Catalysts for selective ring opening reactions and methods of using the same

Abstract

The present disclosure provides a catalyst for SRO reaction. The catalyst comprises a solid acidic substance and a metal. In this case, at least 20% of the total pore volume of the catalyst corresponds to pores of the catalyst having a pore diameter of 10 nm or more. The present disclosure also provides a method using the catalyst.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2021-0142897, filed on October 25, 2021, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] This disclosure relates to a catalyst for selective ring-opening (SRO) reactions and a method for using the catalyst. More specifically, this disclosure relates to an SRO reaction catalyst that can be used in the preparation process of lubricating oil base oils, and to a method for applying the catalyst in the preparation process of lubricating oil base oils. Background Technology

[0004] Lubricating oil base oils are the raw materials for lubricants. Generally, good lubricating oil base oils have a high viscosity index (VI), high stability (resistance to oxidation, heat, UV, etc.), and low volatility. The American Petroleum Institute (API) classifies lubricating oil base oils according to qualities such as sulfur content, saturation, and VI, as shown in Table 1 below.

[0005] [Table 1]

[0006]

[0007] Lubricating oil base oils classified as Group IV are the highest quality oils, with quality decreasing from Group IV to Group I. Higher quality lubricating oil base oils have lower sulfur and nitrogen content, higher VI, lower pour point, lower CCS viscosity, and lower Noack volatility. Furthermore, higher quality lubricating oil base oils tend to have higher alkane content and lower cycloalkanes and aromatic compounds content.

[0008] Viscosity VI (VI) is an important physical property used to evaluate the quality of lubricating oil base oils. VI is an indicator related to viscosity change with temperature. The higher the VI, the smaller the viscosity change with temperature. Therefore, lubricating oil base oils with high VI are advantageous for engine protection due to their relatively high viscosity at high temperatures, and advantageous for driving engine pumps due to their relatively low viscosity at low temperatures. Thus, lubricating oil base oils with high VI are considered high-quality base oils. Furthermore, the market demand for lubricating oil base oils with VI higher than Group III oils (hereinafter referred to as Group III+ lubricating oil base oils) is continuously growing.

[0009] Two main methods are known for manufacturing lubricating oil base oils having a VI higher than that of Group III oils. The two methods are i) preparing synthetic base oils (Group IV) from chemical raw materials, and ii) performing structural isomerization reactions using a feed (raw material) having a high paraffin content. However, in the case of i), there is a problem that the raw material is expensive and the amount of the raw material that can be used is small compared to mineral oil-based lubricating oil base oils. Therefore, the impact on the market is not important. In the case of ii), there is a problem that it is difficult to obtain an oil having a high paraffin content that can be used as a feed. This makes it difficult to supply a large amount of product to the market.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] (Patent Document 1) KR 10-2018-0132101 A1 SUMMARY

[0013] Accordingly, the present disclosure proposes a new solution to be able to supply a large amount of lubricating oil base oil having a high VI to the market. A first aspect of the present disclosure is to provide an SRO reaction catalyst. A second aspect of the present disclosure is to provide a method of increasing the VI of a lubricating oil base oil by using the catalyst of the first aspect. A third aspect of the present disclosure is to provide a method of preparing a lubricating oil base oil by using the catalyst of the first aspect.

[0014] The SRO reaction catalyst that implements the first aspect of the present disclosure includes a solid acidic substance and a metal, wherein the pore diameter of the pores of the catalyst is 10 nm or more for 20% or more of the pore volume of the catalyst with respect to the total pore volume of the catalyst.

[0015] According to one embodiment of the present disclosure, the solid acidic substance includes a first solid acidic substance and a second solid acidic substance, the pore diameter of the first solid acidic substance is 1 nm or less, and the pore diameter of the second solid acidic substance is greater than 1 nm.

[0016] According to one embodiment of the present disclosure, the first solid acidic substance includes a zeolite, a crystalline aluminosilicate, a silica-alumina-phosphate (SAPO), an aluminum phosphate (AlPO), a metal organic framework (MOF), or a combination thereof.

[0017] According to one embodiment of the present disclosure, the second solid acidic substance includes a silica-alumina (amorphous silica-alumina, ASA), a clay, a zirconium sulfate oxide, a zirconium oxide, a titanium dioxide, a niobium oxide, an aluminum oxide, a silicon dioxide, or a combination thereof.

[0018] According to one embodiment of the present disclosure, the metal is a Group VIII metal.

[0019] According to one embodiment of the present disclosure, the content of the metal in the catalyst is 0.05 to 5% by weight relative to the total weight of the catalyst.

[0020] According to one embodiment of the present disclosure, the catalyst further comprises a non-acidic binder.

