Process for the production of base oils from linear alpha-olefins by oligomerization

Abstract

In the oligomerization process, hydrogenation is subsequently carried out on a solid acid catalyst to upgrade linear α-olefins with 10 carbon atoms and heavier to provide hydrogenated oligomers with Group II+ and Group III base oil properties for subsequent use in lubricant formulations and other applications.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 613,516, filed December 21, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to C 14+ Dimerization of linear α-olefins and mixtures thereof in an oligomerization process, said oligomerization process producing hydrogenated oligomers that can be used as base oils having Group II+ / Group III base oil properties. Background Technology

[0004] Higher molecular weight C12 and heavier carbon number linear α-olefins (“LAO”) are commonly used as feedstocks for the production of less branched alcohols for surfactant applications and the heaviest LAOs (C12 and C23) that can be used in synthetic wax applications (e.g., candles, crayons, extrusion aids). 20 -C 24 and C 24+ ) fraction. By making C 12+ Recent work on using LAO dimer to synthesize base oils to improve their quality above that of chemical intermediates or surfactants has been highly challenging and therefore not commonly practiced commercially. Summary of the Invention

[0005] This article provides methods for producing base oils, including: providing oils containing C 14+ LAO raw material; the LAO raw material is contacted with a solid acid catalyst to produce a product containing C. 14+ An oligomer mixture of LAO dimer and monomer; the C during distillation. 14+ Separation of the monomers from the LAO dimer and oligomer mixture; and hydrogenation of the C 14+ LAO dimers are used to produce base oils having a KV100 of 2.7 to 3.5 and a KV40 of 12 to 15 cSt as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270. The solid acid catalyst is an MWW framework zeolite.

[0006] A method for producing a variety of synthetic hydrocarbons is also provided, comprising: providing an LAO feedstock comprising LAO and mixtures thereof; contacting the LAO feedstock with a solid acid catalyst to produce an oligomer mixture comprising at least one dimer of LAO and a monomer; separating the LAO dimer from the monomer; and hydrogenating the LAO dimer to produce a variety of synthetic hydrocarbons having a KV100 of 2.7 to 3.5 and a KV40 of 12 to 15 cSt as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270. The LAO is in the liquid phase and the solid acid catalyst is an MWW-type zeolite.

[0007] These and other features and properties of the catalyst complexes and methods disclosed herein, and their advantageous applications and / or uses, will become apparent from the following detailed description. Attached Figure Description

[0008] To assist those skilled in the art in creating and using this subject matter, please refer to the accompanying drawings, in which:

[0009] Figure 1A This demonstrates the selectivity of the solid acid catalyst ZSM-57 in producing various linear and branched hydrocarbons and its performance for C at three different temperatures and two different feed flow rates. 14 A graph showing the activity of LAO conversion rate.

[0010] Figure 1B This demonstrates the selectivity of the solid acid catalyst ZSM-23 in producing various linear and branched hydrocarbons and its performance for C at three different temperatures and two different feed flow rates. 14 A graph showing the activity of LAO conversion rate.

[0011] Figure 1C This demonstrates the selectivity of the solid acid catalyst MCM-49 in producing various linear and branched hydrocarbons at three different temperatures and two different feed flow rates, as well as its performance for C40. 14 A graph showing the activity of LAO conversion rate.

[0012] Figure 1D This demonstrates the selectivity of the solid acid catalyst HPW in producing various linear and branched hydrocarbons and its effectiveness for C at three different temperatures and two different feed flow rates. 14 A graph showing the activity of LAO conversion rate.

[0013] Figure 2 The C values ​​for each solid acid catalyst ZSM-57, ZSM-23, MCM-49, and HPW are shown. 14 LAO dimer selectivity, C 14 A graph showing LAO conversion rate and yield.

[0014] Figure 3 Conversion and selectivity curves of the dimers produced by the method described in the examples using the solid acid catalyst MCM-49 are provided.

[0015] Figure 4 It is a graph summarizing the carbon number distribution of each collected distillate fraction and the final central fraction of the total reactor effluent from the methods described in the embodiments.

