A molecular sieve composition, a method for preparing the same, and use thereof

Abstract

The present application relates to a molecular sieve composition, a preparation method thereof and application thereof. The molecular sieve composition of the present application comprises a mosaic molecular sieve of a TON structure molecular sieve and a 5A type molecular sieve. The molecular sieve composition of the present application has a dual function of adsorption and hydroisomerization.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, and relates to a molecular sieve composition, its preparation method and its application. Background Technology

[0002] With increasingly stringent environmental regulations and the rapid development of the machinery industry, higher and higher requirements are being placed on the performance of lubricating oil base oils. Traditional lubricating oil base oil production employs a solvent refining process, which mainly involves two steps: solvent refining to remove non-ideal components such as aromatics, and solvent dewaxing to ensure the low-temperature flow properties of the base oil. In addition, supplementary refining with clay or hydrotreating is generally required.

[0003] Currently, the global crude oil market is experiencing a general trend towards lower quality, leading to a gradual decrease in the amount of crude oil suitable for lubricant production. Furthermore, traditional processes are hampered by high energy consumption and heavy pollution, limiting their development and application. In recent years, the hydrotreating process for producing lubricant base oils has developed rapidly. The hydrotreating process refers to the method of producing lubricant base oils using hydrocracking or a combined process of hydrotreating-isomerization dewaxing-hydrorefining. It offers advantages such as greater feedstock flexibility, higher base oil yield, and higher economic value of byproducts.

[0004] Currently, a technical problem in the hydroisomerization dewaxing process is that when using full-range or wide-range feedstocks, it is difficult to simultaneously ensure that both light and heavy lubricating oil components meet the requirements for pour point and viscosity index. Generally, to achieve a suitable pour point for the heavy lubricating oil component, excessive isomerization of the light lubricating oil component is performed, resulting in a loss of viscosity index and making it difficult to produce API Group III light base oil products with a viscosity index higher than 120.

[0005] In existing methods for preparing high viscosity index lubricating oil base oils, some processes involve cutting the raw material into narrow fractions and then using these narrow fractions as feedstocks for hydroisomerization dewaxing, thus addressing the issue of producing high viscosity index light lubricating oil base oils. Other methods utilize full-range or wide-range feedstocks, employing a stepwise isomerization dewaxing-product separation method to produce high viscosity index lubricating oil base oils.

[0006] US7,198,710 discloses a method for producing high viscosity index lubricating oil base oil from Fischer-Tropsch wax. First, the Fischer-Tropsch wax is fractionated to obtain light and heavy components. Then, hydroisomerization dewaxing is performed on each component to lower its pour point, resulting in a light lubricating oil base oil with a pour point that meets the requirements. Since the heavy component does not meet the pour point requirements after hydroisomerization dewaxing, solvent dewaxing is used to further lower the pour point of the heavy component, finally yielding a heavy lubricating oil base oil product with a pour point that meets the requirements.

[0007] CN102911726A discloses a method for producing high viscosity index lubricating oil base oil. The method uses waxy oil that does not require pre-fractionation as feed for hydroisomerization dewaxing. The oil first enters the first hydroisomerization dewaxing reaction zone to complete a hydroisomerization reaction of appropriate depth. The reaction products are then fractionated to obtain a light lubricating oil base oil product with a high viscosity index and a pour point that meets the requirements, as well as a heavy base oil component with a relatively high pour point. The heavy base oil component continues to enter the second hydroisomerization dewaxing reaction zone, where the reaction products are fractionated to obtain a heavy lubricating oil base oil product with a high viscosity index and a pour point that meets the requirements. Summary of the Invention

[0008] During their research, the inventors of this invention discovered that long-chain isoalkanes and long-side-chain monocyclic cycloalkanes are ideal components for high viscosity index lubricating oil base oils. Besides Fischer-Tropsch synthetic oils (FT oils) and polyesters, raw materials for producing lubricating oil base oils from natural petroleum products, such as hydrocracking tail oils, hydrotreated wax oils, hydrorefined wax residues, and hydrorefined wax pastes, generally contain not only long-chain isoalkanes, long-side-chain monocyclic cycloalkanes, and long-chain monocyclic aromatics, but also a certain amount of non-ideal components such as bicyclic or multicyclic cycloalkanes and aromatics. These non-ideal components cannot be converted into high viscosity index components during isomerization dewaxing and pour point depressing, and their presence severely restricts the improvement of the viscosity index of the isomerization dewaxing product-lubricating oil base oil. The inventors propose that if these non-ideal components in the raw materials can be removed beforehand, without subsequent isomerization dewaxing treatment, the viscosity index of the isomerization dewaxing product-lubricating oil base oil can be improved, and the hydrogen consumption in the isomerization dewaxing process can be significantly reduced, lowering equipment operation and production costs. This invention is based on the above-mentioned findings.

[0009] To address the aforementioned problems and shortcomings in the existing technology, the main objective of this invention is to provide a method and system for producing lubricating oil base oil. First, a selective adsorption process is used to separate non-ideal components such as low-viscosity-index bicyclic or higher cycloalkanes and some aromatics from the lubricating oil base oil raw material. Then, the pretreated raw material, rich in long-chain isoalkanes, long-side-chain monocyclic cycloalkanes, and long-chain monocyclic aromatics, undergoes an isomerization and pour point depressant reaction to generate a high-viscosity-index lubricating oil base oil product.

[0010] To achieve the above-mentioned objectives, the first aspect of the present invention provides a molecular sieve composition comprising an embedded molecular sieve of TON structure molecular sieve and 5A type molecular sieve.

[0011] Technical effect

[0012] Compared with the prior art, the present invention has the following advantages:

[0013] 1. The molecular sieve composition provided by this invention is composed of 5A-type molecular sieves and TON-structured molecular sieves interlocked. The 5A-type molecular sieve possesses excellent adsorption capabilities and can enrich alkanes, while the TON-structured molecular sieve has a specific pore structure and suitable acidity, which is beneficial for the selective isomerization of alkanes. The molecular sieve composition provided by this invention combines both of these specific functions and maintains good adsorption performance even after loading with active metals. Catalysts prepared using the molecular sieve composition provided by this invention, after isomerization and regeneration, still maintain good stability.

[0014] 2. In the lubricating oil base oil production method provided by this invention, non-ideal components are separated by pre-adsorption treatment of the raw materials. This ensures that only raw materials rich in ideal components such as long-chain isoalkanes, long-side-chain monocyclic cycloalkanes, and long-chain monocyclic aromatics undergo isomerization and pour point depletion reactions, thereby generating high viscosity index lubricating oil base oil products. This significantly reduces the participation of non-ideal components in the hydrogenation reaction, thus reducing the isomerization and pour point depletion processing load, decreasing hydrogen consumption, and improving the economic efficiency of the equipment. Furthermore, the applicant discovered during the research process that adding 5A type molecular sieves to the currently used hydroisomerization dewaxing catalyst has a selective adsorption effect on the raw materials of lubricating oil base oil under the condition of no hydrogen presence. This can separate low viscosity index non-ideal components such as two-ring or higher cycloalkanes and some aromatics from the raw materials, thereby reducing the content of low viscosity index components in the lubricating oil base oil products and increasing the viscosity index of the lubricating oil base oil products.

[0015] 3. In the lubricating oil base oil production method provided by the present invention, the molecular sieve composition has the ability to selectively adsorb long-chain isomeric alkanes, long-side-chain monocyclic cycloalkanes and long-chain monocyclic aromatics, as well as the ability to selectively isomerize alkanes in the presence of hydrogen and under suitable reaction conditions. This simplifies the production process of high viscosity index lubricating oil base oil, reduces equipment investment, and lowers process hydrogen consumption.