[0021] According to one embodiment of the present disclosure, the catalyst comprises 10 to 100 parts by weight of the first solid acidic substance and 10 to 100 parts by weight of the non-acidic binder relative to 100 parts by weight of the second solid acidic substance.

[0022] According to one embodiment of the present disclosure, the catalyst further comprises a promoter, wherein the promoter includes an alkali metal, an alkaline earth metal, a Group Vb metal, a Group VIb metal, Sn, or a combination thereof.

[0023] The method of improving the VI of a lubricating base oil according to the second aspect of the present disclosure comprises subjecting a reactant to an SRO reaction in the presence of the catalyst according to the first aspect of the present disclosure.

[0024] According to one embodiment of the present disclosure, the reactant comprises: a feedstock for preparing a lubricating base oil; an intermediate oil in a process of preparing a lubricating base oil; or a lubricating base oil.

[0025] According to one embodiment of the present disclosure, the SRO reaction is performed in the presence of hydrogen at a temperature range of 100 to 450°C.

[0026] The method of preparing a lubricating base oil according to the third aspect of the present disclosure comprises the steps of: a) preparing a feedstock; b) introducing the feedstock into either a hydrodewaxing reaction (HDW) or an SRO reaction; and c) introducing the reaction product of step b) into the remaining one of the HDW reaction and the SRO reaction, wherein the SRO reaction is performed in the presence of the catalyst according to the first aspect.

[0027] According to one embodiment of the present disclosure, the method further comprises d) introducing the reaction product of step c) into a hydrofinishing (HDF) reaction.

[0028] According to one embodiment of the present disclosure, the VI of the lubricating base oil prepared by the method is at least 5 higher than the VI of a lubricating base oil prepared by a method without performing the SRO reaction.

[0029] By using the catalyst of the present disclosure, a wider range of feedstocks can be used to prepare a lubricating base oil with improved VI. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a schematic diagram of the performance of each lubricating base oil according to the type of chemical that makes up the lubricating base oil;

[0031] Figure 2 A schematic diagram of the structural change of the hydrocarbon compounds at each stage when the lubricating oil base oil production method according to one embodiment of the present disclosure is performed in the order defined by the method;

[0032] Figure 3 A graph showing the results of the measurement of the pore size distribution of the catalyst according to an example of the present disclosure; and

[0033] Figure 4 A graph showing the change in the viscosity of the lubricating oil base oil determined according to one example of the present disclosure with the number of days of treatment. DETAILED DESCRIPTION

[0034] The above and other objects, features and advantages of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, although the present disclosure is not limited thereto. In describing the present disclosure, when it is considered that a detailed description of the related art would unnecessarily obscure the gist of the present disclosure, the detailed description can be omitted.

[0035] The VI described above is affected by the type of the hydrocarbon compounds present in the lubricating oil base oil. Specifically, the VI of the lubricating oil base oil changes depending on the content of the paraffin compounds / cycloparaffin compounds / aromatic compounds in the lubricating oil base oil. It is generally known that the higher the content of these compounds in the order of paraffin

[0036] aromatic compounds, the higher the VI. Figure 1 The properties of each lubricating oil base oil according to the type of the chemical are shown.

[0037] Reference Figure 1 The first four compounds have a high content of paraffin and a low content of cycloparaffin and aromatic compounds, and thus have excellent VI. Therefore, using these compounds, it is possible to produce a Group III+ lubricating oil base oil. However, as described above, the amount of the first four compounds of the crude oil is very limited. Figure 1 The amount of the first four compounds of the crude oil is very limited.

[0038] The present disclosure relates to providing a method for producing a Group III+ lubricating oil base oil, which uses Figure 1 the first four compounds of the crude oil and the last three compounds as feed for producing a lubricating oil base oil.

[0039] Catalyst for SRO reaction

[0040] The present disclosure provides a catalyst for SRO reaction that can selectively open some of cyclic compounds in a feed to produce a lubricating oil base oil. The SRO reaction opens a ring of a naphthenic compound or an aromatic compound in the feed and converts the naphthenic compound or the aromatic compound into a branched alkane. This makes it possible to obtain a lubricating oil base oil having a higher VI than a conventional lubricating oil base oil from the same feed.

[0041] In the present disclosure, "selective ring opening (SRO)" means preferentially breaking carbon-carbon bonds constituting a cyclic compound in a hydrocarbon compound having two or more rings into carbon-carbon bonds constituting a main chain and carbon-carbon bonds constituting a branched alkane connected to the cyclic compound. The purpose of the ring opening reaction of the present disclosure is to minimize breaking of carbon bonds constituting a main chain and to selectively open only carbon bonds constituting a cyclic compound, thereby maintaining the performance and yield of a lubricating oil base oil.