[0016] Figure 5 The distillation curve is a reconstructed distillation curve of the method in the example embodiment, including (hollow circles) and excluding (solid circles) the added Primol 542 substrate. Detailed Implementation

[0017] Before disclosing and describing the compounds, components, compositions, and / or methods of the present invention, it should be understood that, unless otherwise stated, this disclosure is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, catalyst structures, etc., as they can vary, unless otherwise stated. It should also be understood that the terminology used herein is for the purpose of describing different embodiments and is not intended to be limiting.

[0018] All numerical values ​​in this detailed description and claims should be considered to be modified by “about” or “approximately” to account for experimental error and variation.

[0019] For the sake of brevity, this document only explicitly discloses specific ranges. However, any lower bound can be combined with any upper bound to describe a range that is not explicitly stated, and a range consisting of any lower bound can be combined with any other lower bound to describe a range that is not explicitly stated; similarly, a range consisting of any upper bound can be combined with any other upper bound to describe a range that is not explicitly stated. Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly stated. Therefore, each point or individual value can serve as its own lower or upper bound combined with any other point's individual value or any combination of lower or upper bounds to describe a range that is not explicitly stated.

[0020] For the purposes of this disclosure, the following definitions will apply:

[0021] As used herein, the terms “a” and “the” should be understood to include both the plural and singular forms.

[0022] For the purposes of this invention and its claims, the numbering scheme for the periodic table families is based on the IUPAC periodic table of elements as of January 1, 2020.

[0023] The term “and / or” as used in this article, such as “A and / or B”, is intended to include “A and B”, “A or B”, and “A” and “B”.

[0024] As used herein, the term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond ((R1R2)-C=CH2) in its structure.

[0025] The term "base oil" refers to a lubricant component produced by a single manufacturer to the same specifications (regardless of the source of feed or manufacturer location), meeting the specifications of the same manufacturer, and identified by a unique formula, product identification number, or both. American Petroleum Institute (API) 1509, Engine Oil Licensing and Certification System, 15th Edition, April 2002, Appendix E. API Base Oil Interchangeability Guide for Passenger Car Engine Oils and Diesel Engine Oils, 2004, Section E.1.2, Definitions (Washington, D.C.: American Petroleum Institute).

[0026] Unless otherwise stated, the term "hydrocarbon" refers to a type of compound containing hydrogen bound to carbon and covers (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different n values.

[0027] Term "C" n "or "C n "Hydrocarbon", where n is a positive integer, means (i) any hydrocarbon compound having a total of n carbon atoms in its molecular structure, or (ii) any mixture of two or more such hydrocarbon compounds (i). Such C n Hydrocarbons may contain any degree of unsaturation. For example, unless otherwise specified, C2 hydrocarbons may refer to ethane, ethylene, acetylene, or a mixture of at least two of these hydrocarbons in any proportion.

[0028] Term "C" n+ "Hydrocarbon" means (i) any hydrocarbon compound containing n or more carbon atoms in its molecular structure, or (ii) any mixture of two or more such hydrocarbon compounds (i).

[0029] As used herein, the terms “paraffin,” “alkane,” and “saturated hydrocarbon” are synonymous and refer to hydrocarbons with a carbon content of 1000 kJ / kcal. n H 2n+2 Hydrocarbons of the form of .

[0030] As used in this article, the terms “linear” and “normal” are synonymous and refer to hydrocarbons without side chains.

[0031] As used in this article, the term “cracking” refers to the transformation of a given hydrocarbon molecule into two smaller hydrocarbon molecules.

[0032] As used in this article, the term "isomerization" refers to the rearrangement of the hydrocarbon skeleton, particularly the conversion of orthoparaffin into branched paraffin.

[0033] As used herein, the term “weight time space velocity” (WHSV) refers to a measure of the weight of the feed mixture flowing per hour per unit weight of catalyst.

[0034] As used herein, the term “liquid time space velocity” (LHSV) refers to a measure of the volume of the feed mixture flowing per unit volume of catalyst per hour.

[0035] As used in this article, "lubricant" refers to a substance that can be introduced between two or more moving surfaces and reduce the level of friction between two adjacent surfaces that are moving relative to each other.

[0036] As used herein, “olefin” means an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond in its structure, wherein the carbon-carbon double bond does not form part of an aromatic ring. Olefins can be straight-chain, branched, or cyclic. “Olefin” is intended to include all structural isomers of olefins unless the statement indicates a single isomer or the context clearly indicates otherwise.

