Alkylated naphthalene blends and methods of production thereof

Abstract

Alkylated naphthalene blends and methods of making alkylated naphthalene blends are provided. The process includes mixing an MWW-type catalyst in the form of an acid, a naphthalene, and a solvent to provide a reaction mixture, and adding a linear alpha-olefin to the reaction mixture after heating. The resulting AN blends have an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene, and can be combined with a poly-alpha-olefin base stock to provide a synthetic lubricant formulation without a trifluoromethanesulfonic acid based catalyst and using fewer process steps.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to USSN 63 / 580,733, filed September 6, 2023, which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to a method for producing alkylated naphthalene blends that can be used in synthetic lubricant formulations. Background Technology

[0004] Two alkylated naphthalene blends (AN5 blend with a kinematic viscosity of 5 cSt at 100°C (KV100–5 cSt) and AN12 blend with a kinematic viscosity of 12 cSt at 100°C (KV100–12 cSt)) are combined with a polyalphaolefin base to produce synthetic lubricant formulations with high stability under extreme operating conditions. AN12 is produced using a highly corrosive homogeneous trifluoromethanesulfonic acid catalyst. The production of AN12 blends requires significant capital investment due to the necessary equipment metallurgy, making the production of synthetic lubricant formulations more expensive. Summary of the Invention

[0005] This article provides a method for preparing AN blends, comprising mixing an acid-form MWW-type catalyst, naphthalene, and a solvent to provide a reaction mixture; increasing the temperature of the reaction mixture; and adding a linear α-olefin to the reaction mixture to produce an AN blend having an isomer ratio of less than 45 wt% monoalkylated naphthalene and greater than 55 wt% polyalkylated naphthalene. 2 / g surface area, and total acidity of 0.80 to 1.0 meq / g TPAD.

[0006] AN blends are also provided, comprising monoalkylated and polyalkylated naphthalene, having a KV100 of 7.0 to 9.5 cSt as measured by ASTM D445 and a Noack% of 5.0 to 11.0 as measured by ASTM D5800. The AN blends have an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

[0007] Also provided are acid-form MWW-type catalyst compositions comprising 5.0 wt% to 7.5 wt% alumina; 69 wt% to 80 wt% silica; about 17.0 wt% to 24.0 wt% Si / Al2; less than 0.03 wt% potassium; and less than or equal to 0.05 wt% sodium, as measured by ICP testing. The acid-form MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 μm. 2 Total surface area / g, total acidity of 0.80 to 1.0 meq / g TPAD, and trimethylpyridine absorption of 90 to 145 µmol / g and 125 to 145 µmol / g. Detailed Implementation

[0008] Before disclosing and describing the compounds, components, compositions, and / or methods herein, it should be understood that, unless otherwise indicated, this disclosure is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, catalyst structures, etc., as these can vary, unless otherwise stated. It should also be understood that the technical terms used herein are for the purpose of describing different embodiments and are not intended to be limiting.

[0009] All numerical values ​​in this detailed description and claims should be considered as modified by the terms “about” or “approximately” to account for experimental errors and biases.

[0010] For the sake of brevity, this document only explicitly discloses certain ranges. However, an unspecified range can be described by combining any lower bound with any upper bound, and an unspecified range can be described by combining any lower bound with any other lower bound; similarly, an unspecified range can be described by combining any upper bound with any other upper bound. Furthermore, even if unspecified, a range includes every point or individual value between its endpoints. Therefore, each point or individual value can serve as its own lower or upper bound, combined with any other point or individual value or any other lower or upper bound, thereby describing an unspecified range.

[0011] For the purposes of this disclosure, the following definitions will apply:

[0012] As used herein, the terms “a” and “the” should be understood to encompass both the plural and the singular.

[0013] As used herein, the term "as-synthesized MWW-type zeolite" means and includes commercially available MWW-type zeolite.

[0014] As used herein, the term "acid form MWW-type zeolite" means and includes synthetic MWW-type zeolite that has been modified by ion exchange and incinerated to alter and remove organic impurities. Incineration often involves calcination under N2 followed by calcination under air.

[0015] As used herein, the term “synthetic MWW-type zeolite MCM-22” is interchangeable with the terms “MCM-22”, “zeolite MCM-22”, and “synthetic MCM-22”.

[0016] As used herein, the term “synthetic MWW-type zeolite MCM-49” is interchangeable with the terms “MCM-49”, “zeolite MCM-49”, and “synthetic MCM-49”.

[0017] Zeolites and zeolite materials

[0018] Zeolites and their homologues are classified by the Structural Committee of the International Zeolite Association according to the IUPAC Committee's rules on zeolite nomenclature. Based on this classification, three-letter codes are assigned to framework zeolites and other crystalline microporous molecular sieves (whose structures have been determined) and described in "Atlas of Zeolite Framework Types," edited by Ch. Baerlocher, LB McCusker, and DH Olson, Elsevier, 6th edition, 2007, which is incorporated herein by reference.

[0019] Some zeolites contain an inorganic framework in which silicon tetrahedral atoms are connected to four next-nearest neighbor tetrahedral atoms via oxygen atoms. As used herein, the term "silicate" refers to a substance containing alternating bonds of silicon and oxygen atoms (i.e., -O-Si-O-Si-), and optionally, other types of atoms (including boron, gallium, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc)) within the inorganic framework type. Atoms in the framework other than silicon and oxygen occupy a portion of the lattice sites that would otherwise be occupied by silicon atoms in a "pure silica" framework (also called a "silicate"). Therefore, the terms "framework silicate" or "zeolite framework silicate" refer to an atomic lattice containing silicates, borosilicates, gallium silicates, iron silicates, aluminosilicates, titanosilicates, zinc silicates, vanadium silicates, etc. As noted above, the framework structure within a zeolite determines the size of the pores or channels. The pore or channel size determines the type of process that can be applied to a given zeolite. Currently, there are over 200 known zeolite framework silicates recognized by the Structural Committee of the International Zeolite Association, thus providing a range of defined pore geometries and orientations.

[0020] Zeolite framework silicates are typically characterized by ring size, which refers to the number of silicon atoms (or alternative atoms, such as those listed above) that are tetrahedrally coordinated with oxygen atoms in a ring, thus defining pores or channels within the zeolite. For example, an "8-ring" zeolite is a zeolite with pores or channels defined by eight alternating tetrahedral atoms and eight oxygen atoms in the ring. Depending on the various structural constraints present in the framework silicate, the pores or channels defined within a given zeolite can be symmetrical or asymmetrical.

[0021] Zeolites can be classified into small, medium, large, and supermacroporous structures with pore windows demarcated by 8, 10, 12, and more than 12 T atoms, respectively. Supermacroporous zeolites (>12R) include framework zeolites such as AET (14R, e.g., ALPO-8), SFN (14R, e.g., SSZ-59), VFI (18R, e.g., VPI-5), CLO (20R, e.g., cloverite), and ITV (30R, e.g., ITQ-37). Supermacroporous zeolites typically have a free pore diameter greater than about 0.8 nm. Macroporous zeolites (12R) include, for example, LTL, MAZ, FAU, EMT, OFF, MTW, etc. BEA, MOR, and SFS framework zeolites, such as needle zeolite, kaolinite, zeolite L, zeolite Y, zeolite X, ω, ZSM-2, ZSM-12, zeolite T, β, and SSZ-56. Macroporous zeolites typically have a free pore diameter of 0.6 to 0.8 nm. Medium (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, MRE, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework zeolites, such as ZSM-5, ZSM-11, ZSM-48, ZSM-22, ZSM-23, ZSM-35, MCM-22, MCM-49, silica zeolite-1, and silica zeolite-2. Medium-pore-size zeolites typically have a free pore diameter of 0.45 nm to 0.6 nm. Small-pore-size zeolites (8R) include, for example, CHA, RTH, ERI, KFI, LEV, and LTA framework zeolites, such as ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, and ALPO-17. Small-pore-size zeolites typically have a free pore diameter of 0.3 nm to 0.45 nm.