[0042] The SRO reaction catalyst according to the present disclosure is a bifunctional catalyst comprising a solid acidic material and a metal. While not being bound by any particular theory, it is contemplated that in the present disclosure, the SRO reaction can include reactions that proceed through mechanisms such as the following exemplified.

[0043]

[0044] In this mechanism, dehydrogenation and hydrofining reactions require the action of a metal catalyst, and isomerization and β-scission reactions require the action of an acid catalyst, and thus it is contemplated that the metal and the solid acid used in the catalyst of the present disclosure can each achieve the respective actions.

[0045] In the present disclosure, the solid acidic material means a solid material having a Brønsted acid site or a Lewis acid site. According to one embodiment of the present disclosure, the solid acidic material can include a first solid acidic material and a second solid acidic material. The first solid acidic material has a pore diameter of about 1 nm or less, and the second solid acidic material has a pore diameter of greater than about 1 nm. In the present disclosure, the pore diameter of the second solid acidic material can preferably be in the range of greater than about 1 nm to 100,000 nm. More preferably, the pore diameter can be about 10 nm or more to about 100,000 nm or less.

[0046] According to one embodiment of the present disclosure, the first solid acidic material includes a zeolite, a crystalline aluminosilicate, a silica-alumina-phosphate (SAPO), an aluminum phosphate (AlPO), a metal organic framework (MOF), or a combination thereof. The zeolite can be, for example, SAPO-11, SAPO-41, ZSM-5, ZSM-12, ZSM-23, ZSM-48, FAU, BETA, or MOR.

[0047] The first solid acidic material is responsible for treating compounds other than polycyclic compounds (e.g., paraffin-based compounds or monocyclic compounds) in the feed, and can help to increase the selectivity of the second solid acidic material in treating polycyclic compounds.

[0048] According to one embodiment of the present disclosure, the second solid acidic material can include silica-alumina (amorphous silica-alumina, ASA), clay, zirconium sulfate oxide, zirconium oxide, titanium dioxide, niobium oxide, aluminum oxide, silica, or a combination thereof.

[0049] In the present disclosure, the second solid acidic material can be clay. The clay can be, but is not limited to, kaolinite, montmorillonite, monzonite, illite, chlorite, vermiculite, talc, pyrophyllite, etc., or can be a combination of the foregoing. In the present disclosure, the clay can be kaolinite.

[0050] Due to the presence of multiple rings, the volume of the polycyclic compound can be large compared to monocyclic compounds or paraffin-based hydrocarbon compounds. Since the first solid acidic material has a relatively small pore size, it is difficult for the polycyclic compound to access the active site of the first solid acidic material, and thus the first solid acidic material cannot induce the SRO reaction of the polycyclic compound. On the other hand, the second solid acidic material has a relatively large pore size compared to the first solid acidic material. Therefore, the SRO reaction of the polycyclic compound can proceed within the pores of the second solid acidic material.

[0051] The solid acidic material of the present disclosure can also be used as a carrier and / or a binder. The solid acidic material is used as a carrier, thus playing a role of loading the metal component included in the catalyst of the present disclosure. The solid acidic material can also be used as a binder and help to form a catalyst having sufficient strength, so that the catalyst of the present disclosure can be stably used in a high-temperature, high-pressure reactor.

[0052] According to other embodiments of the present disclosure, the catalyst can further include a non-acidic carrier and / or a binder. In the present disclosure, the term "non-acidic carrier and binder" refers to a substance that does not play an acid catalyst role but can play a carrier or binder role, which is different from the solid acidic material. The non-acidic carrier and binder can be additionally used in the present disclosure to stabilize the catalyst. For example, the non-acidic binder can include carbon, silicon carbide, pseudoboehmite, or a mixture thereof.

[0053] Further, the catalyst of the present disclosure includes a metal. According to one embodiment of the present disclosure, the metal can be a Group VIII metal. Preferably, the metal can be Pt, Pd, Ru, Ir, Ni, Co, Fe, or a combination thereof. In the case of performing an SRO reaction including a reaction following the above-described SRO reaction mechanism, it is expected that the metal promotes dehydrogenation and hydrogenation of the catalyst of the present disclosure.

[0054] It is also expected that the metal can also contribute to preventing the catalyst from deactivating. While not being bound by any particular theory, when the SRO reaction is carried out, the following side reaction also occurs in the case where a reaction following the above-described SRO reaction mechanism is carried out.

[0055]

[0056] As with the SRO reaction, the side reaction also occurs at the active sites of the solid acidic substance, and due to this adsorption, the catalyst would theoretically deactivate. However, since the catalyst of the present disclosure can contain both the metal and the solid acidic substance, the metal can promote the hydrogenation reaction, thereby promoting the desorption reaction to desorb the substance adsorbed to the solid acidic substance.