[0037] As used herein, the term "viscosity index" or "VI" is a measure of how much viscosity changes with temperature; a higher VI indicates less variation, and generally, a higher VI is preferred. VI is typically calculated from measurements taken at 40°C and 100°C. The minimum VI for paraffinic base oils is typically from about 80 to about 95, as established by the demands of the automotive market.

[0038] As used herein, the term "pour point" is the temperature at which the base oil no longer flows. For paraffinic base oils, the pour point can be from about -12°C to about -15°C, as determined by the operation of the dewaxing unit. For specific purposes, the pour point can be much lower. Naphthenic base oils with very low wax content can have much lower pour points (-30°C to -50°C). For very viscous base oils such as bright oils, the pour point reflects the viscosity limit. Pour point is measured according to ASTM D97.

[0039] As used herein, the term “MWW-type zeolite MCM-49” is interchangeable with the terms “MCM-49”, “zeolite MCM-49”, and “synthetic MCM-49”.

[0040] As used herein, “MWW framework-type crystalline microporous materials” include one or more of the following: (1) molecular sieves made of typical primary crystalline building unit cells having an MWW framework topology, which is the spatial arrangement of atoms describing the crystal structure if laid out in three-dimensional space, such crystal structures are described in the “Atlas of Zeolite Framework”. "Types", fifth edition, mid-2001 discussion; (2) a molecular sieve made of ordinary secondary building units, which is a two-dimensional tiling of such MWW framework topology cells to form a monolayer of one cell thickness, preferably a monolayer of one c-cell thickness; (3) a molecular sieve made of ordinary secondary building units, which is a layer of one or more cell thicknesses, wherein the layer of more than one cell thickness is made by stacking, piling or combining monolayers of at least two MWW framework topology cells, wherein such stacking of secondary building units can be in a regular manner, an irregular manner, a random manner or any combination thereof; and (4) a molecular sieve made by any regular or random two-dimensional or three-dimensional combination of cells having an MWW framework topology.

[0041] As used herein, the term "variable oxidation state metal" refers to a metal having two or more available oxidation states other than zero.

[0042] As used herein, the term “total surface area” refers to the total external and internal specific surface area of ​​a dispersed or porous solid (microporous material), which is obtained by measuring the amount of physically adsorbed N2 adsorption / desorption isotherms, as specified in ISO 9277.

[0043] As used herein, the term "corridin absorption" refers to the number of millimoles of corridin (a type of catalyst poison) absorbed per gram of sample. In a non-limiting example, the sample was exposed to corridin and the amount of corridin adsorbed was measured gravimetrically after drying at 200°C under a nitrogen stream for 60 minutes on a thermogravimetric analyzer (model Q5000, manufactured by TA Instruments, New Castle, Delaware).

[0044] The term linear α-olefin (“LAO”), also known as terminal olefin or terminal olefin, means having the chemical formula C x H 2x A linear hydrocarbon having a double bond between the first carbon (C-1) and the second carbon (C-2), where x is an integer greater than or equal to 2.

[0045] LAO is typically separated from petroleum refining streams. Alternatively, linear α-olefins are synthesized from low molecular weight feedstocks, such as via the metathesis of ethylene, or by separation as a byproduct of Fischer-Tropsch synthesis. Biomass-derived linear α-olefins and linear α-olefins can also be obtained from other sources. Industrially, linear α-olefins are typically produced by oligomerization of ethylene or by Fischer-Tropsch synthesis followed by purification. On a small scale, another route for commercially used linear α-olefins is the dehydration of alcohols.

[0046] Low-carbon number (LCO) monomers are used as comonomers in polyethylene production. For example, C4 to C8 LAOs are monomers used in copolymerization processes to produce linear low-density polyethylene (“LLDPE”). C4 to C8 LAOs are also used to produce linear aldehydes via carbonyl synthesis (hydroformylation), which are then used to produce short-chain fatty acids, carboxylic acids, or linear alcohols for plasticizer applications via hydrogenation of the aldehydes. Furthermore, C... 10 The primary application of LAO is as a raw material in the production of polyalphaolefins (“PAO”), which is then blended into high-performance lubricant formulations. LAO C4 to C 12 It is also used for hydroformylation or alkylation and further processing into surfactants.