[0022] Both natural and synthetic molecular sieve materials can be used as adsorbents and exhibit catalytic properties for hydrocarbon conversion reactions. Some molecular sieves, such as zeolites, AlPO, and mesoporous materials, are ordered porous crystalline materials with well-defined crystalline structures determined by X-ray diffraction (“XRD”). Molecular sieves can be ordered and produce specific, recognizable XRD patterns. Within some molecular sieve materials are cavities interconnected by channels or pores. In certain types of molecular sieves, the pores are typically of uniform size. The pore size determines whether molecules can move within the molecular sieve and be absorbed or repelled.

[0023] Molecular sieves are used in a variety of industrial processes, such as cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization. Molecular sieves (including naturally occurring or synthetic crystalline molecular sieves) can be used in catalysis and adsorption.

[0024] The synthesis of molecular sieve materials (zeolites) typically involves hydrothermal crystallization from a synthetic mixture containing sources of all elements present in the molecular sieve (or zeolite), such as silica and alumina. In many cases, a structure-directing agent (“SDA”) is also present. A structure-directing agent is a compound believed to promote the formation of a molecular sieve and is thought to act as a template (around which certain molecular sieve structures can form, and which thereby promote the formation of the desired molecular sieve). Various compounds have been used as structure-directing agents, including various types of quaternary ammonium cations. Typically, molecular sieve (zeolite) crystals form around the structure-directing agent, which occupies the pores in the molecular sieve once crystallization is complete. The “synthetic” (or “as-made”) molecular sieve will therefore contain the structure-directing agent in its pores, and after crystallization, the “synthetic” molecular sieve undergoes a treatment step, such as a calcination step, to remove the structure-directing agent.

[0025] As used herein, "MWW framework-type crystalline microporous materials" or "synthetic MWW-type zeolites" include one or more of the following:

[0026] (1) Molecular sieves made from common primary crystal building blocks have a unit cell with an MWW framework topology. (A unit cell is a spatial arrangement of atoms that, if stacked in three-dimensional space, describes a crystal structure. Such crystal structures are discussed in “Atlas of Zeolite Framework Types”, 5th edition, 2001, the full contents of which are incorporated herein by reference);

[0027] (2) Molecular sieves made from common secondary building blocks are two-dimensional tilings of such MWW framework topology cells, thereby forming a single layer with a cell thickness, preferably a c-cell thickness.

[0028] (3) A molecular sieve made from common secondary building blocks is a layer of one or more unit cell thicknesses, wherein the layer of more than one unit cell thickness is made by stacking, packing, or combining at least two monolayers of MWW framework topological cells. Such stacking of secondary building blocks can be in a regular, irregular, random, or any combination thereof; and

[0029] (4) Molecular sieves made of any regular or random two- or three-dimensional combination of cells with MWW framework topology.

[0030] MWW framework-type crystalline microporous materials include those molecular sieves with X-ray diffraction patterns having maximum d-spacing values ​​of 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07, and 3.42 ± 0.07 Å. X-ray diffraction data used to characterize the materials were obtained using standard techniques with copper K-α doublets as incident radiation and a diffractometer equipped with a scintillation counter and a correlated computer as the collection system.

[0031] Examples of crystalline microporous materials or synthetic MWW-type zeolites of MWW framework type I include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U.S. Patent No. 4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Patent No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97 / 17290), MCM-36 (described in U.S. Patent No. 5,250,277), MCM-49 (described in U.S. Patent No. 5,236,575), and MCM-56 (described in U.S. Patent No. 5,362,697). UZM-8 (described in U.S. Patent No. 6,756,030), UZM-8HS (described in U.S. Patent No. 7,713,513), UZM-37 (described in U.S. Patent No. 7,982,084); EMM-10 (described in U.S. Patent No. 7,842,277), EMM-12 (described in U.S. Patent No. 8,704,025), EMM-13 (described in U.S. Patent No. 8,704,023), MIT-1 (described by Luo et al.) Chem. Sci ., 2015, 6, 6320-6324) and their mixtures.

[0032] In the implementation, the MWW framework type crystalline microporous material can be an aluminosilicate material having a silica to alumina molar ratio of at least 10, for example, at least 10 to less than 50.

[0033] As presented in this paper, MWW framework-type crystalline microporous materials can be contaminated by other crystalline materials such as magnesium alkali zeolite or quartz. These contaminants can be present in amounts of <10% by weight, typically <5% by weight.

[0034] As described herein, a novel method has been developed to produce alkylated naphthalene blends (“AN blends”) with a kinematic viscosity (“KV100”) at 100°C falling between that of AN5 and AN12 blends. This method uses commercially available zeolite materials modified using the ion-exchange process described herein as a catalyst. The catalyst used in this method is less corrosive than homogeneous trifluoromethanesulfonic acid catalysts. Furthermore, the resulting alkylated naphthalene blends (sometimes referred to herein as “medium-viscosity AN blends”) combine the performance benefits of both AN5 and AN12 blends. These blends can be used in the synthesis of circulating and gear oils and other lubricant formulations as described herein.

[0035] The advantages of this method include a new catalyst with lower corrosivity and the elimination of the need for additional investment in metallurgical equipment using specialized equipment. Another advantage is that the one-step process will provide blends equivalent to those produced by existing two-step processes. A third advantage is the ability to produce single formulations without the need to blend two or more alkylated naphthalenes.

[0036] Zeolite MCM-22

[0037] As described in U.S. Patent No. 4,954,325, the synthetic MWW-type zeolite MCM-22 (“synthetic MCM-22”) is not contaminated by other crystal structures and exhibits strong adsorption capacity and catalytic practicality compared to PSH-3. U.S. Patent No. 4,954,325, column 2, lines 21-32. The MCM-22 zeolite (“MCM-22”) has the following molar composition: X₂O₃:(n)YO₂, where X is a trivalent element such as aluminum, boron, iron, and / or gallium, Y is a tetravalent element such as silicon and / or germanium, and n is at least about 10 or about 10–about 150, about 10–about 60, and about 20–about 40. In its synthetic form and on an anhydrous basis, MCM-22 has the following formula (in terms of the number of moles of oxide per n moles of YO2): (0.005-0.1)Na2O:(1-4)R:X2O3:nYO2, where R is the organic structural part. US Patent No. 4,954,325, column 2, lines 40-56, is incorporated herein by reference.

[0038] MCM-22 can be prepared from a reaction mixture containing: (1) an alkali metal or alkaline earth metal (M) such as sodium or potassium; (2) a cation; (3) an oxide of a trivalent element X (i.e., aluminum); (4) an oxide of a tetravalent element Y (i.e., silicon); (5) an organic (R) directing agent; and (6) water. The reaction mixture has a reaction mixture composition within the following range (in terms of the molar ratio of oxides).

[0039] Table 1

[0040] Reactants for producing synthetic MCM-22 zeolite

[0041]

[0042] To synthesize MCM-22, the YO2 source must primarily consist of solid YO2 or at least about 30 wt% solid YO2. When the YO2 is silicon dioxide, the silicon dioxide source contains at least about 30 wt% solid silicon dioxide. Ultrasil is spray-dried silicon dioxide containing about 90 wt% silicon dioxide precipitate. HiSil is hydrated SiO2 containing about 87 wt% silicon dioxide, about 6 wt% free H2O, and about 4.5 wt% bound hydrated H2O precipitate with a particle size of about 0.02 micrometers, which is conducive to crystal formation from the above mixture. On the other hand, if another source of silicon oxide, such as Q-Brand (sodium silicate consisting of about 28.8 wt% SiO2, 8.9 wt% Na2O, and 62.3 wt% H2O), is used, crystallization produces little or no MCM-22 and contains impurity phases of other crystal structures (i.e., ZSM-12) prepared in the latter case. Therefore, the source of YO2 contains at least about 30% by weight of solid YO2 silica, or at least about 40% by weight of solid YO2 silica. (US Patent No. 4,954,325, column 5, lines 14-55)

[0043] Crystallization can be carried out in a suitable reactor vessel, such as a polypropylene tank or a Teflon-lined or stainless steel autoclave. The overall effective temperature range for crystallization is from about 80°C to about 225°C, sustained at said temperature for a time sufficient for crystallization to occur, from about 24 hours to about 60 days. Thereafter, the solid (crystals) is separated from the liquid and recovered. The organic directing agent is cycloheximine or azircycloheptane. (US Patent No. 4,954,325, column 5, lines 56-67). Synthesis is facilitated by the presence of at least 0.01%, 0.10%, and 1% (based on total weight) of seed crystals of the produced MCM-22 product. (US Patent No. 4,954,325, column 6, lines 16-19).

