substance is not sufficient. From the viewpoint of maintaining the yield of the lubricating oil while achieving both a predetermined pour point and a cloud point, V1 / V2 is preferably 2.6 to 7.3, and more preferably 3.0 to 5.7.

  In the present embodiment, for example, when the cross-sectional area when the first catalyst layer and the second catalyst layer of the reaction tower 10 are cut along a plane perpendicular to the flow direction is constant regardless of the cutting position, The ratio [D1 / D2] of the thickness D1 of the first catalyst layer and the thickness D2 of the second catalyst layer shown in FIG. 1 can be in the range of 70/30 to 90/10. 2.6 It is preferable to set it in the range of -7.3, and it is more preferable to set it in the range of 3.0-5.7.

The hydrogenation treatment in the reaction tower 10 can be performed under the following reaction conditions. Examples of the hydrogen partial pressure include 1 to 20 MPa, and 3 to 15 MPa is preferable. The liquid hourly space velocity of the feedstock (LHSV), including but 0.1~5h ^-1, 1~3h ^-1 are preferred. As a hydrogen / oil ratio, 100-1500 NL / L is mentioned, 200-1000 NL / L is preferable.

  Moreover, as reaction temperature in a hydrogenation process, although 200-400 degreeC is mentioned, 250-380 degreeC is preferable and 300-350 degreeC is more preferable.

In the present embodiment, from the viewpoint of obtaining a lubricating base oil having an excellent viscosity index and pour point, the raw material oil is hydrogenated under the condition that the conversion rate of normal paraffin defined by the following formula (I) is 100% by mass. It is preferable to process.
Normal paraffin conversion (%) = [1− (total mass part of normal paraffin having 21 or more carbon atoms contained in 100 parts by mass of product oil obtained after hydrotreating) / (100 mass of feedstock before hydrotreating) Part total mass part of normal paraffin having 21 or more carbon atoms)] × 100

  In the present specification, 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 the carbon number (molecular weight). In catalytic dewaxing reaction using isomerization reaction, even if hydrocarbons and isomerization products of feedstock are decomposed to some extent, the carbon number (molecular weight) of the products constitutes the target base oil. Therefore, the decomposition product may be a constituent of the base oil.

  In the reaction tower 10 shown in FIG. 1, the object to be treated is supplied in a down flow. However, if necessary, the order of the first catalyst layer 12 and the second catalyst layer 14 may be reversed and supplied in an up flow. it can. In this case, the product oil is transferred from the top of the reaction tower 10 to the first distillation tower 15.

  Moreover, in this embodiment, you may implement a hydrogenation process using the reaction tower provided with the catalyst layer of 3 steps | paragraphs or more instead of the reaction tower 10 provided with a 2 step | paragraph catalyst layer. In this case, each catalyst layer only needs to be filled so that the total volume of the first catalyst and the total volume of the second catalyst satisfy the above ratio.

  The hydrotreatment performed in the reaction tower 10 includes both hydrocracking and hydroisomerization. In addition, the case where both the hydrocracking and hydroisomerization reactions proceed in a complicated manner is involved. Decomposition means a chemical reaction accompanied by a decrease in molecular weight, and isomerization means conversion to another compound having a different carbon skeleton while maintaining the molecular weight and the number of carbon atoms constituting the molecule.

  As the first distillation column 15 and the second distillation column 20, a known distillation column can be used.

  In the first distillation column 15, the product oil obtained from the reaction column 10 is fractionated into, for example, a light fraction (naphtha, kerosene fraction) and a lubricating oil fraction by atmospheric distillation. Light fractions (naphtha, kerosene fraction) can be recovered from lines L4 and L5 connected to the first distillation column 15, respectively. The lubricating oil fraction is supplied to the second distillation column 20 from a line L6 connected to the bottom of the first distillation column 15, and is distilled under reduced pressure in the second distillation column 20.

  In the distillation tower 20, the lubricating oil fraction is, for example, 70 Pale (fraction having a boiling point of 330 to 410 ° C.), SAE-10 (fraction having a boiling point of 410 to 470 ° C.), SAE-20 (fraction having a boiling point of 470 to 520 ° C.). Min), SAE-30 (fraction having a boiling point of 520 to 560 ° C.) and bright stock (fraction having a boiling point of 560 ° C. or higher). These fractions can be recovered from, for example, lines L8 to L10 connected to the second distillation column 20.

  According to the lubricating base oil manufacturing apparatus 100 described above, a heavy lubricating base oil having a sufficiently improved cloud point can be obtained.