[0016] 4. In the lubricating oil base oil production method provided by the present invention, the adsorption separation efficiency is characterized by the change in the refractive index of the raw material before and after adsorption treatment. This parameter is simple and convenient to measure and can intuitively reflect the separation effect of ideal components such as long-chain isoalkanes, long-side-chain monocyclic cycloalkanes and long-chain monocyclic aromatics in the raw material.

[0017] 5. Compared with mechanical mixtures of TON-structured molecular sieves and 5A-type molecular sieves, the embedded molecular sieves formed by interlocking are more tightly bound, which can significantly shorten the diffusion distance of n-alkanes from the 5A-type molecular sieve with adsorption function to the TON-structured molecular sieve with isomerization function, and have a significant adsorption-catalytic synergistic effect. Attached Figure Description

[0018] Figure 1 This is a schematic flowchart of the lubricating oil base oil production method according to the first embodiment of the present invention.

[0019] Figure 2 This is a schematic flowchart of a lubricating oil base oil production method according to the second embodiment of the present invention.

[0020] Figure 3 The image shows the XRD pattern of the mosaic molecular sieve obtained in Example 2.

[0021] Figure 4a and Figure 4b SEM images of the embedded molecular sieves obtained in Examples 2 and 3 are shown. In these images, the cubes are type 5A molecular sieves, while the short rod-shaped crystals are TON-structured molecular sieves. These images show that the short rod-shaped TON-structured molecular sieves are embedded on the surface of the type 5A molecular sieve cubes by covering at least a portion of the surface. Detailed Implementation

[0022] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0023] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0024] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0025] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0026] In this document, for ease of description, spatial relative terms such as “below,” “under,” “down,” “above,” “above,” “up,” etc., are used to describe the relationship of one element or feature to another element or feature in the accompanying drawings. It should be understood that spatial relative terms are intended to encompass different orientations of an object in use or operation, in addition to those depicted in the figures. For example, if an object in the figure is flipped, an element described as “below” or “under” another element or feature would be oriented “above” that element or feature. Thus, the exemplary term “below” can encompass both the downward and upward orientations. An object may also have other orientations (rotated 90 degrees or other orientations), and the spatial relative terms used herein should be interpreted accordingly.

[0027] In this document, the terms "first," "second," etc., are used to distinguish two different elements or parts, and are not used to define specific positions or relative relationships. In other words, in some embodiments, the terms "first," "second," etc., can also be used interchangeably.

[0028] In this document, all numeric values ​​of parameters (e.g., quantity or condition) should be understood to be modified by the term “about” in all cases, regardless of whether “about” actually appears before the numeric value.

[0029] In the context of this specification, unless explicitly stated otherwise, both the silicon-aluminum material and the catalyst undergo calcination treatment, sometimes referred to as "calcination form," prior to measurement. The conditions for this calcination treatment include: calcination at 600°C in an air atmosphere for a calcination time of 3 hours or more.

[0030] In the context of this specification, long side-chain hydrocarbons specifically refer to one or more of long side-chain isoalkanes, long side-chain monocyclic cycloalkanes, and long side-chain monocyclic aromatics, excluding other hydrocarbons with long side chains. Furthermore, according to the present invention, a long side chain refers to a straight-chain alkyl group of C8-22 (preferably C10-18) as the side chain.

[0031] In the context of this specification, a mechanical mixture refers to a mixture of two or more materials obtained by mechanical mixing. Here, mechanical mixing includes simple mixing, grinding, pulping, etc.

[0032] In the context of this specification, an embedded molecular sieve refers to a composite crystal in which one or more molecular sieve crystals are embedded on or within their surface, exhibiting structural characteristics of two or more molecular sieves. Compared to mechanical mixtures, the different molecular sieves are more tightly bound in an embedded structure, truly forming an integrated composite structure at the molecular level.

[0033] In the context of this specification, the refractive index was characterized using a Mettler R5 refractometer, the long-chain hydrocarbon content was characterized using an Agilent GC 7890, the XRD patterns of the samples were characterized using a D / max-2500 fully automated rotating target X-ray diffractometer, the specific surface area, pore volume, and average pore size of the embedded molecular sieves and the specific surface area, pore volume, and average pore size of the molecular sieve compositions were characterized using an ASAP 2405 physical adsorption instrument via N2 adsorption-desorption, and the calcium content of the calcium-type molecular sieves was characterized using X-ray fluorescence diffraction.

[0034] In the context of this specification, the content of TON structured molecular sieves in the embedded molecular sieves is quantitatively analyzed by XRD determination.

[0035] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, pressure is gauge pressure, and weight or content is on a dry basis.

[0036] In the context of this specification, any two or more embodiments of the present invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0037] According to one embodiment of the present invention, a molecular sieve composition comprising an embedded molecular sieve of a TON-structured molecular sieve and a 5A-type molecular sieve is provided. Preferably, the TON-structured molecular sieve is embedded on at least a portion of the surface of the 5A-type molecular sieve with a predetermined surface coverage ratio. From the perspective of achieving the technical effects of the present invention, a suitable surface coverage ratio may be 0.5% or more, or 1% or more, and less than 50% or less, or less than 20%, but the present invention is not limited thereto.

[0038] According to one embodiment of the present invention, the calcination form of the embedded molecular sieve has an XRD pattern substantially as shown in Table I or Table II below.

[0039] Table I

[0040]

[0041] Table II

[0042]

[0043] According to the present invention, if the intensity value of the strongest diffraction peak in the XRD pattern is 100, then W = weak, that is, relative intensity >0 to ≤20; M = moderate, that is, relative intensity >20 to ≤40; S = strong, that is, relative intensity >40 to ≤60; VS = very strong, that is, relative intensity >60 to ≤100.

[0044] According to one embodiment of the present invention, the calcination form of the embedded molecular sieve has substantially the following characteristics: Figure 1 The XRD pattern shown.

[0045] According to one embodiment of the present invention, the specific surface area of ​​the embedded molecular sieve is 300 m². 2 / g-600m 2 / g, pore volume 0.15cm 3 / g-0.40cm 3 / g.

[0046] According to one embodiment of the present invention, the specific surface area of ​​the molecular sieve composition is 200 m². 2 / g-550m 2 / g, pore volume 0.25cm 3 / g-0.60cm 3 / g.

[0047] According to one embodiment of the present invention, from the perspective of obtaining a suitable surface coverage, in the embedded molecular sieve, the weight ratio of the 5A type molecular sieve to the TON structure molecular sieve is 1:80-3:1, preferably 1:30-1:1.

[0048] According to one embodiment of the present invention, the content of the TON structure molecular sieve is 10wt%-80wt%, preferably 20wt%-60wt%, and the content of the 5A type molecular sieve is 1wt%-50wt%, preferably 2wt%-20wt%, based on a total weight of 100wt% of the molecular sieve composition.

[0049] According to one embodiment of the present invention, the content of the embedded molecular sieve is 10wt%-90wt%, preferably 20wt%-70wt%, based on a total weight of 100wt% of the molecular sieve composition.

[0050] According to one embodiment of the present invention, the molecular sieve composition further includes inorganic refractory oxides and active metal components.

[0051] According to one embodiment of the present invention, the active metal component has a content of 0.05wt%-5.0wt% based on the metal element, preferably 0.1wt%-1.0wt%, relative to the total weight of the molecular sieve composition of 100wt%.

[0052] According to one embodiment of the present invention, the inorganic refractory oxide is selected from one or more of alumina, titanium oxide, boron oxide, silicon oxide, zirconium oxide and magnesium oxide, preferably alumina.

[0053] According to one embodiment of the present invention, the active metal component is selected from at least one of the noble metals of Group VIII of the periodic table, preferably from at least one of Pt and Pd, especially Pt.

[0054] According to one embodiment of the present invention, the TON structure molecule is selected from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10, preferably ZSM-22.

[0055] According to one embodiment of the present invention, the 5A molecular sieve is derived from 5A molecular sieve.