[0044] Crystalline materials, particularly in their metallic, hydrogen, and ammonium forms, can be advantageously converted into other forms through heat treatment. This heat treatment is typically carried out by heating one of these forms at a temperature of at least 370°C for at least one minute and generally not more than 20 hours. While sub-atmospheric pressure can be used for heat treatment, atmospheric pressure is preferred. Heat treatment can be carried out at temperatures up to about 925°C. (US Patent No. 4,954,325, column 4, lines 59-68). Heat-treated MCM-22 products can be used as catalysts in hydrocarbon conversion reactions. When used as an adsorbent or as a catalyst in organic compound conversion methods, the MCM-22 crystalline material should be dehydrated, at least partially dehydrated. This can be accomplished by heating in an atmosphere such as air or nitrogen at atmospheric pressure, sub-atmospheric pressure, or above atmospheric pressure to a temperature ranging from 200°C to 595°C for 30 minutes to 48 hours. Dehydration can also be carried out at room temperature simply by placing the silicate in a vacuum, but this requires additional time. US Patent No. 4,954,325, column 5, lines 1-13.

[0045] Zeolite MCM-49

[0046] As described in U.S. Patent No. 5,236,575, the synthetic MWW-type zeolite MCM-49 (also referred to herein as "zeolite MCM-49" and "MCM-49") has a composition with the following molar relationship: X₂O₃:(n)YO₂, where X is a trivalent element such as aluminum, boron, iron, and / or gallium; Y is a tetravalent element such as silicon and / or germanium; and n is less than about 35, about 2 to about 35, about 10 to about 35, about 15 to about 31. U.S. Patent No. 5,236,575, column 2, lines 67-68. In synthetic form, the material has the following formula (on anhydrous basis and in terms of the number of moles of oxide per n moles of YO₂): (0.1-0.6)M₂O:(1-4)R:X₂O₃:nYO₂, where M is an alkali metal or alkaline earth metal, and R is an organic structural part. The M and R components are associated with the material due to their presence during crystallization and can be readily removed by the post-crystallization method described in column 3, lines 1-20 of U.S. Patent No. 5,236,575.

[0047] The crystalline material can be prepared from a reaction mixture containing the following sources: an alkali metal or alkaline earth metal (M), a cation, an oxide of a trivalent element X, an oxide of a tetravalent element Y, a directing agent (R), and water. The composition of the reaction mixture, in terms of the molar ratio of oxides, falls within the following ranges.

[0048] Table 2

[0049] Reactants for producing synthetic MCM-49 zeolite

[0050]

[0051] In this synthesis method, if more than one X component is present, at least one must be present such that the YO2 / X2O3 molar ratio is less than about 35. For example, if aluminum oxide and gallium oxide components are used in the reaction mixture, at least one of the YO2 / Al2O3 and YO2 / Ga2O3 molar ratios must be less than about 35. If only aluminum oxide is added to the reaction mixture as a source of X, the YO2 / Al2O3 ratio must be less than about 35.

[0052] Furthermore, the source of YO2 is primarily solid YO2, for example, at least about 30 wt% solid YO2, in order to obtain crystalline products containing at least about 30 wt% solid silica, such as Ultrasil (spray-dried silica containing about 90 wt% silica precipitate) or HiSil (hydrated SiO2 containing about 87 wt% silica, about 6 wt% free H2O and about 4.5 wt% bound hydrated H2O and precipitate with a particle size of about 0.02 micrometers), which is beneficial for the formation of crystallized MCM-49.

[0053] The directing agent R is selected from cycloalkylamines, azacycloalkanes, diazacycloalkanes, and mixtures thereof, wherein the alkyl group contains 5-8 carbon atoms. Non-limiting examples of R include cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclohexylimine, cycloheptylimine, piperazine, and combinations thereof. See U.S. Patent 5,236,575, column 6, lines 24-68, and column 7, lines 1-2.

[0054] The synthesis of MCM-49 can be facilitated by the presence of at least 0.01%, 0.10%, and % seed crystals based on the total weight of the crystalline product. Available seed crystals include MCM-22 and / or MCM-49. (US Patent 5,236,575, column 7, lines 19-23). ​​Furthermore, MCM-49 can be converted to another form by heat treatment (typically by heating at a temperature of at least about 370°C for at least 1 minute and no more than 20 hours). While sub-atmospheric pressure can be used for heat treatment, atmospheric pressure is preferred for convenience. Heat treatment can be performed at temperatures up to about 925°C. (US Patent No. 5,236,575, column 5, lines 59-67). When MCM-49 is used as an adsorbent or as a catalyst in methods for converting organic compounds, it should be dehydrated, at least partially dehydrated. This can be accomplished by heating in an atmosphere such as air or nitrogen to a temperature ranging from 200°C to approximately 370°C for 30 minutes to 48 hours at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. Dehydration can also be performed at room temperature simply by placing MCM-49 in a vacuum, but this requires a longer time to achieve dehydration. (See U.S. Patent No. 5,236,575, column 6, lines 13-23).

[0055] Blend

[0056] AN5 blends are API Group V alkylated naphthalene blends. AN5 blends exhibit high hydrolytic, thermal, and oxidative stability and can be used as blends in synthetic lubricant applications requiring high stability under extreme operating conditions. Table 3 below provides the general properties of AN5 blends.

[0057] Table 3

[0058] Properties of AN5 blends

[0059]

[0060] Add 1% diphenylamine and phenylnaphthylamine antioxidants.

[0061] AN12 blends are API Group V alkylated naphthalene blends. Like AN5 blends, AN12 blends exhibit high hydrolytic, thermal, and oxidative stability and can be used as blends in synthetic lubricant applications requiring high stability under extreme operating conditions. Table 4 below provides the general properties of AN12 blends.

[0062] Table 4

[0063] Properties of AN12 blends

[0064]

[0065] Add 1% diphenylamine and phenylnaphthylamine antioxidants.

[0066] Table 5 below compares the performance properties of alkylated naphthalene AN5 and AN12 blends. The oxidative stability of the blends is described in WO2016 / 0416647. As described in WO2011 / 041647, the oxidation test determines the amount of time it takes for a lubricant to undergo oxidative degradation or decomposition to lead to a catastrophic increase in viscosity. To perform this test, the sample is placed in an oxidation bath along with various organometallic catalysts dissolved in solution, and then placed in a test bath. The bath and its contents are placed in a heating block maintained at a specified temperature, and a measured volume of dry gas is blown into the test bath at a pressure maintained between 0 and 100 psig for the duration of the test, with an air flow rate of up to 250 cc / min. The specified temperature is maintained using an electric heater and a thermostat equipped with a temperature control within a 1℉ (0.5℃) range from 200℉ (93℃) to 450℉ (232℃). Periodically sampled test tanks are used for viscosity testing until the oil has oxidized, which is confirmed by a rapid increase in oil viscosity. Oil conditions are checked by measuring its kinematic viscosity (“KV100”) at 100°C. The original kinematic viscosity at 100°C can then be compared. Good performance in this test is demonstrated by little or no viscosity increase at the end of the test. Typically, high-viscosity blends have a KV of at least 100 cSt. Low-viscosity base materials have a KV of less than 2 cSt. Kinematic viscosity is determined by the ASTM D-445 method, by measuring the time it takes for a given volume of liquid to flow under gravity through a calibrated glass capillary viscometer.