[0047] In the dimerization method, C 4+ LAO is the preferred raw material. However, C4 to C 10 LAO is an expensive commercial raw material with high demand. 12+ Existing dimerization methods for LAO include metathesis, Lewis acid (BF3) routes, or metallocene-based (homogeneous) catalyst routes. See, for example, U.S. Publication Nos. 2023 / 0127018 and WO2020 / 068527. These methods using LAO feedstocks with a large carbon number are relatively expensive compared to oligomerization over solid acid catalysts.

[0048] For example, linear α-olefin dimerization via metathesis using a metal carbene catalyst provides linear olefin dimers and an equal amount of ethylene loss. A single linear α-olefin can self-dimerize to form a linear olefin dimer, or two different linear α-olefins can form an asymmetric linear olefin dimer. Mixtures of linear olefin dimers with different carbon chain lengths can also be formed in this manner. The linear olefin dimers contain two fewer carbon atoms than the total number of carbon atoms in the linear α-olefin from which they are produced (as a result of ethylene loss). See paragraph

[0017] of US20230127018A1.

[0049] Methods for LAO dimerization via metathesis include the need to purify the olefin feedstock to remove one or more impurities. Purification can mitigate the presence of one or more of these impurities (e.g., oxygen-containing compounds, moisture, metals, heteroatoms, and any combination thereof), particularly during metathesis processes (e.g., dimerization) catalyzed by metal carbene catalysts. Purification may include contacting the feedstock with an adsorbent, bubbling the feedstock with an inert gas, or any combination thereof at the same or different locations (one or more), and purifying the linear olefin dimer from light substances and unreacted feedstock by distillation / flash evaporation and / or falling film evaporation, thereby limiting the amount of impurities returned to the metathesis reaction when the feedstock is recycled. US20230127018A1, paragraph

[0067] .

[0050] Furthermore, since metathesis is a reversible reaction, the formation of linear olefin dimers requires the removal of ethylene produced during the metathesis reaction. Removing ethylene can drive the reaction equilibrium toward the linear olefin dimer product. For example, during the metathesis reaction, parallel stripping and ethylene gas removal can be performed. Ethylene stripping can be performed using an inert gas feed stream, bubbling the reaction products with an inert gas, or applying a partial vacuum. See, for example, paragraph

[0078] of US20230127018A1.

[0051] Furthermore, during metathesis reactions, deactivated metal carbene catalysts and metal carbene catalyst residues can act as poisons to the fresh catalyst. Used catalysts (e.g., transition metals, ligands, or any combination thereof) need to be removed from the reaction products. Used catalysts can be further deactivated by quenching treatments containing, for example, vinyl halides or vinyl ethers (e.g., ethyl vinyl ether). See paragraph

[0080] of US20230127018A1.

[0052] The method of this invention produces hydrogenated oligomers and / or multiple hydrogenated oligomers (multiple synthetic hydrocarbons) without the need for cooling or quenching prior to the step of separating the dimers from the monomers. The resulting hydrogenated oligomers can be used as base oils. The method of this invention provides a route for upgrading LAO with 10 or more carbon atoms to base oil products with a higher performance / cost ratio than chemical intermediates or surfactants, by dimerizing LAO into synthetic hydrocarbons to produce base oils with group II+ / III base oil properties. In one embodiment, the method of this invention has the advantage of using C at a reduced cost. 14+ Advantages of LAO feedstock in producing base oils.

[0053] The raw materials used in the method of the present invention include one or more of the following: C 10+ LAO monomer, C 12+ LAO monomer, C 14+ LAO monomers and / or C16+ LAO monomer; C 10+ LAO monomer, C 12+ LAO monomer, C 14+ LAO monomers and / or C 16+ A mixture of one or more LAO monomers; and C 10+ LAO, C 12+ LAO, C 14+ LAO, C 16+ LAO and / or C 18+ LAO or a mixture of higher grades. In the embodiment, the raw materials are C with a 1:1:1 ratio. 12 LAO, C 14 LAO and C 16 A mixture of LAO in a molar ratio of 1:2:1. In the embodiment, the raw materials are C... 12 LAO, C 14 LAO and C 16 A mixture of LAO in a molar ratio of 1:2:3:2:1. In an embodiment, the raw materials are C4O4 with a molar ratio of 1:2:3:2:1. 10 LAO, C 12 LAO, C 14 LAO, C 16 LAO and / or C 18 The molar ratio of LAO to LAO in a mixture.