[0056] According to one embodiment of the present invention, the molecular sieve composition has dual functions of adsorption and hydroisomerization, and can selectively enrich long side-chain hydrocarbons, and then further hydroisomerize them to avoid the occurrence of excessive isomerization.

[0057] According to one embodiment of the present invention, a method for preparing an embedded molecular sieve is provided, which can be used to manufacture an embedded molecular sieve of the TON structure molecular sieve and the 5A type molecular sieve described above in this specification.

[0058] According to one embodiment of the present invention, the method for preparing the embedded molecular sieve includes the following steps:

[0059] (1) A gel mixture is obtained by contacting a silicon source, an aluminum source, and an alkali source in the presence of a template agent, a TON-structured molecular sieve, and water.

[0060] (2) The gel mixture is subjected to hydrothermal crystallization, then washed, dried and calcined to obtain the first embedded molecular sieve.

[0061] According to one embodiment of the present invention, the preparation method further includes the following steps:

[0062] (3) The first embedded molecular sieve is subjected to calcium exchange, and then washed, dried and calcined to obtain the second embedded molecular sieve.

[0063] According to one embodiment of the present invention, in step (1), the silicon source is selected from at least one of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.

[0064] According to one embodiment of the present invention, in step (1), the alkali source is selected from at least one of alkali metal hydroxides, preferably sodium hydroxide.

[0065] According to one embodiment of the present invention, in step (1), the aluminum source is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate, aluminum hydroxide, aluminum oxide, and boehmite.

[0066] According to one embodiment of the present invention, in step (1), the template agent is selected from at least one of polyethylene oxide triblock copolymer (P123) and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC).

[0067] According to one embodiment of the present invention, in step (1), the TON structure molecule is selected from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10, preferably ZSM-22.

[0068] According to one embodiment of the present invention, in step (1), the operating conditions for contact include: a temperature of 15°C-30°C and a time of 1h-4h in the presence of stirring.

[0069] According to one embodiment of the present invention, in step (1), the molar ratio of the alkali source (calculated as oxide), the silicon source (calculated as SiO2), the aluminum source (calculated as Al2O3), the template agent and water is (0.5-2.5):1:(0.4-0.7):(0.001-0.08):(30-200), and the amount of the TON structure molecular sieve is 0.3-8 times, preferably 1-7 times, the amount of silicon source added.

[0070] According to one embodiment of the present invention, in step (2), the hydrothermal crystallization temperature is 60℃-120℃ and the crystallization time is 2h-16h.

[0071] According to one embodiment of the present invention, in step (2), the drying temperature is 80℃-200℃ and the drying time is 2h-24h.

[0072] According to one embodiment of the present invention, in step (2), the calcination temperature is 400℃-600℃ and the calcination time is 2h-12h.

[0073] According to one embodiment of the present invention, in step (3), the operating conditions for calcium exchange include: an exchange temperature of 60℃-100℃, an exchange time of 1h-12h, and a calcium ion concentration in the calcium exchange solution of 0.1mol / L-2.5mol / L.

[0074] According to one embodiment of the present invention, in step (3), the drying temperature is 80℃-150℃ and the drying time is 2h-12h.

[0075] According to one embodiment of the present invention, in step (3), the calcination temperature is 300℃-500℃ and the calcination time is 2h-8h.

[0076] According to one embodiment of the present invention, a method for producing a lubricating oil base oil is also disclosed, which uses the molecular sieve composition described above in this specification.

[0077] According to one embodiment of the present invention, the method for producing the lubricating oil base oil includes the following steps:

[0078] (1) The raw material containing long side-chain hydrocarbons is contacted with the molecular sieve composition described above in this specification, for example, in the presence or absence of hydrogen, to obtain a residual liquid with adsorbed molecular sieve composition and reduced content of long side-chain hydrocarbons.

[0079] (2) The adsorbed molecular sieve composition is treated under hydroisomerization reaction conditions to obtain an isomerization product mixture and a desorbed molecular sieve composition, and

[0080] (3) Separate the mixture of isomerized products to obtain the lubricating oil base oil.

[0081] According to one embodiment of the present invention, the raw material is repeatedly contacted with the molecular sieve composition multiple times until the refractive index of the residual liquid is 0.1%-5% higher than that of the raw material, preferably 0.5-2.5% higher.

[0082] According to one embodiment of the present invention, the residual liquid can be further processed or used as white oil.

[0083] According to one embodiment of the present invention, step (1) can be performed in one or more reaction zones (e.g., including a first reaction zone and a second reaction zone, etc.), and step (2) can be performed in one or more reaction zones (e.g., including a first reaction zone and a second reaction zone, etc.). Preferably, steps (1) and (2) are performed in the same reaction zone.

[0084] According to one embodiment of the present invention, and more specifically, the method for producing the lubricating oil base oil of the first embodiment includes:

[0085] (1) The raw material enters the first reaction zone, which is filled with the molecular sieve composition. The first material stream obtained after processing is returned to the first reaction zone for recycling.

[0086] (2) When the refractive index (20℃) of the first material stream is 0.1-5% higher than the refractive index (20℃) of the raw material, stop the raw material and the first material stream from entering the first reaction zone;

[0087] (3) Introduce hydrogen into the first reaction zone, so that the adsorbate undergoes an isomerization decondensation reaction under the action of the molecular sieve composition and hydrogen. The reaction product is separated to obtain the lubricating oil base oil product.

[0088] The second embodiment of the method for producing lubricating oil base oil includes:

[0089] (1) The raw material enters the first reaction zone, which is filled with the molecular sieve composition. The first material stream obtained after processing is returned to the first reaction zone for recycling.

[0090] (2) When the refractive index (20℃) of the first material stream is 0.1-5% higher than the refractive index (20℃) of the raw material, stop the raw material and the first material stream from entering the first reaction zone;

[0091] (3) Introduce hydrogen into the first reaction zone, so that the adsorbate undergoes an isomerization decondensation reaction under the action of the molecular sieve composition and hydrogen. The reaction product is separated to obtain the lubricating oil base oil product.

[0092] (4) The raw material is introduced into the second reaction zone, which is filled with the molecular sieve composition. The second material stream obtained after processing is returned to the second reaction zone for recycling.

[0093] (5) When the refractive index (20°C) of the second material stream is 0.1-5% higher than that of the raw material (20°C), stop the raw material and the second material stream from entering the second reaction zone;

[0094] (6) Introduce hydrogen into the second reaction zone to cause the adsorbate to undergo isomerization and decondensation reaction under the action of the molecular sieve composition and hydrogen. The reaction product is separated to obtain the lubricating oil base oil product.

[0095] (7) Reintroduce the raw materials into the first reaction zone and repeat steps (1) to (6).

[0096] According to one embodiment of the present invention, the first reaction zone and the second reaction zone can be connected in parallel and switched according to the actual production process requirements. The first reaction zone can be equipped with one or more reactors, which can be one or more of existing fixed-bed hydrogenation reactors, fluidized-bed hydrogenation reactors, and slurry-bed hydrogenation reactors, preferably a fixed-bed hydrogenation reactor. The second reaction zone can be equipped with one or more reactors, which can be one or more of existing fixed-bed hydrogenation reactors, fluidized-bed hydrogenation reactors, and slurry-bed hydrogenation reactors, preferably a fixed-bed hydrogenation reactor.

[0097] According to one embodiment of the present invention, the molecular sieve compositions used in the first reaction zone and the second reaction zone may be the same or different, preferably the same.

[0098] According to one embodiment of the present invention, the raw material is selected from one or more of hydrocracking tail oil, hydrotreated wax oil, hydrotreated bright oil, hydrotreated wax paste, and hydrotreated wax residue.