[0067] Table 5

[0068] Compare performance attributes

[0069] AN5 blend and AN12 blend

[0070]

[0071] Ion exchange treatment: zeolite MCM-22 and zeolite MCM-49

[0072] As presented herein, economically viable zeolite catalyst systems have been confirmed that can alkylate naphthalene to the desired isomer ratio in acceptable yields. These novel catalyst systems are capable of producing alkylated naphthalene blends (“AN blends”) that closely match the isomer distributions of the AN5 and AN12 blends when combined. The ratio of monoalkylated naphthalene (“MA”) to dialkylated naphthalene (“DA”) plus trialkylated naphthalene (“TA”) is equivalent to the same ratio in a combined blend containing 35% AN5 and 65% AN12, and significantly reduces production costs. For example, the AN blends presented herein have an MA to (DA+TA) ratio of approximately 40% MA to 60% (DA+TA), similar to a combination of 35% by weight of AN5 and 65% by weight of AN12 blends having approximately 40% MA and approximately 60% DA+TA.

[0073] The method for producing AN blends of the present invention is catalyzed by one or more commercially available zeolites, which are modified by ion exchange to provide modified zeolites referred to herein as "acid-form zeolites" or "MWW-type acid-form zeolites". Acid-form zeolites are less corrosive than trifluoromethanesulfonic acid. To provide acid-form zeolites, the synthesized zeolite is converted from basic to acidic by removing alkali metals. By using the method of preparing alkylated naphthalene blends catalyzed by acid-form zeolites, the AN blends combine the performance benefits from AN5 and AN12 blends.

[0074] As described in U.S. Patent No. 3,140,251, alkali metal removal is achieved by contacting zeolite crystals with a solution of an ammonium salt (e.g., ammonium nitrate, ammonium chloride) capable of converting to hydrogen ions until the metal cations originally present in the zeolite reach the desired concentration or are almost completely eliminated. Ion exchange can be performed in a batch (using an exchange column with a recirculating solution), semi-batch (filter press), or continuous (horizontal belt filter or extractor) manner. After the ion exchange method, the treated zeolite is washed with water until the effluent has the pH value of the wash water.

[0075] As described in the following examples, the synthetic MWW-type zeolites MCM-22 and MCM-49 (described above) were synthesized via NH4 +The ion exchange process, followed by calcination, transforms the zeolite into its acidic form, MWW-type zeolite. The ion exchange method for providing the acidic form of MWW-type zeolite involves contacting an aqueous solution of an ammonium salt, such as ammonium nitrate, ammonium chloride, or ammonium acetate, with sodium from the zeolite. The aqueous solution has a concentration of approximately 1 molar. The zeolite is contacted with the aqueous solution in a stirred tank or via filtration. Various types of filters can be used, including filter presses or belt filters, but other filter arrangements are also feasible. A large quantity of ammonium solution must be used to ensure that most of the sodium or other cations are removed from the crystals. Typically, the sodium content is less than 500 ppm by weight. After ion exchange, the zeolite crystals are washed with deionized water to remove excess ammonium solution. The filter is then dried at approximately 300℉ to remove any remaining water.

[0076] The zeolite is then calcined at a temperature of 500°C to 700°C to remove any present organic matter and adsorbed ammonium, with the preferred temperatures being 500°C and 600°C. The calcination step can be carried out in a single step using an oxygen-containing atmosphere of 1 wt% to 22 wt% O2. Alternatively, the calcination step is a two-step method, wherein the zeolite is first heat-treated in an inert atmosphere such as N2, He, or Ar, followed by heat-treated in an oxygen-containing atmosphere (1 wt% to 22 wt% O2). This heat treatment can be carried out in a fixed-bed reactor or a rotary calcining furnace. A calcination time of 1 to 4 hours is used, followed by a calcination time of 1 to 4 hours in an air atmosphere. A preferred calcination time is 1 to 2 hours in a nitrogen atmosphere, followed by a calcination time of 1 to 2 hours in an air atmosphere.

[0077] Key properties and characteristics of modified MWW-type zeolite (acid form MWW-type zeolite) (the product of ion exchange and calcination of synthetic MWW-type zeolite) include: modified MWW-type zeolite contains less than 0.05 wt% carbon, less than 500 ppm wt% sodium, and has a molecular weight greater than 400 m 2 The total surface area per g is greater than 65 m² 2 The surface area is / g. The acid form of MWW-type zeolite has a surface acidity of 125 to 145 μmol / g / trimethylpyridine absorption and a total acidity of 0.80 to 1.0 meq / g, as measured by TPAD.

[0078] Temperature-programmed ammonia desorption (“TPAD”) is a measure of the acidity of a zeolite or catalyst composition. For this TPAD analysis, the catalyst sample (0.2 g) was first dried at 500 °C for 3 h at a helium (He) flow rate of 10 cc / min. The temperature was then lowered to 100 °C, followed by saturation of the catalyst sample with ammonia. After saturation with ammonia, the catalyst sample was desorbed at 100 °C using a helium flow rate to desorb the physically adsorbed ammonia from the catalyst sample. TPAD was performed at a desorption heating rate of 18.4 °C / min at a helium flow rate of 16 cc / min. The desorbed ammonia and water (if present) were monitored during TPAD, in meq / g.

[0079] Trimethylpyridine absorption is a measure of the acidity of a zeolite or catalyst composition. The trimethylpyridine absorption of zeolite and catalyst compositions is determined as the number of micromoles of trimethylpyridine (a type of catalyst poison) absorbed per gram of zeolite or catalyst composition sample (dried for 60 minutes at 200°C under a nitrogen stream on a thermogravimetric analyzer (Model Q5000, manufactured by TA Instruments, New Castle, Delaware)). After drying the catalyst sample, trimethylpyridine (as a catalyst poison) was sprayed onto the sample at a partial pressure of 3 Torr for 60 minutes. The trimethylpyridine absorption was calculated using the following formula: (Weight of catalyst sample after spraying with trimethylpyridine - Weight of dried catalyst sample) × 10⁶ ÷ (Molecular weight of trimethylpyridine × Weight of dried catalyst sample).

[0080] MWW-type zeolites are known to exhibit selectivity for monoalkylation of naphthalene. However, we have unexpectedly discovered that acidic MWW-type zeolites modified to have a surface acidity of 125 to 145 μmol / g / trimethylpyridine uptake and a total acidity of 0.80 to 1.0 meq / g (as measured by TPAD) can be used to produce blends of mono- and di- and tri-isomers. Although previously thought to lack selectivity, the properties of MWW-type zeolites with high surface acidity drive the yield of trialkylated naphthalene and the final yield of polyalkylates.

[0081] Blend

[0082] This article provides a method for preparing naphthalene blends with KV100 alkylated between KV100 in AN5 and AN12 blends. In developing this method, the following assumptions are made: (a) x%C 14 Monoalkylated naphthalenes exhibit similar performance to x%C in lubricant formulations. 16 Monoalkylated naphthalene is equivalent to; (b) x% C 14 Dialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 16Dialkylated naphthalene is equivalent to; (c)x%C 14 Dialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 14 Trialkylated naphthalene equivalent; (d)x%C 14 Dialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 16 Trialkylated naphthalene is equivalent to; (e)x%C 16 Dialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 14 Trialkylated naphthalene is equivalent to; (f)x%C 16 Dialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 16 Trialkylated naphthalene equivalent; (g) x% C 14 Trialkylated naphthalene exhibits similar behavior to x%C in lubricant formulations. 16 Trialkylated naphthalene is equivalent to; and (h)x%C 14 Dialkylated naphthalene + y%C 14 Trialkylated naphthalene exhibits similar behavior to n%C in lubricant formulations. 16 Dialkylated naphthalene + m% C 16 Trialkylated naphthalene is equivalent to (x+y=n+m).

[0083] Based on the above assumptions, production includes C 14 AN blends and C 16 The AN blend is an alkylated naphthalene (“AN”) blend having an isomer ratio (di+tri) of <40% monoalkylated naphthalene and >60% polyalkylated naphthalene. In embodiments, the AN blend comprises greater than 30% by weight of dialkylated naphthalene. In embodiments, the AN blend of the present invention replaces the AN5 and AN12 blends in lubricant formulations. In embodiments, the AN blend of the present invention replaces the AN12 blend in lubricant formulations and may partially replace the AN5 blend.