[0057] According to one embodiment of the present disclosure, the amount of the metal contained by the catalyst can be 0.05 to 5% by weight, based on the total weight of the catalyst. Preferably, the amount of the metal contained by the catalyst can be 0.1 to 3% by weight, and this amount is more preferably about 0.2 to 1% by weight. When the content of the metal is less than about 0.05% by weight, since the content of the metal contained by the catalyst is too low, the metal cannot sufficiently function. In particular, there can be a problem in that the catalyst deactivates in a very short time of using the catalyst. On the other hand, when the content of the metal exceeds 5% by weight, the hydrogenation reaction is excessively promoted, thereby causing a decrease in the efficiency of the SRO reaction, or causing the solid acid active sites in the solid acidic substance to be clogged by the metal.

[0058] According to one embodiment of the present disclosure, in the catalyst of the present disclosure, the pore diameter of the pores of the catalyst for 20% or more of the total pore volume of the catalyst is 10 nm or more. The pore diameter of the pores corresponding to preferably at least about 30%, more preferably at least about 50%, even more preferably at least about 70%, still even more preferably at least about 80%, and most preferably at least about 85% of the total pore volume of the catalyst can be about 10 nm or more. The pores corresponding to about 90% of the total pore volume can have such a pore diameter. Preferably, the pore diameter can be about 50 nm or more, and more preferably about 100 nm or more. The upper limit of the pore diameter range can be about 1,000,000 nm. The catalyst of the present disclosure contains a specific percentage of pores having a size greater than or equal to a specific nanometer size, thereby enabling the SRO reaction of bulky polycyclic compounds. When the pore distribution of the catalyst is lower than the level as listed above, it will be difficult to expect an improvement in VI by the catalyst of the present disclosure.

[0059] In one embodiment of the present disclosure, the catalyst comprising a non-acidic binder can comprise about 10 parts by weight to 100 parts by weight of the first solid acidic material and about 10 parts by weight to 100 parts by weight of the non-acidic binder, with respect to 100 parts by weight of the second solid acidic material. Preferably, the catalyst can comprise about 30 parts by weight to 90 parts by weight, more preferably about 40 parts by weight to 80 parts by weight, more preferably about 50 parts by weight to 70 parts by weight of the first solid acidic material, with respect to 100 parts by weight of the second solid acidic material. Preferably, the catalyst can comprise about 20 parts by weight to 80 parts by weight, more preferably about 20 parts by weight to 60 parts by weight, more preferably about 30 parts by weight to 50 parts by weight of the non-acidic binder, with respect to 100 parts by weight of the second solid acidic material. When the content of the first solid acidic material and the non-acidic binder falls outside of the range, there can occur a problem of a decrease in the yield of the lubricating oil base oil due to degradation at the time of reaction. In particular, when the content of the non-acidic binder is lower than the lower limit of the above range, there can occur a problem of breakage of the catalyst in a harsh reaction environment due to insufficient strength of the prepared catalyst.

[0060] According to one embodiment of the present disclosure, the catalyst of the present disclosure can further comprise a promoter as needed. The promoter can be included to adjust the reactivity of the metal contained in the catalyst. The promoter can be an alkali metal, an alkaline earth metal, a Group Vb metal, a Group VIb metal, Sn, or a combination thereof. In the present disclosure, the promoter can preferably comprise Mg, Ca, or a combination thereof. In one embodiment of the present disclosure, the content of the promoter in the catalyst of the present disclosure can be in the range of about 1 wt% to 10 wt%, based on the total weight of the catalyst.

[0061] The SRO reaction catalyst of the present disclosure can be used in the following method.

[0062] Process for increasing the VI of a lubricating oil base oil

[0063] The present disclosure also provides a method of improving the VI of a lubricating oil base oil by using the above catalyst. The method comprises subjecting a reactant to SRO reaction in the presence of the SRO reaction catalyst. According to one embodiment of the present disclosure, the reactant comprises: a feedstock for preparing a lubricating oil base oil; an intermediate oil in the process of preparing a lubricating oil base oil; or a lubricating oil base oil. Preferably, the reactant can be a feedstock for preparing a lubricating oil base oil; or an intermediate oil in the process of preparing a lubricating oil base oil. Most preferably, the reactant can be an intermediate oil in the process of preparing a lubricating oil base oil.

[0064] The intermediate oil refers to an oil produced when the feedstock for preparing a lubricating oil base oil has passed through at least one reactor and present before entering a hydrofining reaction. For example, the intermediate oil in the present disclosure can be an oil present before or after the HDW reaction.

[0065] According to one embodiment of the present disclosure, the reactant can be an oil containing a cyclic hydrocarbon compound. The reactant can satisfy the condition 5 wt% ≤ C N + C A <100 wt%, and preferably satisfies the condition C P > 50 wt% and 20 wt% ≤ C N + C A ≤ 50 wt%.