  FIG. 2 is a flowchart showing another example of a hydrocarbon oil production apparatus in which the method for producing a lubricating base oil according to the present invention is implemented. A lubricating base oil production apparatus 110 shown in FIG. 2 includes two reaction towers 30 and 40 connected in series via a transfer line L8 in place of the reaction tower 10 in the lubricating base oil production apparatus 100. It has the same configuration as the lubricating base oil manufacturing apparatus 100 except that it is provided. In the lubricating base oil production apparatus 110, the reaction tower 30 includes the catalyst layer 16 similar to the first catalyst layer described above, and the reaction tower 40 includes the catalyst layer 18 similar to the second catalyst layer described above. These two reaction towers 30 and 40 carry out the hydrogenation treatment of the feedstock.

The hydrogenation treatment in the reaction tower 30 and the counter response 40 can be performed under the following reaction conditions. Examples of the hydrogen partial pressure include 1 to 20 MPa, and 3 to 15 MPa is preferable. The liquid hourly space velocity (LHSV) of the raw material oil is 0.1 to 5 h ^−1, but 0.5 to 3 h ⁻¹ is preferable. As a hydrogen / oil ratio, 100-1500 NL / L is mentioned, 200-1000 NL / L is preferable.

  In the present embodiment, the ratio V1 / V2 between the volume V1 of the first catalyst constituting the catalyst layer 16 and the volume V2 of the second catalyst constituting the catalyst layer 18 is 70/30 to 90/10. . For the same reason as in the manufacturing apparatus 100, V1 / V2 is preferably 2.6 to 7.3, and more preferably 3.0 to 5.7.

  In the present embodiment, for example, the cross-sectional area when the first catalyst layer included in the reaction tower 30 and the second catalyst layer included in the reaction tower 40 are cut along a plane perpendicular to the flow direction is independent of the cutting position. When the ratio is constant, the ratio [D3 / D4] of the thickness D3 of the first catalyst layer and the thickness D4 of the second catalyst layer shown in FIG. 2 may be in the range of 70/30 to 90/10. It is preferably within the range of 2.6 to 7.3, more preferably within the range of 3.0 to 5.7.

  In the method for producing a lubricating base oil according to the present embodiment, the product oil obtained through the hydrogenation treatment can be further processed by, for example, hydrofinishing. The hydrofinishing can be generally carried out by bringing the work to be finished into contact with a supported metal hydrogenation catalyst (for example, alumina on which platinum and / or palladium is supported) in the presence of hydrogen. By performing such a hydrofinishing, the hue and oxidation stability of the product oil can be improved, and the quality of the product can be improved. The hydrofinishing may be performed in a reaction facility different from the line containing the first catalyst and the second catalyst, but includes the second catalyst according to the present invention provided in the reactor. Alternatively, a hydrogenation finishing catalyst layer may be provided on the downstream side of the second catalyst layer.

[Manufacture of 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 mass% with respect to the mass of ZSM-22 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 E-1. .

  Furthermore, the micropore volume per unit mass 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) per unit mass 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 unit mass of the hydroisomerization catalyst, and M _z represents the content ratio (mass%) of the zeolite contained in the catalyst.

  The micropore volume per unit mass of the hydroisomerization catalyst E-1 is 0.055 cc / g, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.079 cc / g. there were.

(Production Example 2)
First, in the same manner as in Production Example 1, ZSM-22 having a Si / Al ratio of 45 was obtained. ZSM-22 was filled in a quartz tube furnace, heated in a nitrogen stream, heated to 400 ° C. at a rate of 5 ° C./min, and held for 6 hours. Thereafter, the flowing gas was switched to oxygen gas, and the temperature was further increased to 550 ° C. at a rate of 5 ° C./min, and kept at 550 ° C. overnight.

After the calcined ZSM-22 was cooled to room temperature, it was transferred to a flask, 0.5 M aqueous ammonium chloride solution was added and heated to reflux overnight to perform ion exchange. After completion of the ion exchange, the solid content was collected by filtration, washed with ion exchanged water, and dried overnight in a dryer at 60 ° C. to obtain NH ₄ type ZSM-22.

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 and palladium were supported on the carrier precursor obtained above by the following method.