[0084] In order to produce C 14 AN blends and / or C 16 AN blends, the following schemes are shown below:

[0085]

[0086] Method for producing AN blends

[0087] To produce the AN blend, naphthalene, linear α-olefin (“LAO”), and acidic MWW-type zeolite (i.e., MCM-22H and / or MCM-49H) are fed into the alkylation reactor along with a solvent stream and a recycle stream (from the vacuum distillation section). In this embodiment, the method is a batch process using a CSTR alkylation reactor with a filtration section (1 micrometer) and a vacuum distillation section. In this embodiment, unreacted olefin, naphthalene, solvent, and possible monoalkylates are each recycled to the alkylation reactor via a recycle stream fluidly connected between the vacuum distillation section and the alkylation reactor. In this embodiment, the recycled components can be collected in a drum and fed into the reactor at the start of the next batch. After the reaction is complete, a neutralizing agent and a filter aid are fed into the alkylation reactor. Solvents include, but are not limited to, Sasol 1012 solvent. Neutralizing agents and filter aids include, but are not limited to, lime, sodium carbonate, activated carbon, and celite.

[0088] To produce the AN blends of the present invention, the alkylation reaction is typically operated at atmospheric pressure at approximately 200°C to 210°C (375°F and 410°F). At this temperature and pressure, the reaction time is typically about 2 hours to convert more than 98.5% of the naphthalene feed to the reactor. Optionally, the reaction pressure is typically ambient pressure, and the reaction temperature is 200°C to 210°C to maximize selectivity and yield for highly alkylated naphthalene isomers without producing large amounts of LAO oligomer byproducts (LAO dimers, trimers). Lowering the reaction temperature results in decreased polyalkylate selectivity. Increasing the maximum temperature leads to the formation of LAO oligomers (PAO). Increasing the time at the maximum temperature also increases the formation of LAO oligomers (PAO). The olefin to naphthalene molar ratio also affects polyalkylate selectivity and the degree of LAO oligomer formation. Increasing the molar ratio above the optimal conditions (1.75 for LAO14 and 1.81 for LAO16) increases LAO oligomer formation. Lowering the reaction time below optimal conditions reduces selectivity for polyalkylate molecules. The reaction time can be varied depending on the alkylation strength of the catalyst.

[0089] Typically, the CSTR reactor is charged with naphthalene, a small amount of solvent, and catalyst at 90°C, and then heated to 200°C with stirring. Olefins are then continuously added to the hot naphthalene blend. The olefin addition rate is adjusted to take one hour. The reactor is then rapidly heated to 210°C, and the contents are stirred for 1–3 hours (alkylation conditions). Significant monoalkylate formation occurs during olefin addition, but the main alkylation to dialkylates and trialkylates occurs at higher temperatures. The reactor effluent is distilled under vacuum to remove unreacted naphthalene, unreacted olefins, and solvent at the top. Naphthalene tends to precipitate in the top system. A small amount of added solvent helps dissolve the naphthalene in the top system. 16The vacuum distillation section of the AN blend operates at a pressure of approximately 100 Torr to 3 Torr and a temperature of approximately 120°C to 205°C. 14 The vacuum distillation section of the AN blend was operated at pressures of approximately 100 Torr to 3 Torr and temperatures of approximately 120°C to 180°C. The operating conditions in experiments A through D represent optimized reaction conditions.

[0090] Table 6 lists exemplary components of the inputs and outputs of the alkylation reactor.

[0091] Table 6

[0092]

[0093] Catalyst charge amount affects the isomer ratio. Higher catalyst charge (more catalyst) improves selectivity for polyalkylated naphthalene products, but at a higher production cost. Catalyst charge can be minimized to produce the desired product selectivity and yield. In a laboratory reactor (Parr), the catalyst charge was reduced to 1 wt% / reactor batch while maintaining the desired isomer ratio in AN products of MA < 45 wt% and polyalkylates > 55 wt%. We believe that the catalyst charge can be further reduced in large-scale commercial reactors due to the much lower hot surface area to volume ratio. This must be confirmed in plant testing. Examples 2 through 5 list optimized conditions, including olefin to naphthalene feed ratio, olefin addition rate, catalyst charge amount, stirring rate (500 rpm), reaction temperature during olefin addition, reaction temperature during alkylation, alkylation time, catalyst neutralization, catalyst removal with a 1-micron filter, and fractionation conditions to meet the target molecular properties. Typically, the catalyst charge amount is from about 0.1 wt% to 2.0 wt% of the total weight of the reactor feed. Each of the following can be optimized to meet the target molecular properties: olefin to naphthalene feed ratio, olefin addition rate, catalyst charge, stirring rate, reaction temperature during olefin addition, reaction temperature during final cooking, final cooking time, catalyst removal efficiency, and fractionation conditions.

[0094] As shown in Tables 7A and 7B below, the physical and structural properties of the produced AN blends fall between those of the AN5 and AN12 blends. As shown in Tables 7A and 7B, RPVOT, min improves with the addition of 150 ppm L109 antioxidant.

[0095] Table 7A

[0096]

[0097] Table 7B

[0098]

[0099] Lubricant formulation

[0100] The lubricant formulations of this invention are typically formulated from synthetic base materials with a high viscosity index. The lubricant formulations (synthetic lubricant formulations) of this invention are characterized by low fluid friction to provide rust and corrosion protection, bearing wear protection (i.e., low FAG FE8 bearing test score), reduced power consumption, demulsification and foam control, and venting properties.

[0101] Alkylated naphthalene synthetic blends (sometimes also called "co-bases") are solubility enhancers used in lubricant formulations in a range of applications. For example, engine oils (diesel and gasoline) contain 1% to 5% wt% alkylated naphthalene to improve additive solubility and reduce sludge formation. In industrial applications, alkylated naphthalene is used in circulating and compressor oils for harsh operating conditions and to provide long drain intervals. In these applications, 10% to 65% wt% alkylated naphthalene is typically used in the total formulation. Alkylated naphthalene can also be used in power generation equipment (gas and steam turbines) at concentrations of 1% to 10% wt%. In these applications, alkylated naphthalene provides solubility and varnish reduction benefits. Gear oils also use alkylated naphthalene as a co-blender to improve additive solubility when used at 1% to 15% wt% of the lubricant formulation. Similarly, for particularly demanding applications, hydraulic oils rely on alkylated naphthalene in amounts up to 20% wt% of the total formulation.

[0102] As provided herein, the lubricant formulations of the present invention comprise one or more polyalphaolefin (“PAO base”) and one or more AN blends. PAO bases are typically used in automotive fluids, as well as hydraulic oils, gear oils, and bearing oils, operating in extremely cold or hot applications. PAO bases are also used as base fluids in some greases with a wide temperature range. However, PAO bases cause seal shrinkage and are insoluble in common oil additives. Therefore, PAO bases are combined with or blended with blends to provide lubricant formulations.

[0103] As provided herein, the PAO base material for the lubricant formulations of the present invention can be a conventional PAO base material and / or a metallocene PAO base material. Typically, polyalphaolefins (“PAOs”) are manufactured through synthetic chemistry derived from ethylene produced by cracking crude oil or natural gas. The polyalphaolefins produced in and exiting the reactor are olefins. Downstream hydrogenation converts the polyalphaolefins into hydrogenated PAOs. These PAOs do not contain cyclic structures, double bonds, sulfur, nitrogen components, or waxy hydrocarbons. The absence of these structures and materials results in nonpolar base oils with high viscosity index, excellent low-temperature flow and pour point characteristics, good oxidative stability, and compatibility with mineral oils, varnishes, and sealants commonly found in lubricant systems. Due to their controlled structure, PAOs do not contain lighter, more volatile (smaller) hydrocarbons, which reduces volatility, increases flash point, and produces less hydrocarbon tail gas emissions.