[0099] According to one embodiment of the present invention, in step (1), through the contact, the molecular sieve composition selectively adsorbs long-chain hydrocarbons from the raw material. The long-chain hydrocarbons are selectively adsorbed within the pores of the molecular sieve composition. The raw material undergoes cyclic adsorption, resulting in the continuous accumulation of long-chain hydrocarbons on the molecular sieve composition, thereby obtaining a molecular sieve composition adsorbed with long-chain hydrocarbons (referred to as the adsorbed molecular sieve composition) and the residual liquid. The contact is carried out under conditions where hydrogen is absent. Here, "absence of hydrogen" means that no hydrogen is actively or intentionally introduced or added to the contact reaction system.

[0100] According to one embodiment of the present invention, in step (1), the operating conditions for contact include: a temperature of 40°C-250°C, preferably 60°C-200°C; a pressure of 0.01 MPa-0.5 MPa, preferably 0.08-0.1 MPa; and a volume hourly space velocity of 0.05 h⁻¹. -1 -5.0h -1 Preferably 0.1h -1 -2.0h -1 .

[0101] According to one embodiment of the present invention, in step (2), the operating conditions of the hydroisomerization reaction include: in the presence of hydrogen, the reaction temperature is 200-420°C, preferably 270-380°C, the hydrogen partial pressure is 1.0-20.0 MPa, preferably 3.0-15.0 MPa, the reaction time is 0.1h-10h, preferably 0.3h-2h, and the hydrogen-to-oil volume ratio is 100:1-1500:1, preferably 100:1-400:1.

[0102] According to one embodiment of the present invention, in step (3), the separation process includes the following steps:

[0103] (3-1) The isomerization product mixture is subjected to gas-liquid separation to obtain a gas stream and a liquid stream, optionally recycling at least a portion of the gas stream as at least a portion of the raw material back to step (1), and

[0104] (3-2) Fractionate the liquid phase stream to obtain the lubricating oil base oil, preferably light lubricating oil base oil, medium lubricating oil base oil and heavy lubricating oil base oil, optionally recycling at least a portion of the heavy lubricating oil base oil as at least a portion of the raw material back to step (1).

[0105] According to one embodiment of the present invention, in step (3-1), the gas-liquid separation operation is achieved by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 1-100 mmHg, preferably 2-20 mmHg, and the temperature at the bottom of the distillation column is 200℃-370℃, preferably 290℃-350℃.

[0106] According to one embodiment of the present invention, in step (3-2), the fractionation operation is carried out by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 1-100 mmHg, preferably 2-20 mmHg, and the temperature at the bottom of the distillation column is 200℃-370℃, preferably 290℃-350℃.

[0107] According to one embodiment of the present invention, a production system for lubricating oil base oil is also disclosed, comprising:

[0108] One or more reaction zones (e.g., including a first reaction zone and a second reaction zone, etc.) are filled with the molecular sieve composition described above in this specification and are configured to contact a feedstock containing long-chain hydrocarbons with the molecular sieve composition described above in this specification to obtain an adsorbed molecular sieve composition and a residual liquid with reduced long-chain hydrocarbon content. The adsorbed molecular sieve composition is then treated under hydroisomerization reaction conditions to obtain a mixture of isomerized products and a desorbed molecular sieve composition.

[0109] A gas-liquid separation zone is configured to perform gas-liquid separation on the isomerization product mixture to obtain a gas phase stream and a liquid phase stream.

[0110] A fractionation tower is configured to fractionate the liquid stream to obtain the lubricating oil base oil.

[0111] According to one embodiment of the present invention, more specifically, the lubricating oil base oil production system includes:

[0112] The first reaction zone is used to receive raw materials. The first reaction zone is filled with the molecular sieve composition. The raw materials undergo an adsorption reaction in the presence of the molecular sieve composition. The first material stream obtained after adsorption treatment is returned to the first reaction zone for recycling. When the refractive index (20°C) of the first material stream is 0.1-5% higher than the refractive index (20°C) of the raw materials, the entry of the raw materials and the first material stream into the first reaction zone is stopped. At the same time, hydrogen is introduced into the first reaction zone, so that the adsorbate undergoes an isomerization and decondensation reaction under the action of the molecular sieve composition and hydrogen. The reaction products are separated to obtain the lubricating oil base oil product.

[0113] The second reaction zone is used to receive raw materials when the first reaction zone stops feeding. The second reaction zone is filled with the molecular sieve composition. The raw materials undergo an adsorption reaction in the presence of the molecular sieve composition. The second material stream obtained after adsorption treatment is returned to the second reaction zone for recycling. When the refractive index (20°C) of the second material stream is 0.1-5% higher than the refractive index (20°C) of the raw materials, the raw materials and the second material stream are stopped from entering the second reaction zone, and the raw materials are switched back to enter the first reaction zone. At the same time, hydrogen is introduced into the second reaction zone, so that the adsorbate undergoes an isomerization and decondensation reaction under the action of the molecular sieve composition and hydrogen. The reaction products are separated to obtain the lubricating oil base oil product.

[0114] The gas-liquid separation zone is used to receive the isomerization decondensation reaction products from the first separation zone or the second separation zone, and separate them to obtain a gas phase stream and a liquid phase stream.

[0115] A fractionation tower is used to receive liquid feed from the gas-liquid separation zone and fractionate it to obtain light lubricating oil base oil, medium lubricating oil base oil and heavy lubricating oil base oil.

[0116] The first and second reaction zones can be connected in parallel and switched according to the actual production process requirements. The first reaction zone can contain one or more reactors, which can be one or more of existing fixed-bed hydrogenation reactors, fluidized-bed hydrogenation reactors, and slurry-bed hydrogenation reactors, with a fixed-bed hydrogenation reactor being preferred. Similarly, the second reaction zone can contain one or more reactors, which can be one or more of existing fixed-bed hydrogenation reactors, fluidized-bed hydrogenation reactors, and slurry-bed hydrogenation reactors, with a fixed-bed hydrogenation reactor being preferred.

[0117] The gas-liquid separation zone can be any of the existing devices in the art that can achieve gas-liquid two-phase separation, such as a gas-liquid separator, a flash tower, etc.

[0118] The invention will be described in further detail below with reference to the accompanying drawings, but the invention is not limited to these drawings.

[0119] like Figure 1As shown, in the first embodiment of the lubricating oil base oil production method of the present invention, the raw material 1 enters the first reaction zone 2 (at which time an adsorption reaction occurs in the first reaction zone). The raw material 1 reacts under the action of the molecular sieve composition to obtain the first feed stream 3. The first feed stream 3 is recycled back to the first reaction zone 2. When the refractive index of the first feed stream 3 is 0.1-5% higher than that of the raw material 1, the entry of the raw material 1 and the first feed stream 3 into the first reaction zone 2 is stopped. At the same time, hydrogen gas 4 is introduced into the first reaction zone 2, so that the adsorbate undergoes an isomerization and decondensation reaction under the action of the molecular sieve composition and hydrogen gas 4. The reaction product 5 enters the gas-liquid separation zone 6, where it is separated into a gas stream 13 and a liquid stream 7. The gas stream 13 is recycled back to the first reaction zone 2 for use (at this time, the isomerization and decondensation reaction occurs in the first reaction zone). The liquid stream 7 further enters the fractionation tower 8 for separation, where it is separated into light lubricating oil base oil 9, medium lubricating oil base oil 10, and heavy lubricating oil base oil. The heavy lubricating oil base oil is divided into two streams, one of which, heavy lubricating oil base oil 11, exits the unit, while the other, heavy lubricating oil base oil 12, can be recycled back to the first reaction zone 2 to continue the reaction.