[0066] Here, C P represents the content of paraffin, C N represents the content of cycloparaffin, and C A represents the content of aromatic compound. In the present disclosure, C A may be 5 wt% or less, and preferably 1 wt% or less.

[0067] According to one embodiment of the present disclosure, the SRO reaction can be performed in the presence of hydrogen at a temperature range of 100°C to 450°C. The reaction conditions other than the catalyst and the temperature can be the same as the processing conditions of the conventional HDW processing.

[0068] According to one embodiment of the present disclosure, the VI of the lubricating base oil passing through the method is at least 5 higher than the VI of the lubricating base oil not passing through the method. Preferably, the difference in VI between the lubricating base oils can be greater than or equal to 8, and more preferably greater than or equal to 10.

[0069] Process for the preparation of a lubricating oil base oil

[0070] The present disclosure provides a method of preparing a lubricating base oil by using the above-described catalyst. The method includes the steps of: a) preparing a feed; b) introducing the feed into either one of an HDW reaction and an SRO reaction; and c) introducing the reaction product of step b) into the remaining one of the HDW reaction and the SRO reaction. Here, the SRO reaction is performed in the presence of the above-described catalyst of the present disclosure.

[0071] There is no particular limitation on the feed in the present disclosure, as long as it can be used as a raw material in a conventional lubricating base oil preparation process. The feed in the present disclosure can include oils having a large amount of cycloparaffin and aromatic compound, which are difficult to use as a raw material in a conventional lubricating base oil preparation process for high-quality lubricating base oils such as Group III or higher.

[0072] According to one embodiment of the present disclosure, the feed can be an oil containing a cyclic hydrocarbon compound. The reactant can satisfy the condition 5 wt% ≤ C N + C A <100 wt%, and preferably satisfies the condition C P> 50 wt% and 20 wt% ≤ C N + C A ≤ 50 wt%. Here, C P represents the content of paraffins, C N represents the content of naphthenes, and C A represents the content of aromatics. In the present disclosure, C A may be 5 wt% or less, and preferably 1 wt% or less.

[0073] In the present disclosure, the HDW reaction refers to a reaction in which a wax component such as a normal paraffin is isomerized to an isoparaffin, thereby removing the wax component. The HDW reaction can lower the pour point of a lubricating oil base oil, thereby improving the low-temperature properties of the lubricating oil base oil. Figure 2 is a schematic diagram of the structural changes of the hydrocarbon compounds at each stage when the lubricating oil base oil production method according to one embodiment of the present disclosure is performed in the order as defined. According to one embodiment of the present disclosure, as shown in Figure 2 , the feed can be first introduced into the HDW reaction, and then introduced into the SRO reaction. According to another embodiment of the present disclosure, the feed can be first introduced into the SRO reaction, and then introduced into the HDW reaction. As can be seen from Figure 2 , in the aspect in which the HDW reaction uses a normal paraffin as the main reactant, and the SRO reaction uses a cyclic hydrocarbon compound such as a naphthene and an aromatic compound as the main reactant, the two reactions are independent of each other. Therefore, it is immaterial which order the reactions are performed. On the other hand, the HDW reaction is generally performed under more severe reaction conditions than the SRO reaction. Therefore, from the viewpoint of the yield of the lubricating oil base oil, it is appropriate that the HDW reaction and the SRO reaction are performed separately. Furthermore, from the viewpoint of the yield of the lubricating oil base oil, the SRO reaction is more preferably performed after the HDW reaction. This is because when the SRO reaction is performed after the removal of a small amount of aromatic compounds, impurities, and the like present in the feed by the HDW reaction, the side reactions due to cracking are minimized, thereby preventing the yield loss in production.

[0074] In the present disclosure, the reaction conditions of the HDW reaction can be the same as those of a conventional HDW reaction, and can not be particularly limited. According to one embodiment of the present disclosure, the HDW reaction is performed under the following conditions: the reaction temperature is 250°C to 410°C, the reaction pressure is 30 kg / cm 2 to 200 kg / cm 2 , the space velocity (LHSV) is 0.1 hr -1 to 3.0 hr -1 , and the volume ratio of hydrogen to the feed is 150 Nm 3 / m 3 to 1000 Nm 3 / m 3 .

[0075] The catalysts that can be used for the HDW reaction include: a support having an acid site; and one or more hydrogenation metals selected from the group consisting of elements in Group 2, Group 6, Group 9, and Group 10 of the periodic table. In particular, among Group 9 and Group 10 metals (i.e., Group VIII metals), Co, Ni, Pt, and Pd are preferably used, and among Group 6 metals (i.e., Group VIB metals), Mo and W are preferably used. The types of supports having an acid site include molecular sieves, alumina, silica-alumina, and the like. Among them, the molecular sieves refer to crystalline aluminosilicates (zeolites), SAPO, AlPO, and the like. Mesoporous molecular sieves having a 10-membered oxygen ring, such as SAPO-11, SAPO-41, ZSM-11, ZSM-22, ZSM-23, ZSM-35, or ZSM-48, can be used, and macroporous molecular sieves having a 12-membered oxygen ring can be used.