[0104] Conventional polyalphaolefins (“conventional PAO”) are homopolymers made from a single alpha-olefin (typically LAO8, LAO10, or LAO12). Conventional PAO can also be copolymers made from two or more alpha-olefins (typically LAO8, LAO10, or LAO12). Typically, the kinematic viscosity at 100°C ranges from 1 to 100. The viscosity index of conventional PAO ranges from 100 to 200. Conventional PAO can be produced using a BF3 catalyst system. Typically, BF3 is activated with one or more promoters, including alcohols such as methanol, ethanol, propanol, butanol, and other alcohols. Moderators such as acetates like ethyl acetate, ethyl butyrate, and others are often added.

[0105] Metallocene polyalphaolefins (“mPAOs”) are copolymers made from at least two or more alpha-olefins, or homopolymers made from a single alpha-olefin feedstock, or homopolymers made from a single alpha-olefin feedstock via a metallocene catalyst system. (WO2011 / 041647, paragraph

[0026] ). In embodiments, the activated metallocene catalyst for the production of PAOs may be a simple metallocene, substituted metallocene, or bridged metallocene catalyst activated or promoted by, for example, methylaluminoxane (MAO) or a noncoordinate anion such as N,N-dimethylphenylammonium tetra(perfluorophenyl)borate or other equivalent noncoordinate anions and optionally with a co-activator (typically a trialkylaluminum compound). (WO2011 / 041647, paragraph

[0031] ).

[0106] Hybrid PAO is another type of PAO. Hybrid PAO is produced by combining metallocene process steps with conventional BF3 process steps. For example, in the metallocene process steps, single LAOs (C6, C8, C...) are combined... 10 C 12 C 14 Or C 16The dimer is a LAO dimer olefin. This dimer, along with other LAO monomers, is fed into a BF3 reactor, where they copolymerize to produce a mixed PAO. The method for preparing mixed PAO can produce many different products, which can be blended with AN blends in lubricant formulations.

[0107] For example, in the implementation scheme, at least two and up to 26 different linear α-olefins (selected from C3-C4) are used. 30 The mPAO base is prepared by a mixed feed of linear α-olefins (“LAO”) from LAO. The mixed feed LAO is obtained by ethylene growth using an alumina catalyst or a metallocene catalyst (also known as a Ziegler-Natta catalyst). The grown olefins contain C6-C... 18 LAO. In the embodiment, a treatment step is performed to remove peroxides, oxygen, sulfur, nitrogen-containing organic compounds, and alkynes from the catalyst. See, for example, paragraphs

[0032] and

[0056] of WO2011 / 041647.

[0108] To prepare the lubricant formulation of the present invention, at least one alkylated naphthalene blend is blended with one or more PAO base materials. In an embodiment, the PAO base material has a viscosity KV100°C of about 2 centipoise (“cps”) to 300 cps. Additionally, the PAO base material contains amine antioxidant additives, defoamer additives, and / or inhibitor additives. In an embodiment, the lubricant formulation has a viscosity KV100°C of at least 4 cps and less than 100 cps, a metal content of 10 ppm to 1000 ppm, a sulfur content of less than 100 ppm and up to 8000 ppm, and a viscosity index (“VI”) greater than 95.

[0109] Table 8 provides the properties of exemplary lubricant formulations containing AN5 and AN12 blends for enhanced performance. The amount of alkylated naphthalene blend in the lubricant formulation can vary from (35+x) wt% AN5 blend to (65-x) wt% AN12 blend. The ratio of combined isomers in the lubricant formulation will vary from (39+x) wt% monoalkylated naphthalene to (61-x) wt% polyalkylated naphthalene.

[0110] Table 8

[0111] Exemplary Lubricant Formulation Properties

[0112]

[0113] As described herein, the AN blends of the present invention reduce the process cost of preparing lubricant formulations while maintaining the performance benefits currently provided by the combination of AN5 and AN12 blends. A method for preparing lubricant formulations is carried out without combining two blends by combining the AN blends of the present invention with a polyalphaolefin base. This method for preparing lubricant formulations omits the step of preparing a second blend and is carried out without the step of preparing a second blend. This method for preparing lubricant formulations does not require a trifluoromethanesulfonic acid catalyst and is carried out without a trifluoromethanesulfonic acid catalyst. Similarly, this method for preparing AN blends does not require a trifluoromethanesulfonic acid catalyst. The AN blends of the present invention are prepared without a trifluoromethanesulfonic acid catalyst. Furthermore, this method for preparing lubricant formulations (including AN blends) is carried out in a single-step method or in a method that does not require the combination of two blends. Although an optional second blend can be added to the lubricant formulations of the present invention, the lubricant formulations of the present invention do not require two or more blends.

[0114] The advantages and benefits of using this method for preparing lubricant formulations include reduced raw material transportation and improved economies of scale, along with the additional benefit of removing perfluorinated alkyl substances from the synthesis. The AN blends of this invention provide the solubility and oxidation benefits of AN5 blends and the optimal elastomer compatibility of AN12 blends.

[0115] The various aspects of the disclosure are described in more detail through specific embodiments. The following embodiments are provided for illustrative purposes and are not intended to limit the disclosure in any way. Those skilled in the art will readily recognize that various parameters can be changed or modified to obtain substantially the same results.

[0116] Example

[0117] Features of this disclosure are described in the following non-limiting embodiments.

[0118] Example 1

[0119] MCM-22 and MCM-49 are converted into acidic zeolites MCM-22H and MCM-49H.

[0120] Samples of synthesized MWW-type zeolites MCM-22 and MCM-49 were obtained via NH4 +The zeolite is exchanged and then calcined to transform into its acidic form (MCM-22H and MCM-49H, respectively). Ion exchange is carried out by contacting the zeolite with a 0.5 to 1 N ammonium nitrate solution, although other ammonium salt solutions such as NH4Cl can also be used for the same purpose. Ion exchange can be performed in batch (using an exchange column with a recirculating solution), semi-batch (using a filter press), or continuous (using a horizontal belt filter or extractor) operation, with the aim of removing sodium or other alkali metals from the synthetic zeolite crystals to low levels, typically <500 ppm. In batch operation, fresh ammonium salt solution is used for each subsequent exchange until the desired alkali metal concentration is achieved. Ion exchange is carried out at ambient temperature and pressure.

[0121] Following ion exchange, the zeolite crystals were washed with deionized water to remove residual ammonium salts before calcination. The zeolite crystals were first calcined in flowing nitrogen at 842℉ (450℃), followed by calcination in a nitrogen / air mixture at 1000℉ (538℃). The properties of the acid forms of zeolites MCM-22H and MCH-49H are then provided in Table 9.

[0122] Table 9

[0123] Characterization of ion exchange and TOSOH ion exchange zeolites (laboratory scale).

[0124]

[0125] Using the catalysts described above, we prepared C in the acidic forms MCM-22H and MCM-49H of MCM-22 and MCM-49 in a stepwise batch process. 14 AN blends and C 16 AN blends, as described below in Examples 2 to 5.

[0126] Example 2

[0127] C 16 AN blend step-by-step intermittent method

[0128] We are prepared to produce C using a step-by-step intermittent method. 16Four experiments with the AN blend (Experiment A, Tables 7A and 7B) were conducted. First, 605.3 g of 1-hexadecene (LAO16) was weighed and placed in an addition flask connected to a metering pump. 190.7 g of naphthalene, 12.4 g of MCM-22H catalyst, and 16.5 g of Sasol 1012 n-alkane co-solvent were added to a 2-liter Parr reactor. The reactor headspace was pressurized with nitrogen and evacuated. This nitrogen pressurization and evacuation process was repeated several times. The reactor contents were then heated to 90°C and stirred at an increased speed of 500 rpm. The reactor temperature was raised to 200°C before adding LAO16. LAO16 was then added to the reactor by opening the LAO16 feed valve and operating the feed pump at a flow rate of 10.1 g / min for 60 minutes. Once the addition of LAO16 was complete, the feed pump was turned off and the feed valve was closed. To complete the alkylation reaction, the reactor temperature was rapidly raised to 210°C and maintained at this temperature for 60 minutes. The reactor temperature was then cooled to room temperature using a water cooling system, and the pressure was released from the reactor. The reactor effluent was double-filtered at ambient temperature using a fresh filter bed (Celite 545 filter aid). The filtered reactor effluent was then loaded into a vacuum distillation apparatus, and unreacted naphthalene, LAO16, and Sasol 1012 solvent were removed at the top to achieve <0.5% by weight of unreacted naphthalene and unreacted olefins. Losses due to sampling were accounted for. 16 Yield of An blend >80% by weight.