[0120] like Figure 2As shown, in the second embodiment of the lubricating oil base oil production method of the present invention, the raw material 1 enters the first reaction zone 2 (at which time an adsorption reaction occurs in the first reaction zone). The raw material 1 reacts under the action of the molecular sieve composition to obtain the first feed stream 3. The first feed stream 3 is recycled back to the first reaction zone 2. When the refractive index of the first feed stream 3 is 0.1-5% higher than that of the raw material 1, the entry of the raw material 1 and the first feed stream 3 into the first reaction zone 2 is stopped. At the same time, hydrogen gas 5 is introduced into the first reaction zone 2, so that the adsorbate undergoes a reaction under the action of the molecular sieve composition and hydrogen gas 5. The isomerization decondensation reaction yields reaction product 6, which enters the gas-liquid separation zone 7. After gas-liquid separation in the gas-liquid separation zone 7, gas phase stream 15 and liquid phase stream 8 are obtained. Gas phase stream 15 is recycled back to the first reaction zone 2 for use (at this time, the isomerization decondensation reaction occurs in the first reaction zone). Liquid phase stream 8 further enters the fractionation tower 9 for separation. After separation, light lubricating oil base oil 10, medium lubricating oil base oil 11 and heavy lubricating oil base oil 12 can be obtained. Some or all of the heavy lubricating oil base oil 12 can be recycled back to the first reaction zone 2 to continue the reaction. Simultaneously, while the first reaction zone 2 switches to the isomerization-decondensation reaction mode, raw material 1 is switched to the second reaction zone 4. Under the action of the molecular sieve composition, raw material 1 reacts to obtain the second feed stream 14. The second feed stream 14 is recycled back to the second reaction zone 4. When the refractive index of the second feed stream 14 is 0.1-5% higher than that of the raw material 1, the entry of raw material 1 and the second feed stream 14 into the second reaction zone 4 is stopped. At the same time, hydrogen gas 5 is introduced into the second reaction zone 4, causing the adsorbate to undergo an isomerization-decondensation reaction under the action of the molecular sieve composition and hydrogen gas 5. The reaction product 13 is obtained and enters the gas-liquid separation zone 7. After gas-liquid separation in the gas-liquid separation zone 7, gas phase stream 15 and liquid phase stream 8 are obtained. Gas phase stream 15 is recycled back to the first reaction zone 2 for use (at this time, isomerization and decondensation reaction occurs in the first reaction zone). Liquid phase stream 8 further enters the fractionation tower 9 for separation. After separation, light lubricating oil base oil 10, medium lubricating oil base oil 11 and heavy lubricating oil base oil 12 can be obtained. Some or all of the heavy lubricating oil base oil 12 can be recycled back to the second reaction zone 4 to continue the reaction. Example

[0121] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0122] In the following examples and comparative examples, all the pharmaceuticals and raw materials are either commercially available or manufactured based on existing knowledge.

[0123] Example 1

[0124] 48g sodium hydroxide, 208g tetraethyl orthosilicate, 73.8g sodium aluminate, 3.97g dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), and 720g water were mixed evenly and placed into a crystallization vessel. Then, 36g of ZSM-22 molecular sieve was added and stirred. The vessel was sealed, and hydrothermal crystallization was carried out at 120℃ for 3 hours. After crystallization, the crystallized product was washed, dried at 110℃ for 5 hours, and then calcined at 500℃ for 4 hours to obtain the first embedded molecular sieve Z1. Molecular sieve Z1 was then subjected to ion exchange in a 0.8mol / L CaCl2 solution at 65℃ for 6 hours, filtered and washed, dried at 100℃ for 4 hours, and then calcined at 450℃ for 3 hours to obtain the second embedded molecular sieve GZ-1, with a specific surface area of ​​584 m². 2 / g, pore volume is 0.22mL / g, and the mass fraction of TON structured molecular sieve is 85%.

[0125] 210g of the above-prepared embedded molecular sieve GZ-1 was thoroughly mixed with 90g of pseudoboehmite (dry basis) and 20g of guar gum powder. 9ml of concentrated nitric acid (65% by mass) and an appropriate amount of water were added, and the mixture was thoroughly kneaded and then extruded into strips. The shaped support was dried at 100℃ for 4h and calcined at 550℃ for 4h to obtain support ES-1. Then, noble metal Pt was impregnated using a saturated impregnation method, with a Pt loading of 0.28wt% of the support. After drying at 100℃ for 6h and calcining at 500℃ for 3h, the catalyst of this invention, designated E-1, was obtained.

[0126] Example 2

[0127] 128g sodium hydroxide, 208g tetraethyl orthosilicate, 82g sodium aluminate, 14.88g dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), and 1800g water were mixed evenly and placed into a crystallization vessel. Then, 300g of ZSM-22 molecular sieve was added and stirred. The vessel was sealed, and the temperature was raised to 110℃ for hydrothermal crystallization for 6 hours. After crystallization, the crystallized product was washed, dried at 110℃ for 6 hours, and then calcined at 500℃ for 5 hours to obtain the first embedded molecular sieve Z2. Molecular sieve Z2 was then subjected to ion exchange in a 1.8mol / L CaCl2 solution at 90℃ for 4 hours, filtered and washed, dried at 100℃ for 4 hours, and then calcined at 400℃ for 3 hours to obtain the second embedded molecular sieve GZ-2, with a specific surface area of ​​452 m². 2 / g, pore volume is 0.25mL / g, and the mass fraction of TON structured molecular sieve is 85%.

[0128] The preparation process of catalyst E-2 of the present invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-2, the Pt loading is 0.50 wt% of the support, and the catalyst prepared is numbered E-2.

[0129] Example 3

[0130] 80g sodium hydroxide, 184g sodium silicate, 65.6g sodium aluminate, 4.96g dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), and 540g water were mixed evenly and placed into a crystallization vessel. Then, 42g of ZSM-22 molecular sieve was added and stirred. The vessel was sealed, and hydrothermal crystallization was carried out at 120℃ for 5 hours. After crystallization, the crystallized product was washed, dried at 120℃ for 5 hours, and then calcined at 500℃ for 4 hours to obtain the first embedded molecular sieve Z3. Molecular sieve Z3 was then subjected to ion exchange in a 1.2mol / L CaCl2 solution at 70℃ for 6 hours, filtered and washed, dried at 100℃ for 4 hours, and then calcined at 450℃ for 3 hours to obtain the second embedded molecular sieve GZ-3, with a specific surface area of ​​573 m². 2 / g, pore volume is 0.19mL / g, and the mass fraction of TON structured molecular sieve is 47%.

[0131] The preparation process of catalyst E-3 of the present invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-3, the Pt loading is 0.31 wt% of the support, and the catalyst prepared is numbered E-3.

[0132] Example 4

[0133] 200g sodium hydroxide, 208g tetraethyl orthosilicate, 98.4g sodium aluminate, 39.68g dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), and 3600g water were mixed evenly and placed into a crystallization vessel. Then, 420g of ZSM-22 molecular sieve was added and stirred. The vessel was sealed, and hydrothermal crystallization was carried out at 100℃ for 8 hours. After crystallization, the crystallized product was washed, dried at 100℃ for 8 hours, and then calcined at 500℃ for 3 hours to obtain the first embedded molecular sieve Z4. Molecular sieve Z4 was then subjected to ion exchange in a 2.1mol / L CaCl2 solution at 100℃ for 2 hours, filtered and washed, dried at 100℃ for 3 hours, and then calcined at 500℃ for 3 hours to obtain the second embedded molecular sieve GZ-4, with a specific surface area of ​​387 m². 2 / g, pore volume is 0.33mL / g, and the mass fraction of TON structured molecular sieve is 89%.

[0134] The preparation process of catalyst E-4 of the present invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-4, the Pt loading is 0.47 wt% of the support, and the catalyst prepared is numbered E-4.