[0054] As provided in this article, LAO with 14 or more carbon atoms and including C 10 LAO, C 12 LAO, C 14 LAO, C 16 LAO and / or C 18 The LAO mixture is converted over a solid acid catalyst to produce a variety of synthetic hydrocarbons (also referred to herein as hydrogenated oligomers) with properties similar to those of Group II+ / III base oils. The conversion is carried out through the dimerization and isomerization of a combination of olefins, followed by hydrogenation. As described herein, the solid acid catalyst comprises an MWW framework zeolite, preferably MCM-49.

[0055] Typically, the polymerization of linear α-olefin monomers in the presence of a catalyst system can produce a large number of molecules with varying degrees of oligomerization. Therefore, the oligomers can be dimers (generated from two terminal olefin molecules), trimers (generated from three terminal olefin molecules), tetramers (generated from four terminal olefin molecules), or any other oligomers or polymers comprising two or more structural units derived from one or more terminal olefin monomers. As described herein, oligomerization conditions affect the distribution of oligomers produced by the method. Oligomerization methods are typically carried out in the presence of a catalyst system and at temperatures ranging from 120°C to 220°C and pressures up to 300 bar.

[0056] The oligomerization method steps include: (i) providing C 10 C 12 and / or C 14+ LAO feedstock and mixtures thereof; (ii) contacting the LAO feedstock with a catalyst system under oligomerization conditions in at least one oligomerization reactor to obtain an oligomerization reaction mixture comprising unreacted olefin monomers (one or more), dimers and higher oligomers, and the catalyst system; (iii) separating the unreacted monomers (one or more) from the oligomerization reaction mixture to obtain an unsaturated product precursor; and (iv) hydrogenating the unsaturated product precursor in the presence of hydrogen under hydrogenation conditions in a hydrogenation reactor to obtain hydrogenated oligomers (synthetic hydrocarbons). Optionally, the hydrogenated oligomers undergo a second distillation step. Optionally, the monomers are recycled as feedstock. The hydrogenated oligomers (i.e., dimers and optional other oligomers) can be used as base oils, and more particularly, base oils having the properties of Group II+ or Group III base oils.

[0057] The specific key characteristics of the hydrogenated oligomers (various synthetic hydrocarbons) produced by the method of this invention include one or more of the following properties: (a) a KV100 of 2.7 cSt to 3.5 cSt as measured by ASTM Test Method D445; (b) a KV40 of 15.0 cSt to 12.0 cSt as measured by ASTM Test Method D445; (c) a viscosity index greater than 100 as measured by ASTM Test Method D2270; (d) a Noack volatility of less than 30% by weight as measured by ASTM Test Method D5800; (e) a pour point below -60°C as measured by ASTM Test Method D5960; (f) a cold start simulator (CCS) performance of less than 600 cP at 30°C as measured by ASTM Test Method D5293; and (g) a flash point above 200°C. The hydrogenated oligomers, as base oils, can be used in synthetic lubricant formulations (also known as lubricant formulations).

[0058] In the implementation plan, C is included. 14+ LAO dimer base oils have C nHydrocarbon distribution and a narrower main C content than reported for Group II+ or Group III base oils. n Hydrocarbons. As shown in Table 1 below, C produced by the method of the present invention... 14+ C of LAO dimer n Hydrocarbon distribution and main C n The reported C values ​​for hydrocarbons and each of Groups II+ and III are as follows. n Hydrocarbon distribution and main C n Hydrocarbons are compared.

[0059] Table 1

[0060]

[0061] As shown in Table 1, C n The hydrocarbon distribution shows a normal distribution. Additionally, the main C... n Hydrocarbons represent C in the highest proportion. n Hydrocarbons. When compared with reported data for Group II+ and Group III base oils, C produced by the method of this invention... 14+ LAO hydrogenated dimers have a narrow distribution. See Lee, S. et al. Chemical Composition of Group II Lubricant Oil Studied by High-Resolution Gas Chromatography and Comprehensive Two-Dimensional Gas Chromatograph , Energy Fuels 2007, 21, 6, 3477-3483.