[0129] Example 3

[0130] C treated with baking soda ash 16 Synthesis of AN blends

[0131] We are prepared to produce C using a step-by-step intermittent method. 16Six experiments with the AN blend (Experiment B, Tables 7A and 7B) were conducted. First, 607.8 g of 1-hexadecene (LAO16) was weighed and placed in an addition flask connected to a metering pump. 191.5 g of naphthalene, 8.2 g of MCM-22H catalyst, and 16.5 g of Sasol 1012 n-alkane co-solvent were added to a 2-liter Parr reactor. The reactor headspace was pressurized with nitrogen and evacuated. This nitrogen pressurization and evacuation process was repeated several times. The reactor contents were then heated to 90°C and stirred at an increased speed of 500 rpm. The reactor temperature was raised to 200°C before adding LAO16. LAO16 was then added to the reactor by opening the LAO16 feed valve and operating the feed pump at a flow rate of 10.1 g / min for 60 minutes. Once the addition of LAO16 was complete, the feed pump was turned off and the feed valve was closed. To complete the alkylation reaction, the reactor temperature was rapidly raised to 210°C and maintained at this temperature for 60 minutes. The reactor temperature was then cooled to room temperature using a water cooling system, and the pressure was released from the reactor. 1 gram of soda ash was added to the reactor to neutralize the catalyst, and the reactor contents were stirred for 60 minutes. The reactor effluent was double-filtered at ambient temperature using a fresh filter bed (Celite 545 filter aid). The filtered reactor effluent was then loaded into a vacuum distillation apparatus, and unreacted naphthalene, LAO16, and Sasol 1012 solvent were removed at the top to achieve <0.5% by weight of unreacted naphthalene and unreacted olefins. Losses due to sampling were accounted for. 16 Yield of An blend >80% by weight.

[0132] Example 4

[0133] C 14 AN blend step-by-step intermittent method

[0134] We are prepared to produce C using a step-by-step intermittent method. 14Four experiments with the AN blend (Experiment C, Tables 7A and 7B) were conducted. First, 581.0 g of 1-tetradecene (LAO14) was weighed and placed in an addition flask connected to a metering pump. 217.2 g of naphthalene, 8.2 g of MCM-22H catalyst, and 16.5 g of Sasol 1012 n-alkane co-solvent were added to a 2-liter Parr reactor. The reactor headspace was pressurized with nitrogen and evacuated. This nitrogen pressurization and evacuation process was repeated several times. The reactor contents were then heated to 90°C and stirred at an increased speed of 500 rpm. The reactor temperature was raised to 200°C before adding LAO14. LAO14 was then added to the reactor by opening the LAO14 feed valve and operating the feed pump at a flow rate of 9.7 g / min for 60 minutes. Once the addition of LAO14 was complete, the feed pump was turned off and the feed valve was closed. To complete the alkylation reaction, the reactor temperature was rapidly raised to 210°C and maintained at this temperature for 60 minutes. The reactor temperature was then cooled to room temperature using a water cooling system, and the pressure was released from the reactor. Double filtration of the reactor effluent was performed at ambient temperature using a fresh filter bed (Celite 545 filter aid). The filtered reactor effluent was then loaded into a vacuum distillation apparatus, and unreacted naphthalene, LAO14, and Sasol 1012 solvent were removed at the top to achieve <0.5% by weight of unreacted naphthalene and unreacted olefins. Losses due to sampling were accounted for. 14 Yield of An blend >80% by weight.

[0135] Example 5

[0136] C treated with baking soda ash 14 Synthesis of AN blends

[0137] We are prepared to produce C using a step-by-step intermittent method. 14The experiment with the AN blend (Experiment D, Tables 7A and 7B) began with 581.0 g of 1-tetradecene (LAO14) weighed and placed in an addition flask connected to a metering pump. 217.2 g of naphthalene, 8.2 g of MCM-22H catalyst, and 16.5 g of Sasol 1012 n-alkane co-solvent were added to a 2 L Parr reactor. The reactor headspace was pressurized with nitrogen and evacuated. This nitrogen pressurization and evacuation process was repeated several times. The reactor contents were then heated to 90°C and stirred at an increased speed of 500 rpm. The reactor temperature was raised to 200°C before adding LAO14. LAO14 was then added to the reactor by opening the LAO14 feed valve and operating the feed pump at a flow rate of 9.7 g / min for 60 minutes. Once the addition of LAO14 was complete, the feed pump was turned off and the feed valve was closed. To complete the alkylation reaction, the reactor temperature was rapidly raised to 210°C and maintained at this temperature for 60 minutes. The reactor temperature was then cooled to room temperature using a water cooling system, and the pressure was released from the reactor. 1 gram of soda ash was added to the reactor to neutralize the catalyst, and the reactor contents were stirred for 60 minutes. The reactor effluent was double-filtered at ambient temperature using a fresh filter bed (Celite 545 filter aid). The filtered reactor effluent was then loaded into a vacuum distillation apparatus, and unreacted naphthalene, LAO14, and Sasol 1012 solvent were removed at the top to achieve <0.5% by weight of unreacted naphthalene and unreacted olefins. Losses due to sampling were accounted for. 14 Yield of An blend >80% by weight.

[0138] Example 6

[0139] Lubricant formulations using AN blends

[0140] The alkylated naphthalene blends from Experiments A, B, C, and D were then tested as blends for lubricant formulations, which reduced costs while maintaining the performance benefits provided by the combination of AN5 and AN12 blends. Using a single-step synthesis (compared to two different synthesis steps at two different locations) offers benefits in terms of reduced raw material transportation, improved economies of scale, and removal of perfluorinated alkyl substances from the synthesis. The AN blends provide the solubility and oxidation benefits of the AN5 blend and the optimal elastomer compatibility of the AN12 blend.

[0141] Tables 10A, 10B, 11A, and 11B below provide available lubricant formulations.

[0142] Table 10A

[0143]

[0144] Table 10B

[0145]

[0146] Table 11A

[0147]

[0148] Table 11B

[0149]

[0150] As shown in Table 12, performance tests demonstrate the performance of the AN blends of lubricant formulations D in Tables 11A and 11B (both based on C) when used in fully formulated lubricants. 14 and C 16 Equivalences between [the present invention and its AN blends] are provided. Data are compared with reference lubricant formulations, and performance comparable to that of the AN blends of the present invention is shown. The AN blends provided herein can be used in product applications ranging from 1% to 60% by weight, such as for lubricant formulations for passenger vehicles, commercial vehicles, industrial applications, and greases and additives.

[0151] Table 12

[0152] Properties of Lubricant Formulation C using AN blends

[0153]

[0154]

[0155] Additional implementation schemes

[0156] Alternatively or concurrently, the present invention relates to:

[0157] Implementation Scheme 1. A method for preparing AN blends, comprising the following steps:

[0158] A mixed acid form of MWW-type catalyst, naphthalene, and a solvent are used to provide a reaction mixture, wherein the acid form of the MWW-type catalyst has an average particle size distribution of 55 to 85 µm and a particle size distribution of 475 to 600 µm. 2 / g surface area, and total acidity of 0.80 to 1.0 meq / g TPAD;

[0159] Increase the temperature of the reaction mixture; and

[0160] Linear α-olefins are added to the reaction mixture to produce AN blends having an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

[0161] Implementation Scheme 2. The method for preparing AN blends according to Implementation Scheme 1, wherein the AN blends have a kinematic viscosity KV100 between about 7.0 and about 9.5 cSt as measured by D445.

[0162] Implementation Scheme 3. The method for preparing AN blends according to Implementation Scheme 1, wherein the acid form MWW-type catalyst is MCM-22H.

[0163] Implementation Scheme 4. The method for preparing AN blends according to Implementation Scheme 1, wherein the catalyst loading is less than 1.5% by weight.