[0135] Example 5

[0136] 40g sodium hydroxide, 208g tetraethyl orthosilicate, 285.6g aluminum isopropoxide, 5.75g polyethylene oxide triblock copolymer (P123), and 1440g water were mixed evenly and placed into a crystallization reactor. Then, 60g of KZ-2 molecular sieve was added and stirred. The reactor was sealed, and the temperature was raised to 90℃ for hydrothermal crystallization for 10 hours. After crystallization, the crystallized product was washed, dried at 110℃ for 6 hours, and then calcined at 450℃ for 8 hours to obtain the first embedded molecular sieve Z5. Molecular sieve Z5 was then subjected to ion exchange in a 1.0mol / L CaCl2 solution at 60℃ for 8 hours, filtered and washed, dried at 100℃ for 4 hours, and then calcined at 300℃ for 8 hours to obtain the second embedded molecular sieve GZ-5, with a specific surface area of ​​531 m². 2 / g, pore volume is 0.21mL / g, and the mass fraction of TON structured molecular sieve is 53%.

[0137] The preparation process of catalyst E-5 of the present invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-5, the Pt loading is 0.33 wt% of the support, and the catalyst prepared is numbered E-5.

[0138] Example 6

[0139] 64g sodium hydroxide, 208g tetraethyl orthosilicate, 98.4g sodium aluminate, 24.8g dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC), and 2700g water were mixed evenly and placed into a crystallization vessel. Then, 240g of ZSM-22 molecular sieve was added and stirred. The vessel was sealed, and the temperature was raised to 100℃ for hydrothermal crystallization for 7 hours. After crystallization, the crystallized product was washed, dried at 100℃ for 6 hours, and then calcined at 450℃ for 8 hours to obtain the first embedded molecular sieve Z6. Molecular sieve Z6 was then subjected to ion exchange in a 1.5mol / L CaCl2 solution at 80℃ for 4 hours, filtered and washed, dried at 100℃ for 5 hours, and then calcined at 350℃ for 6 hours to obtain the second embedded molecular sieve GZ-6, with a specific surface area of ​​498m². 2 / g, pore volume is 0.23mL / g, and the mass fraction of TON structured molecular sieve is 82%.

[0140] The preparation process of catalyst E-6 of the present invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-6, the Pt loading is 0.48 wt% of the support, and the catalyst prepared is numbered E-6.

[0141] Comparative Example 1

[0142] Take 134g of ZSM-22 molecular sieve (silicon-to-aluminum ratio 90), 200g of 5A molecular sieve, 150g of aluminum hydroxide (SB produced by Condean GmbH, Germany) and 30g of guar gum powder and mix them evenly. Then add water and concentrated nitric acid (mass concentration of 66.5wt%) and knead thoroughly to make a paste-like plastic material. Extrude cylindrical strips with a diameter of 1.5mm on an extruder. Dry the cylindrical strips at 100℃ for 12 hours and then calcine them at 550℃ in air for 4 hours to obtain the catalyst support ES-7 of this invention.

[0143] The catalyst of this invention, containing 0.49 wt% Pt, was prepared by loading 300 g of support ES-7 with precious metal Pt using a saturated impregnation method, drying at 110 °C for 7 hours, and calcining at 500 °C for 3 hours in air atmosphere. The catalyst was designated as C-1.

[0144] Comparative Example 2

[0145] 40g sodium hydroxide, 208g tetraethyl orthosilicate, 285.6g aluminum isopropoxide, 5.75g polyethylene oxide triblock copolymer (P123), and 1440g water were mixed evenly and placed into a crystallization vessel. Then, 60g Hβ molecular sieve was added and stirred. The vessel was sealed, and hydrothermal crystallization was carried out at 90℃ for 10 hours. After crystallization, the crystallized product was washed, dried at 110℃ for 6 hours, and then calcined at 450℃ for 8 hours to obtain the first embedded molecular sieve Z7. Molecular sieve Z7 was then subjected to ion exchange in a 1.8mol / L CaCl2 solution at 90℃ for 4 hours, filtered and washed, dried at 100℃ for 4 hours, and then calcined at 400℃ for 3 hours to obtain the second embedded molecular sieve GZ-7.

[0146] The preparation process of the comparative catalyst C-2 of this invention is the same as that in Example 1, except that the embedded molecular sieve used is GZ-7, the Pt loading is 0.30 wt% of the support, and the catalyst prepared is designated as C-2.

[0147] Table 1. Main physicochemical properties of catalysts prepared in each embodiment (comparative example)

[0148] catalyst Molecular sieve Pt / wt% <![CDATA[S / (m 2 / g)]]> V / (mL / g) E-1 GZ-1 0.28 382 0.30 E-2 GZ-2 0.50 363 0.33 E-3 GZ-3 0.31 393 0.31 E-4 GZ-4 0.47 325 0.35 E-5 GZ-5 0.33 371 0.32 E-6 GZ-6 0.48 416 0.29 C-1 ZSM-22 / 5A 0.49 374 0.27 C-2 GZ-7 0.30 615 0.41

[0149] The feedstock oils used in the embodiments and comparative examples of the present invention include five types: hydrocracking tail oil, hydrotreated light deoil, hydrotreated wax oil, hydrotreated wax paste, and hydrotreated wax off-oil. The specific properties of the feedstock oils are shown in Table 3.

[0150] Table 3 Properties of Feed Oil

[0151] crude oil Hydrocracking tail oil Hydrogenation light deoiling Hydrogenated wax oil Hydrogenated wax paste Hydrogenated wax oiling <![CDATA[Density, kg / m 3 > 835 895 857 822 842 Distillation range, ℃ 375～530 350～750 386-515 380～480 370～510 <![CDATA[Viscosity (100 °C), mm 2 / s ]]> 4.02 9.87 5.63 3.85 4.51 Pour point, ℃ 36 45 41 49 38 Sulfur, μg / g 12.5 20.0 9.6 5.8 6.5 Nitrogen, μg / g <1.0 2.5 1.8 1.0 1.2 Refractive index (20℃) 1.4680 1.5984 1.4921 1.4342 1.4511 Mass spectrometry composition, % Alkanes 57.7 38.6 48.3 77.25 55.8 Cycloalkanes 39.0 48.9 41.93 19.85 40.6 Single ring / Double ring / Triple ring 16.5 / 14.6 / 5.0 22.4 / 20.2 / 4.0 17.9 / 20.43 / 3.3 9.75 / 7.31 / 2.55 17.7 / 16.2 / 5.3 Fourth Ring Road / Fifth Ring Road / Sixth Ring Road 2.9 / - / - 1.6 / 0.5 / 0.2 0.3 / - / - 0.24 / - / - 1.4 / - / - Aromatics 3.3 12.5 9.77 2.9 3.6 Single ring / double ring 2.5 / 0.5 7.6 / 3.5 6.11 / 2.66 2.1 / 0.5 4.2 / 1.5 Third Ring Road / Fourth Ring Road / Fifth Ring Road 0.2 / 0.1 / - 0.8 / 0.4 / 0.1 0.8 / 0.2 / - 0.2 / 0.1 / - 0.2 / 0.1 / - Unidentified - 0.1 - - -

[0152] Examples 8-15

[0153] Examples 8-15 used the hydrocracking tail oil from Table 3 as feedstock and adopted... Figure 1 The process shown in the figure involves loading catalysts E-2, E-6, E-4, E-5, E-3, E-1, E-2, and E-2 into the adsorption reaction zone, respectively. The process conditions and results are shown in Table 4.