[0076] In the lubricating oil base oil production method according to the present disclosure, the reaction conditions of the SRO reaction can be the same as the reaction conditions of the SRO reaction used in the method of increasing the VI of the lubricating oil base oil described above.

[0077] As shown in FIG. 1, according to one embodiment of the present disclosure, the production method can further include introducing the reaction product of step c) into a hydrofining reaction. The hydrofining reaction can remove olefins and residual polycyclic aromatic compounds in the oil to ensure the stability of the produced lubricating oil base oil. Figure 2

[0078] In the present disclosure, the reaction conditions of the hydrofining reaction can be the same as the reaction conditions of a conventional hydrofining reaction, and can not be particularly limited. According to one embodiment of the present disclosure, the hydrofining reaction is performed at a reaction temperature of 250°C to 300°C, a reaction pressure of 30 kg / cm 2 to 200 kg / cm 2 , a space velocity (LHSV) of 0.1 hr -1 to 3 hr -1 , and a volume ratio of hydrogen to feed of 300 Nm 3 / m 3 to 1500 Nm 3 / m 3 .

[0079] ​Further, the catalyst used for the hydrofinishing reaction can be a catalyst in which a metal is supported on a support. The metal includes one or more metals selected from Group 6, Group 8, Group 9, Group 10, and Group 11 elements having a hydrogenation action. Preferably, a metal sulfide of Ni-Mo, Co-Mo, or Ni-W, or a noble metal such as Pt or Pd can be used. Further, the support of the catalyst used for the hydrofinishing reaction can be silica, alumina, silica-alumina, titania, zirconia, or a zeolite, each of which has a large surface area. Preferably, alumina or silica-alumina can be used.

[0080] According to one embodiment of the present disclosure, the feed can be first introduced into the HDW reaction, and then the HDW reaction product can be simultaneously introduced into the SRO reaction and the hydrofinishing reaction. The SRO reaction and the hydrofinishing reaction can be performed under similar reaction conditions except for the catalyst. In this case, an advantage is that the method of the present disclosure can be implemented using a conventional hydrofinishing reactor without adding a new reactor in a conventional lubricating base oil production apparatus including an HDW reactor and a hydrofinishing reactor.

[0081] According to one embodiment of the present disclosure, the production method can further include fractionating the reaction product after the hydrofinishing reaction to separate a lubricating base oil having a desired specification.

[0082] According to one embodiment of the present disclosure, the VI of the lubricating base oil produced by the lubricating base oil production method of the present disclosure is at least 5 higher than that of a lubricating base oil produced by a conventional lubricating base oil production method without performing the SRO reaction. Preferably, the VI difference can be greater than or equal to 8, and more preferably greater than or equal to 10. Hereinafter, preferred examples are given to help understand the present disclosure, but the following examples are provided only to make it easier to understand the present disclosure, and thus the present disclosure is not limited thereto.

[0083] Example

[0084] 1. Preparation of a catalyst for an SRO reaction

[0085] (1) Sample 1

[0086] A USY zeolite, kaolin, and a pseudo-boehmite as a binder were mixed in a weight ratio of about 30:50:20, and then co-milled. Subsequently, the mixture of the zeolite, clay, and binder was impregnated with an aqueous solution of [Pt(NH3)4](NO3)2 so that the content of Pt was 0.1% by weight based on the total weight of the catalyst, and then the impregnated mixture was shaped. The shaped mixture was then dried at a temperature of about 120°C for about 3 hours, and calcined at about 500°C for about 3 hours. The catalyst thus obtained was used as Sample 1.

[0087] (2) Sample 2

[0088] In addition to the impregnation step, a catalyst in which Pt was not impregnated was prepared using the same preparation method as Sample 1. The catalyst thus obtained was used as Sample 2.

[0089] (3) Sample 3

[0090] ZSM-48 zeolite and pseudoboehmite as a binder were mixed at a weight ratio of about 1:1, and then co-milled. Subsequently, the mixture of zeolite and binder was impregnated with an aqueous solution of [Pt(NH3)4](N03)2 so that the content of Pt was 0.5% by weight based on the total weight of the catalyst, and then the impregnated mixture was shaped. The shaped mixture was then dried at a temperature of about 120°C for about 3 hours, and calcined at about 500°C for about 3 hours. The catalyst thus obtained was used as Sample 3.