[0164] Implementation Scheme 5. The method for preparing AN blends according to Implementation Scheme 1, wherein the linear α-olefin comprises LAO14.

[0165] Implementation Scheme 6. The method for preparing AN blends according to Implementation Scheme 1, wherein the linear α-olefin comprises LAO16.

[0166] Implementation Scheme 7. The method for preparing AN blends according to Implementation Scheme 1, wherein the polyalkylated naphthalene comprises dialkylated naphthalene and trialkylated naphthalene.

[0167] Implementation Scheme 8. The method for preparing AN blends according to Implementation Scheme 1, wherein the AN blends contain more than 30% by weight of dialkylated naphthalene.

[0168] Implementation Scheme 9. The method for preparing AN blends according to Implementation Scheme 1, wherein at least 98% by weight of naphthalene is converted.

[0169] Implementation Scheme 10. The method for preparing AN blends according to Implementation Scheme 1, wherein the AN blends are prepared without a trifluoromethanesulfonic acid catalyst.

[0170] Implementation Scheme 11. A lubricant formulation comprising an AN blend produced by the method according to any of the foregoing implementation schemes.

[0171] Implementation Scheme 12. A method for preparing a lubricant formulation, comprising a step of blending a PAO base material with an AN blend in a single step, wherein the lubricant formulation has a kinematic viscosity of 25 to 30 KV100 as measured by D445-3 and has an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

[0172] Implementation Scheme 13. The method for preparing a lubricant formulation according to Implementation Scheme 12, wherein the method does not include the step of combining two or more blends.

[0173] Implementation Scheme 14. The method for preparing a lubricant formulation according to Implementation Scheme 12, wherein the AN blend is prepared without a trifluoromethanesulfonic acid catalyst.

[0174] Implementation Scheme 15. AN blend comprising monoalkylated naphthalene and polyalkylated naphthalene AN blend having a KV100 of 7.0 to 9.5 cSt as measured by ASTM D445 and a Noack% of 5.0 to 11.0 as measured by ASTM D5800, wherein the AN blend has an isomer ratio of less than 40% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

[0175] Implementation Scheme 16.AN blend, provided by the following: a mixture of an acidic form of MWW-type catalyst, naphthalene, and a solvent to provide a reaction mixture, wherein the acidic form of the MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 µm. 2 / g surface area, and total acidity of 0.80 to 1.0 meq / g TPAD; increasing the temperature of the reaction mixture; and adding linear α-olefins to the reaction mixture, the AN blend having an isomer ratio of less than 45 wt% monoalkylated naphthalene and greater than 55 wt% polyalkylated naphthalene and a kinematic viscosity of 7.0 to 9.5 cSt KV100 as measured by ASTM D445.

[0176] Implementation Scheme 17. An acidic MWW-type catalyst composition comprising:

[0177] 5.0% to 7.5% by weight of alumina;

[0178] 69% to 80% by weight of silicon dioxide;

[0179] Approximately 17.0 wt% to 24.0 wt% Si / Al2;

[0180] Less than 0.03% by weight of potassium; and

[0181] Sodium content less than or equal to 0.05% by weight, measured by ICP test.

[0182] The acidic MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 μm. 2 Total surface area per g, total acidity of 0.80 to 1.0 meq / g TPAD, and trimethylpyridine absorption of 125 to 145 µmol / g.

[0183] Implementation Scheme 18. The method for preparing AN blends according to Implementation Scheme 1, wherein the linear α-olefin is mPAO.

[0184] Implementation Scheme 19. The method for preparing AN blends according to Implementation Scheme 1, wherein the linear α-olefin is a blend of PAO.

[0185] Implementation Scheme 20. A method for preparing AN blends according to Implementation Scheme 1, wherein the linear α-olefin comprises at least two different C3-C4 olefins. 30 Linear α-olefins of LAO.

[0186] In view of the foregoing description, many changes, modifications and variations will be apparent to those skilled in the art without departing from the spirit or scope of this disclosure, and when lower and upper limits of numerical values ​​are listed herein, a range from any lower limit to any upper limit is covered.

Claims

1. A method for preparing AN blends, comprising the following steps: A mixed acid form of MWW-type catalyst, naphthalene, and a solvent are used to provide a reaction mixture, wherein the acid form of MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 µm. 2 / g surface area, and total acidity of 0.80 to 1.0 meq / g TPAD; Increase the temperature of the reaction mixture; and Linear α-olefins are added to the reaction mixture to produce AN blends having an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

2. The method for preparing AN blends according to claim 1, wherein the AN blends have a kinematic viscosity KV100 of about 7.0 to about 9.5 cSt as measured by D445.

3. The method for preparing AN blends according to claim 1, wherein the acid-form MWW-type catalyst is MCM-22H.

4. The method for preparing AN blends according to claim 1, wherein the catalyst loading is less than 1.5% by weight.

5. The method for preparing AN blends according to claim 1, wherein the linear α-olefin comprises LAO14.

6. The method for preparing AN blends according to claim 1, wherein the linear α-olefin comprises LAO16.

7. The method for preparing AN blends according to claim 1, wherein the polyalkylated naphthalene comprises dialkylated naphthalene and trialkylated naphthalene.

8. The method for preparing AN blends according to claim 1, wherein the AN blends contain more than 30% by weight of dialkylated naphthalene.

9. The method for preparing AN blends according to claim 1, wherein at least 98% by weight of naphthalene is converted.

10. The method for preparing AN blends according to claim 1, wherein the AN blends are prepared without a trifluoromethanesulfonic acid catalyst.

11. A lubricant formulation comprising an AN blend produced by the method according to any one of the preceding claims.

12. A method for preparing a lubricant formulation, comprising a step of blending a PAO base material with an AN blend in a single step, wherein the lubricant formulation has a kinematic viscosity of 25 to 30 KV100 as measured by D445-3 and has an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

13. The method for preparing a lubricant formulation according to claim 12, wherein the method does not include the step of combining two or more blends.

14. The method for preparing a lubricant formulation according to claim 12, wherein the AN blend is prepared without a trifluoromethanesulfonic acid catalyst.

15. AN blends comprising monoalkylated naphthalene and polyalkylated naphthalene AN blends having a KV100 of 7.0 to 9.5 cSt as measured by ASTM D445 and a Noack% of 5.0 to 11.0 as measured by ASTM D5800, wherein the AN blends have an isomer ratio of less than 45% by weight of monoalkylated naphthalene and greater than 55% by weight of polyalkylated naphthalene.

16. An AN blend, formed by providing a reaction mixture of a mixed acid-form MWW-type catalyst, naphthalene, and a solvent, wherein the acid-form MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 μm. 2 / g surface area, and total acidity of 0.80 to 1.0 meq / g TPAD; increasing the temperature of the reaction mixture; and adding linear α-olefins to the reaction mixture, the AN blend having an isomer ratio of less than 45 wt% monoalkylated naphthalene and greater than 55 wt% polyalkylated naphthalene and a kinematic viscosity of 7.0 to 9.5 cSt KV100 as measured by ASTM D445.

17. An acidic MWW-type catalyst composition comprising: 5.0% to 7.5% by weight of alumina; 69% to 80% by weight of silicon dioxide; Approximately 17.0 wt% to 24.0 wt% Si / Al2; Less than 0.03% by weight of potassium; and Sodium content less than or equal to 0.05% by weight, measured by ICP test. The acidic MWW-type catalyst has an average particle size distribution of 55 µm to 85 µm and a particle size distribution of 475 to 600 μm. 2 Total surface area per g, total acidity of 0.80 to 1.0 meq / g TPAD, and trimethylpyridine absorption of 125 to 145 µmol / g.

18. The method for preparing AN blends according to claim 1, wherein the linear α-olefin is mPAO.

19. The method for preparing AN blends according to claim 1, wherein the linear α-olefin is a blend of PAO.

20. The method for preparing AN blends according to claim 1, wherein the linear α-olefin comprises at least two different C3-C4 olefins. 30 Linear α-olefins of LAO.

Images