[0154] Table 4. Process conditions and results of Examples 8-15

[0155] Example number Implementation 8 Implementation 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative Example 1 Comparative Example 2 catalyst E-2 E-6 E-4 E-5 E-3 E-1 E-2 E-2 C-1 C-2 crude oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Hydrocracking tail oil Adsorption reaction process conditions in the first reaction zone Adsorption temperature / ℃ 130 130 130 130 130 130 130 130 130 130 Adsorption pressure / MPa 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 <![CDATA[Space velocity per hour -1 > 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 First material flow refractive index (20℃) 1.4900 1.4900 1.4900 1.4900 1.4900 1.4900 1.4724 1.5120 1.4900 1.4900 The increase in the refractive index of the first feed stream compared to the refractive index of the raw material / % 1.5 1.5 1.5 1.5 1.5 1.5 0.3 3.0 1.5 1.5 Isomerization dewaxing process conditions in the first reaction zone Reaction temperature / ℃ 325 325 325 325 325 325 325 325 325 325 Reaction pressure / MPa 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Hydrogen-to-oil volume ratio 300 300 300 300 300 300 300 300 300 300 Reaction time / h 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Vacuum distillation process conditions Distillation column top pressure / mmHg 11 11 11 11 11 11 11 11 11 11 Distillation column bottom temperature / ℃ 320 320 320 320 320 320 320 320 320 320 Base oil properties Light lubricating oil base oil Pour point / ℃ -30 -24 -23 -20 -16 -13 -30 -26 -9 -6 <![CDATA[Viscosity (100 °C), mm / s 2 > 2.100 2.108 2.093 2.089 2.120 2.097 2.106 2.131 2.079 2.108 Viscosity Index 100 99 98 98 99 97 98 104 93 88 medium-quality lubricating oil base oil Pour point / ℃ -27 -22 -20 -18 -14 -10 -27 -22 -7 -3 <![CDATA[Viscosity (100 °C), mm / s 2 > 4.020 4.035 4.010 4.000 4.108 4.050 4.065 4.200 4.061 4.036 Viscosity Index 116 113 113 113 110 112 112 122 106 101 Heavy lubricating oil base oil Pour point / ℃ -15 -11 -10 -9 -7 -4 -14 -11 -2 1 <![CDATA[Viscosity (100 °C), mm / s 2 > 6.011 6.020 6.110 6.000 6.100 6.036 6.155 6.201 6.160 6.032 Viscosity Index 125 121 121 120 120 119 122 129 111 109

[0156] Examples 16-19

[0157] Examples 16-19 use the hydrogenated light deoiling, hydrogenated wax oil, hydrogenated wax paste, and hydrogenated wax off-oil from Table 3 as raw materials, employing... Figure 2 The process shown in the figure involves loading catalyst E-2 into both the first and second adsorption reaction zones. The process conditions and results are shown in Table 5.

[0158] Table 5. Process conditions and results of Examples 16-19

[0159] Example number Example 16 Example 17 Example 18 Example 19 catalyst E-2 E-2 E-2 E-2 crude oil Hydrogenation light oil removal Hydrogenated wax oil Hydrogenated wax paste Hydrogenated wax oiling Adsorption reaction process conditions in the first reaction zone Adsorption temperature / ℃ 230 190 120 50 Adsorption pressure / MPa 0.02 0.12 0.30 0.45 <![CDATA[Space velocity per hour -1 > 4.6 2.5 0.08 1.60 First material flow refractive index (20℃) 1.6000 1.5040 1.5059 1.4888 The increase in the refractive index of the first feed stream compared to the refractive index of the raw material / % 0.1 0.8 5.0 2.6 Isomerization dewaxing process conditions in the first reaction zone Reaction temperature / °C 400 250 350 280 Reaction pressure / MPa 2.0 18.0 12.0 8.0 Hydrogen-to-oil volume ratio 1500 300 1000 600 Reaction time / h 2 0.5 9 5 Adsorption reaction process conditions in the second reaction zone Adsorption temperature / ℃ 230 190 120 50 Adsorption pressure / MPa 0.02 0.12 0.30 0.45 <![CDATA[Space velocity per hour -1 > 4.6 2.5 0.08 1.60 First material flow refractive index (20℃) 1.6000 1.5040 1.5059 1.4888 The increase in the refractive index of the first feed stream compared to the refractive index of the raw material / % 0.1 0.8 5.0 2.6 Isomerization dewaxing process conditions in the second reaction zone Reaction temperature / °C 400 250 350 280 Reaction pressure / MPa 2.0 18.0 12.0 8.0 Hydrogen-to-oil volume ratio 1500 300 1000 600 Reaction time / h 2 0.5 9 5 Vacuum distillation process conditions Distillation column top pressure / mmHg 100 50 1 23 Distillation column bottom temperature / ℃ 200 280 370 330 Light lubricating oil base oil Pour point / ℃ -35 -24 -33 -28 <![CDATA[Viscosity (100 °C), mm / s 2 > 2.45 2.21 1.98 2.06 Viscosity Index 96 104 108 110 medium-quality lubricating oil base oil Pour point / ℃ -31 -20 -30 -25 <![CDATA[Viscosity (100 °C), mm / s 2 > 8.033 5.510 3.702 3.920 Viscosity Index 112 118 121 125 Heavy lubricating oil base oil Pour point / ℃ -17 -8 -15 -13 <![CDATA[Viscosity (100 °C), mm / s 2 > 13.71 11.90 9.10 10.80 Viscosity Index 121 127 130 132

[0160] Comparative Example 1

[0161] Using the hydrocracking tail oil in Table 3 as feedstock, and employing Figure 1 The process shown in Table 3 involves loading catalyst C-1 into the adsorption reaction zone, and the process conditions and results are as follows.

[0162] Comparative Example 2

[0163] Using the hydrocracking tail oil in Table 3 as feedstock, and employing Figure 1 The process shown in Table 3 involves loading catalyst C-2 into the adsorption reaction zone.

Claims

1. A molecular sieve composition comprising an embedded molecular sieve of TON structure molecular sieve and 5A type molecular sieve.

2. The molecular sieve composition according to claim 1, wherein the TON structure molecular sieve is embedded on at least a portion of the surface of the 5A type molecular sieve.

3. The molecular sieve composition according to claim 1, wherein the calcination form of the embedded molecular sieve has the XRD pattern shown in Table I or Table II below. Table I Table II Let the intensity value of the strongest diffraction peak in the XRD pattern be 100. Then W = weak, that is, relative intensity >0 to ≤20; M = moderate, that is, relative intensity >20 to ≤40; S = strong, that is, relative intensity >40 to ≤60; VS = very strong, that is, relative intensity >60 to ≤100.

4. The molecular sieve composition according to claim 1, wherein the specific surface area of ​​the embedded molecular sieve is 300 m². 2 / g-600m 2 / g, pore volume 0.15cm 3 / g-0.40cm 3 / g, or, the specific surface area of ​​the molecular sieve composition is 200m². 2 / g-550m 2 / g, pore volume 0.25cm 3 / g-0.60cm 3 / g.

5. The molecular sieve composition according to claim 1, wherein in the embedded molecular sieve, the weight ratio of the 5A type molecular sieve to the TON structure molecular sieve is 1:80-3:

1.

6. The molecular sieve composition according to claim 1, wherein in the embedded molecular sieve, the weight ratio of the 5A type molecular sieve to the TON structure molecular sieve is 1:30-1:

1.

7. The molecular sieve composition according to claim 1, wherein the content of the TON structure molecular sieve is 10wt%-80wt%, the content of the 5A type molecular sieve is 1wt%-50wt%, and the content is based on 100wt% of the total weight of the molecular sieve composition, or the content of the embedded molecular sieve is 10wt%-90wt%, and the content is based on 100wt% of the total weight of the molecular sieve composition.

8. The molecular sieve composition according to claim 1, wherein the content of the TON structure molecular sieve is 20wt%-60wt%, the content of the 5A type molecular sieve is 2wt%-20wt%, based on a total weight of 100wt% of the molecular sieve composition, or the content of the embedded molecular sieve is 20wt%-70wt%, based on a total weight of 100wt% of the molecular sieve composition.