  First, tetraamminedinitroplatinum (II) and tetraamminedinitropalladium were dissolved in a minimum amount of ion-exchanged water. This solution was impregnated with the above carrier precursor by an initial wetting method, and supported so that the amount of platinum was 0.1% by mass and the amount of palladium was 0.3% by mass with respect to the mass of ZSM-22. . Next, these are dried overnight in a dryer at 60 ° C., fired at 400 ° C. for 3 hours under air flow, formed into a disk shape by tableting, further coarsely pulverized, and sieved. It was set as the irregular-shaped granule of the largest particle size 125-250 micrometers. Thus, catalyst E-2 was obtained.

(Production Example 3)
Catalyst E-3 was obtained in the same manner as in Production Example 2 except that the supported amounts of platinum and palladium were 0.1% by mass and 0.1% by mass, respectively.

(Production Example 4)
Catalyst E-4 was obtained in the same manner as in Production Example 2, except that the supported amounts of platinum and palladium were 0.1% by mass and 0.2% by mass, respectively.

(Production Example 5)
Catalyst E-5 was obtained in the same manner as in Production Example 2 except that the amounts of platinum and palladium supported were 0.01% by mass and 0.01% by mass, respectively.

[Raw oil]
The following raw oils were prepared.
R-1: FT synthetic oil vacuum distillation bottom oil (boiling point 560 ° C. or higher, hydrocarbon content 21 or more hydrocarbon content: 100% by mass)
R-2: Deasphalted oil obtained by removing asphalt from the vacuum distillation column bottom oil of Middle East crude oil in the propane desulfurization step (content ratio of hydrocarbons having a boiling point of 550 ° C. or higher and 21 or more carbon atoms: 100% by mass)
R-3: A mixed oil obtained by mixing R-1 and R-2 at a capacity ratio R-1 / R-2 = 50/50.

[Manufacture of lubricating base oil]
Example 1
80 ml of catalyst E-1 was packed on the upstream side (upper layer) of the fixed bed reactor, and 20 ml of catalyst E-2 was packed on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, R-1 is supplied as raw material oil at LHSV: 1.0 h ^-1 from the top of the reactor (upper layer of the catalyst layer), and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 331 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 159, a pour point of -15 ° C, and a cloud point of -10 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 80 mass%.

  The viscosity index, pour point, and cloud point were measured according to a viscosity index calculation method specified by JIS K2283, a pour point test method specified by JIS K2269, and a cloud point test method specified by JIS K2269, respectively.

(Example 2)
90 ml of catalyst E-1 was packed on the upstream side (upper layer) and 10 ml of catalyst E-3 on the downstream side (lower layer) of the fixed bed reactor, and a two-layer catalyst layer was provided in the reactor.

Next, R-1 is supplied as raw material oil at LHSV: 1.0 h ^-1 from the top of the reactor (upper layer of the catalyst layer), and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 321 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. The fraction had a viscosity index of 159, a pour point of -15 ° C, and a cloud point of -4 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 78 mass%.

(Example 3)
The fixed bed reactor was filled with 70 ml of catalyst E-1 on the upstream side (upper layer) and 30 ml of catalyst E-4 on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, R-1 is supplied as a raw material oil from the top of the reactor (upper layer of the catalyst layer) at LHSV: 1.0 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 318 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 158, a pour point of -15 ° C, and a cloud point of -13 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 74 mass%.

Example 4
80 ml of catalyst E-1 was packed on the upstream side (upper layer) of the fixed bed reactor, and 20 ml of catalyst E-2 was packed on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, from the top of the reactor (upper layer side of the catalyst layer), R-2 is supplied as a raw oil at LHSV: 1.0 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 10 MPa and a reaction temperature of 341 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 110, a pour point of -12.5 ° C, and a cloud point of -10 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 79 mass%.

(Example 5)
80 ml of catalyst E-1 was packed on the upstream side (upper layer) of the fixed bed reactor, and 20 ml of catalyst E-2 was packed on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, from the top of the reactor (upper side of the catalyst layer), R-3 is supplied as a raw oil at LHSV: 1.5 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 10 MPa and a reaction temperature of 345 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 131, a pour point of -15 ° C, and a cloud point of -8 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 82 mass%.

(Comparative Example 1)
A fixed bed reactor was filled with 100 ml of catalyst E-1 alone, and a catalyst layer having a single layer structure was provided in the reactor.

Next, from the tower top (upper layer side of the catalyst layer), R-1 is supplied as a raw oil at LHSV: 1.0 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 330 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. The fraction had a viscosity index of 159, a pour point of -15 ° C, and a cloud point of 15 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 68 mass%.