[0091] 2. Measurement of physical properties of catalyst

[0092] The physical properties of Sample 2 and Sample 3 were measured using a Hg porosimetry apparatus, and the results are shown in Table 2 below.

[0093] [Table 2]

[0094]

[0095] The pore size distribution of Sample 2 and Sample 3 was also analyzed with a Hg porosimetry apparatus (MicroActive AutoPore V 9600), and the results are shown in Figure 3 .

[0096] In the case of Sample 2, it was confirmed that the pore volume of pores having a size of 100 nm or more accounted for about 85% with respect to the total pore volume of 0.71 mL / g. On the other hand, in the case of Sample 3, it was confirmed that the pore volume of pores having a size of 100 nm or more accounted for about 6% or less with respect to the total pore volume of 0.35 mL / g.

[0097] 3. SRO reaction experiment

[0098] (1) Comparative Example 1

[0099] The feed was introduced into the HDW reaction and the HDF reaction in this order to produce a lubricating oil base oil. The reaction conditions are shown in Table 3 below. The properties of the lubricating oil base oil produced are shown in Table 4.

[0100] (2) Example 1

[0101] The feed was introduced into the HDW reaction, the SRO reaction and the HDF reaction in this order to produce a lubricating oil base oil. The SRO reaction was performed in the presence of the catalyst of Sample 2, and the reaction conditions are shown in Table 3. The properties of the produced lubricating oil base oil are shown in Table 4.

[0102] (3) Experimental Example 2

[0103] A lubricating oil base oil was produced in the same manner as in Experimental Example 1, except that the reaction temperature of the SRO reaction was changed to 280°C. The reaction conditions are shown in Table 3. The properties of the produced lubricating oil base oil are shown in Table 4.

[0104] (4) Comparative Experimental Example 2

[0105] A lubricating oil base oil was produced in the same manner as in Experimental Example 1, except that the reaction temperature of the SRO reaction was changed to 320°C, and the SRO reaction was performed in the presence of the catalyst of Sample 3. The reaction conditions are shown in Table 3. The properties of the produced lubricating oil base oil are shown in Table 4.

[0106] [Table 3]

[0107]

[0108] [Table 4]

[0109]

[0110] Referring to Comparative Experimental Example 1 and Comparative Experimental Example 2 in Table 4, the lubricating oil base oil produced in Comparative Experimental Example 1 in which the SRO reaction was not performed exhibited a higher VI than the lubricating oil base oil produced in Comparative Experimental Example 2 in which the SRO reaction was performed in the presence of the catalyst of Sample 3. It can be seen that the pour point of the lubricating oil base oil produced in Comparative Experimental Example 2 was lower. Since the catalyst of Sample 3 has fewer pores having a large pore diameter of 10 nm or more, it seems that the catalyst cannot promote the ring-opening reaction of bulky polycyclic hydrocarbon compounds. On the contrary, in view of the results of Comparative Experimental Example 2, it is considered that the catalyst of Sample 3 promotes the cracking reaction of oil.

[0111] On the other hand, it can be seen from the results of Experimental Example 1 and Experimental Example 2 that the VI is increased compared to Comparative Experimental Example 1 since the SRO reaction was performed in the presence of the catalyst of Sample 2. In view of the results of the pore diameter distribution in Figure 3 In view of the results of the pore diameter distribution in Table 1, it is considered that since the proportion of the pore volume of the pores having a pore diameter of 10 nm or more with respect to the total pore volume of the catalyst of Sample 2 is 20% or more in the case of the catalyst of Sample 2, the catalyst promotes the ring-opening reaction of ring hydrocarbon compounds having two or more rings.

[0112] 4. Comparison of the composition between the produced lubricating oil base oils

[0113] The composition of each of the lubricating oil base oils prepared in Comparative Experimental Example 1 and Experimental Example 1 was analyzed, respectively. The results of the analysis are shown in Table 5 below.

[0114] [Table 5]

[0115] Comparative experimental example 1 Experimental example 1 VI 120 129 Isoparaffins 58.9 wt% 62.2 wt% 1 -ring naphthenes 30.9 wt% 29.7 wt% 2-ring naphthenes 6.2 wt% 4.9 wt% 2-ring naphthenes 2.6 wt% 2.4 wt% More than 4-ring naphthenes 1.3 wt% 0.9 wt%

[0116] Referring to Table 5 above, it can be seen that the cycloparaffin content in the lubricating oil base oil decreases and the isoparaffin content increases through the SRO reaction. In particular, the cycloparaffin compounds having two or more rings have a significant effect on VI improvement even if the amount of these compounds is slightly reduced. Therefore, it can be expected that the SRO reaction using the catalyst of the present disclosure will be very advantageous in improving the VI of the lubricating oil base oil.