9. The molecular sieve composition according to claim 1 further comprises an inorganic refractory oxide and an active metal component, wherein the active metal component is present in an amount of 0.05 wt% to 5.0 wt% based on the metal element, and is based on 100 wt% of the total weight of the molecular sieve composition.

10. The molecular sieve composition according to claim 1 further comprises an inorganic refractory oxide and an active metal component, wherein the active metal component is present in an amount of 0.1 wt%-1.0 wt% based on the metal element, and is based on 100 wt% of the total weight of the molecular sieve composition.

11. The molecular sieve composition according to claim 9 or 10, wherein the inorganic refractory oxide is selected from one or more of alumina, titanium oxide, boron oxide, silicon oxide, zirconium oxide and magnesium oxide, and the active metal component is selected from at least one of the noble metals of Group VIII of the periodic table.

12. The molecular sieve composition according to claim 9 or 10, wherein the inorganic refractory oxide is selected from alumina, and the active metal component is selected from at least one of Pt and Pd.

13. The molecular sieve composition according to claim 12, wherein the active metal component is selected from Pt.

14. The molecular sieve composition according to claim 1, wherein the TON structure molecule is screened from one or more of ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10, and the 5A type molecule is screened from 5A molecular sieve.

15. The molecular sieve composition according to claim 1, wherein the TON structure molecule is screened from ZSM-22, and the 5A type molecule is screened from 5A molecular sieve.

16. The molecular sieve composition according to claim 1, which has the dual functions of adsorption and hydroisomerization.

17. A method for preparing the mosaic molecular sieve according to any one of claims 1-16, comprising the following steps: (1) A gel mixture is obtained by contacting a silicon source, an aluminum source, and an alkali source in the presence of a template agent, a TON-structured molecular sieve, and water. (2) The gel mixture is subjected to hydrothermal crystallization, then washed, dried and calcined to obtain the first embedded molecular sieve.

18. The preparation method according to claim 17 further comprises the following steps: (3) The first embedded molecular sieve is subjected to calcium exchange, and then washed, dried and calcined to obtain the second embedded molecular sieve.

19. The preparation method according to claim 17, wherein in step (1), the silicon source is selected from at least one of water glass, sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; the alkali source is selected from at least one of alkali metal hydroxides; the aluminum source is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate, aluminum hydroxide, alumina, and boehmite; the template agent is selected from at least one of polyethylene oxide triblock copolymer and dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride; and the TON structure molecule is screened from one or more of ZSM-22, Theta-1, ISI-1, KZ-2, and NU-10.

20. The preparation method according to claim 17 or 19, wherein in step (1), the alkali source is selected from sodium hydroxide, and the TON structure molecule is screened from ZSM-22.

21. The preparation method according to claim 17, wherein in step (1), the operating conditions for contact include: The mixture is stirred at a temperature of 15℃-30℃ for 1h-4h. The alkali source is calculated as an oxide, the silicon source as SiO2, the aluminum source as Al2O3, and the molar ratio of the template agent and water is (0.5-2.5):1:(0.4-0.7):(0.001-0.08):(30-200). The amount of TON structured molecular sieve used is 0.3-8 times the amount of silicon source added.

22. The preparation method according to claim 21, wherein in step (1), the amount of the TON structure molecular sieve is 1-7 times the amount of silicon source added.

23. The preparation method according to claim 17, wherein in step (2), the hydrothermal crystallization temperature is 60℃-120℃, the crystallization time is 2h-16h, the drying temperature is 80℃-200℃, the drying time is 2h-24h, the calcination temperature is 400℃-600℃, and the calcination time is 2h-12h.

24. The preparation method according to claim 17, wherein in step (3), the operating conditions for calcium exchange include: The exchange temperature is 60℃-100℃, the exchange time is 1h-12h, and the calcium ion concentration in the calcium exchange solution is 0.1mol / L-2.5mol / L; the drying temperature is 80℃-150℃, the drying time is 2h-12h, and the calcination temperature is 300℃-500℃, the calcination time is 2h-8h.

25. A method for producing a lubricating oil base oil, comprising the following steps: (1) The raw material containing long side-chain hydrocarbons is contacted with the molecular sieve composition according to any one of claims 1-16 in the presence or absence of hydrogen to obtain a residual liquid with adsorbed molecular sieve composition and reduced content of long side-chain hydrocarbons, wherein the long side-chain hydrocarbons are selected from one or more of long side-chain isoalkanes, long side-chain monocyclic cycloalkanes and long side-chain monocyclic aromatics. (2) The adsorbed molecular sieve composition is treated under hydroisomerization reaction conditions in the presence of hydrogen to obtain a mixture of isomerized products and a desorbed molecular sieve composition, and (3) Separate the mixture of isomerized products to obtain the lubricating oil base oil.

26. The production method according to claim 25, wherein the raw material is repeatedly contacted with the molecular sieve composition multiple times until the refractive index of the residual liquid is 0.1%-5% higher than that of the raw material.

27. The production method according to claim 25, wherein the raw material is repeatedly contacted with the molecular sieve composition multiple times until the refractive index of the residual liquid is 0.5-2.5% higher than that of the raw material.

28. The production method according to claim 25, wherein the raw material is selected from one or more of hydrocracking tail oil, hydrotreated wax oil, hydrotreated bright oil, hydrotreated wax paste, and hydrotreated wax residue.

29. The production method according to claim 25, wherein in step (1), the operating conditions for contact include: Temperature range: 40℃-250℃; pressure range: 0.01MPa-0.5MPa; volumetric hourly space velocity: 0.05h⁻¹ -1 -5.0h -1 , .

30. The production method according to claim 25, wherein in step (1), the operating conditions for the contact include: Temperature range: 60℃-200℃; pressure range: 0.08-0.1MPa; volumetric hourly space velocity: 0.1h. -1 -2.0h -1 .

31. The production method according to claim 25, wherein in step (2), the operating conditions of the hydroisomerization reaction include: In the presence of hydrogen, the reaction temperature is 200-420℃, the hydrogen partial pressure is 1.0-20.0MPa, the reaction time is 0.1h-10h, and the hydrogen-to-oil volume ratio is 100:1-1500:

1.

32. The production method according to claim 25, wherein in step (2), the operating conditions of the hydroisomerization reaction include: In the presence of hydrogen, the reaction temperature is 270-380℃, the hydrogen partial pressure is 3.0-15.0MPa, the reaction time is 0.3h-2h, and the hydrogen-to-oil volume ratio is 100:1-400:

1.

33. The production method according to claim 25, wherein in step (3), the separation comprises the following steps: (3-1) The isomerization product mixture is subjected to gas-liquid separation to obtain a gas stream and a liquid stream, optionally recycling at least a portion of the gas stream as at least a portion of the raw material back to step (1), and (3-2) Fractionate the liquid phase stream to obtain the lubricating oil base oil.

34. The production method according to claim 33, wherein light lubricating oil base oil, medium lubricating oil base oil and heavy lubricating oil base oil are obtained in step (3-2), and optionally at least a portion of the heavy lubricating oil base oil is recycled back to step (1) as at least a portion of the raw material.

35. The production method according to claim 33, wherein in step (3-1), the gas-liquid separation process is achieved by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 1-100 mmHg, and the temperature at the bottom of the distillation column is 200℃-370℃; or in step (3-2), the fractionation process is achieved by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 1-100 mmHg, and the temperature at the bottom of the distillation column is 200℃-370℃.

36. The production method according to claim 33, wherein in step (3-1), the gas-liquid separation process is achieved by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 2-20 mmHg, and the temperature at the bottom of the distillation column is 290℃-350℃; or in step (3-2), the fractionation process is achieved by vacuum distillation, and the conditions for vacuum distillation are: the pressure at the top of the distillation column is 2-20 mmHg, and the temperature at the bottom of the distillation column is 290℃-350℃.

37. The production method according to claim 25, wherein steps (1) and (2) are carried out in the same reactor.

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