(Comparative Example 2)
A fixed bed reactor was filled with 100 ml of catalyst E-1 alone, and a catalyst layer having a single layer structure was provided in the reactor.

Next, from the top of the reactor (upper layer side of the catalyst layer), R-2 is supplied as a raw oil at LHSV: 1.0h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 331 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 108, a pour point of -12.5 ° C, and a cloud point of 6 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 62 mass%.

(Comparative Example 3)
95 ml of catalyst E-1 was packed on the upstream side (upper layer) of the fixed bed reactor, and 5 ml of catalyst E-2 was packed on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, R-1 is supplied as a raw material oil from the top of the reactor (upper layer of the catalyst layer) at LHSV: 1.0 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 5 MPa and a reaction temperature of 318 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. The fraction had a viscosity index of 159, a pour point of -15 ° C, and a cloud point of 10 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 76 mass%.

(Comparative Example 4)
80 ml of catalyst E-1 was packed on the upstream side (upper layer) of the fixed bed reactor, and 20 ml of catalyst E-5 was packed on the downstream side (lower layer), and a two-layer catalyst layer was provided in the reactor.

Next, R-1 is supplied as a raw material oil from the top of the reactor (upper layer of the catalyst layer) at LHSV: 1.0 h ⁻¹ , and hydrogen is supplied at a hydrogen pressure of 10 MPa and a reaction temperature of 345 ° C. in a hydrogen stream. Processed.

  The product oil was distilled to obtain a fraction having a boiling point of 550 ° C. or higher. This fraction had a viscosity index of 157, a pour point of -15 ° C, and a cloud point of 14 ° C. Moreover, the yield with respect to the raw material oil of this fraction was 81 mass%.

  As shown in the table, a high viscosity index and a low viscosity are obtained by passing the raw material oil through the catalyst layer in which the first catalyst and the second catalyst according to the present invention are laminated at a predetermined ratio and performing the hydrogenation treatment. A lubricating base oil having a pour point and a sufficiently low cloud point can be obtained.

DESCRIPTION OF SYMBOLS 10, 30, 40 ... Reaction tower, 12 ... 1st catalyst layer, 14 ... 2nd catalyst layer, 15 ... 1st distillation tower, 16 ... Catalyst layer (1st catalyst layer), 18 ... Catalyst layer (1st) 2 catalyst layers), 20 ... second distillation tower, 100, 110 ... lubricating base oil production apparatus.

Claims (2)

A step of bringing a feedstock containing hydrocarbons having 21 or more carbon atoms into contact with the first catalyst and the second catalyst in this order in the presence of hydrogen;
The first catalyst contains a zeolite having a 10-membered ring one-dimensional pore structure, and a support containing a binder, and platinum and / or palladium supported on the support, and per unit mass of the catalyst. A hydroisomerization catalyst having a micropore 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. , Derived from ion-exchanged zeolite obtained by ion exchange in a solution containing ammonium ions and / or protons, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.04 to 0.005. 12cc / g,
The second catalyst includes a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support, and the total support of the platinum and / or palladium. The amount of the catalyst is 0.05 to 0.4 parts by mass with respect to 100 parts by mass of the carrier in terms of metal atoms,
A method for producing a lubricating base oil, wherein a ratio V1 / V2 of the volume V1 of the first catalyst and the volume V2 of the second catalyst is 70/30 to 90/10. A step of bringing a feedstock containing hydrocarbons having 21 or more carbon atoms into contact with the first catalyst and the second catalyst in this order in the presence of hydrogen;
An ion-exchanged zeolite obtained by ion-exchanging an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure in a solution containing ammonium ions and / or protons; , A first step of obtaining a support precursor by heating a mixture containing a binder at a temperature of 250 to 350 ° C. in an N ₂ atmosphere, and including a platinum salt and / or a palladium salt in the support precursor. A second step of obtaining a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite by calcining the obtained catalyst precursor in an atmosphere containing molecular oxygen at a temperature of 350 to 400 ° C .; A hydroisomerization catalyst obtained in a method for producing a hydroisomerization catalyst comprising:
The second catalyst includes a support containing zeolite having a 10-membered ring one-dimensional pore structure, and platinum and / or palladium supported on the support, and the total support of the platinum and / or palladium. The amount of the catalyst is 0.05 to 0.4 parts by mass with respect to 100 parts by mass of the carrier in terms of metal atoms,
A method for producing a lubricating base oil, wherein a ratio V1 / V2 of the volume V1 of the first catalyst and the volume V2 of the second catalyst is 70/30 to 90/10.

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