[0117] 5. Discussion of catalyst activity change over time

[0118] The same feed as in Experimental Example 1 was sequentially introduced into the HDW reaction, the SRO reaction, and the HDF reaction to prepare a lubricating oil base oil over 10 days. The catalysts of Sample 1 and Sample 2 were used as catalysts for the SRO reaction. The kinematic viscosity of each of the prepared lubricating oil base oils was measured every other day starting from the 2nd day. The results are shown in Table 6 below. Figure 4 .

[0119] Referring to Table 6 above, when the catalyst of Sample 2 was used, the kinematic viscosity gradually increased as the number of processing days increased, and thus the VI value decreased (KV at 40°C = 17.80 cSt, KV at 100°C = 4.011 cSt, VI = 127, KV at 40°C = 19.43 cSt, KV at 100°C = 4.228 cSt, and VI = 124). Figure 4

[0120] On the other hand, when the catalyst of Sample 1 was used, it can be seen that the kinematic viscosity and the VI were maintained regardless of the number of processing days (in the case of using the catalyst of Sample 1, for the reaction products on the 2nd day and the 10th day, KV at 40°C = 18.40 cSt, KV at 100°C = 4.123 cSt, VI = 128).

[0121] The above results indicate that the metal in the catalyst also has the effect of inhibiting the deactivation of the ring-opening reaction catalyst.

[0122] All modifications and alterations of this disclosure are intended to be included within the scope of this disclosure, and the specific protection granted by the claims is not to be construed as limited to the specific embodiments disclosed by the disclosure.​

Claims

1. A catalyst for selective ring-opening reactions, said catalyst comprising: Solid acidic substances; and Metal, The solid acidic substance comprises a first solid acidic substance and a second solid acidic substance. The pore size of the first solid acidic substance is less than 1 nm, and The second solid acidic substance has a pore size greater than 1 nm. The first solid acidic substance includes crystalline aluminosilicates, silica-alumina-phosphates, aluminum phosphates, metal-organic frameworks, or combinations thereof. The second solid acidic substance includes silicon dioxide-alumina, clay, zirconium sulfate, zirconium oxide, titanium dioxide, niobium oxide, aluminum oxide, silicon dioxide, or combinations thereof. The metal in question is a Group VIII metal. Of these, more than 50% of the pore volume of the catalyst has a pore diameter of more than 100 nm.

2. The catalyst according to claim 1, wherein the silica-alumina is amorphous silica-alumina, the silica-alumina-phosphate is SAPO, and the aluminum phosphate is AlPO.

3. The catalyst according to claim 1, wherein the crystalline aluminosilicate comprises zeolite.

4. The catalyst according to claim 1, wherein the second solid acidic substance is clay.

5. The catalyst according to claim 1, wherein the metal is Pt, Pd, Ru, Ir, Ni, Co, Fe, or a combination thereof.

6. The catalyst according to claim 1, wherein the amount of the metal contained in the catalyst is from 0.05% by weight to 5% by weight relative to the total weight of the catalyst.

7. The catalyst according to claim 2, wherein the catalyst further comprises a non-acidic binder.

8. The catalyst according to claim 7, wherein, relative to 100 parts by weight of the second solid acidic substance, the catalyst comprises 10 to 100 parts by weight of the first solid acidic substance and 10 to 100 parts by weight of the non-acidic binder.

9. The catalyst according to claim 1, wherein the catalyst further comprises a promoter, and the promoter comprises an alkali metal, an alkaline earth metal, a Group VB metal, a Group VIB metal, Sn, or a combination thereof.

10. A method for improving the viscosity index of a lubricating oil base oil, the method comprising: The reactants undergo a selective ring-opening reaction in the presence of the catalyst according to claim 1.

11. The method of claim 10, wherein the reactant comprises: Feed material used to prepare lubricating oil base oil; Intermediate oil in the preparation process of lubricating oil base oil; or Lubricating oil base oil.

12. The method of claim 10, wherein the selective ring-opening reaction is carried out in the presence of hydrogen within a temperature range of 100°C to 450°C.

13. A method for preparing a lubricating oil base oil, the method comprising: a) Prepare for material feeding; b) Introducing the feed into either a hydrodewaxing reaction or a selective ring-opening reaction; c) Introduce the reaction product of step b) into the remaining component of the hydrodewaxing reaction and the selective ring-opening reaction. The selective ring-opening reaction is carried out in the presence of the catalyst according to claim 1.

14. The method according to claim 13, further comprising d) introducing the reaction product of step c) into the hydrorefining reaction.

15. The method of claim 13, wherein the viscosity index of the lubricating oil base oil prepared by the method of claim 13 or 14 is at least 5 higher than the viscosity index of the lubricating oil base oil prepared by a method without selective ring-opening reaction.

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