[0062] The narrow distribution of Cn hydrocarbons is one of the several advantages provided by the method of the present invention. Furthermore, it is desirable to provide olefin feed streams that can be oligomerized with high efficiency / high yield and operated for long periods without resulting in premature catalyst replacement or regeneration. Additionally, it is desirable to utilize olefin feed streams that require less pretreatment for use in oligomerization systems. The method of the present invention provides each of these advantages.

[0063] Oligopolymerization of olefin compounds is conventionally accomplished via catalytic reactions. As described herein, the oligomerization catalyst of the present invention is a solid acid-based catalyst, wherein the method is preferably carried out in a flow-through, fixed-bed arrangement. In the method of the present invention, dimer molecules are isomerized to form terminal or internal olefins. Some of the dimer molecules or isomers further react with an additional monomer molecule to form a trimer molecule. Some of the dimer molecules or isomers react with each other to form a tetramer molecule. Trimer molecules may react with an additional monomer molecule to form a tetramer. Higher oligomers than tetramers can also be formed. See paragraph

[0064] of WO2020 / 068527 A1.

[0064] As provided herein, the method of the present invention includes a heterogeneous catalyst. The heterogeneous catalyst and / or oligomer mixture does not require quenching or cooling prior to the hydrogenation of the oligomers, thus saving energy and manufacturing costs in the production of base oils. Furthermore, the solid acid-based catalyst used in the method of the present invention does not require a separation step or separation from the oligomer mixture. The absence of this separation process also saves energy and manufacturing costs. Moreover, after separation, the monomers can be recycled and provided as feedstock.

[0065] The method of the present invention includes using C in an isothermal fixed-bed reactor. 14+ The step of dimerization of LAO and / or mixtures thereof on one or more solid acid catalysts. 14+ LAO has a relatively high boiling point and high molecular weight. Therefore, until this disclosure, C 14+ Dimerization of LAO on solid acid catalysts presents significant challenges. Firstly, the high selectivity for cracking dimer products leads to greater yield losses. Secondly, generally speaking, C... 14+ The high molecular weight of LAO feedstocks keeps them in the liquid phase under reaction conditions, leading to mass transfer limitations and faster catalyst deactivation due to coking. See, for example, Wulfers, M. et al. Assessment of Mass Transfer Limitations in Oligomerization of Butene at High Pressure on H-Beta, Applied Catalysis , Applied Catalysis, Vol. 505, 394-401 (2015); Corma, A. et al. Designing MFI-Based Catalysts with Improved Catalyst Life Journal of Catalysis, Vol. 300, pp. 183-196 (2013); Peratello, S. et al. Olefins Oligomerization: Thermodynamics and Kinetics Over Mesoporous Silica-Alumina Catalysis Today, Vol. 52, pp. 271-277 (1999); Catalysis:An Integrated Approach Volume 123 (1999), page 426. At higher molecular weights, the diffusion rate is lower, and internal mass transfer confinement has a greater impact. Therefore, C 14+ Dimerization / oligomerization of feedstocks with lower carbon numbers (i.e., 10 or fewer carbon numbers) is generally not commercially practiced.

[0066] Typically, the primary deactivation mechanism (in the absence of feed poisons) is the formation of heavy hydrocarbons and coke (high molecular weight polyaromatic hydrocarbons), which hinder pathways to zeolite pores and active sites. Other effects include irreversible adsorption of alkaline substances, oxygen-containing compounds, sulfur, etc. However, these effects can be managed and / or eliminated. As shown in the example below, slower deactivation (using MWW-type materials to deactivate heavy C...) 14+The feed dimerization is due to the high acid site density (compared to HPW catalysts) and greater accessibility (compared to ZSM-57 / ZSM-23) of the MWW-type 12-membered ring pores, which results in the formation of dimer molecules that desorb more rapidly before they can react further to form high molecular weight substances that block active sites and pathways to pores.

[0067] As discussed in this paper, we have found that high accessibility to active sites is crucial for solid acid catalysts. The combination of a low Si / Al2 ratio and high surface area shows promise for the efficient use of C. 10+ LAO feedstocks are highly convertible into synthetic hydrocarbons with good base oil properties. Quantitative acid site accessibility, obtained through thermogravimetric analysis (TGA) of substituted pyridines (e.g., 2,4,6-trimethylpyridine (Clarin)) that are too large to enter micropores, is shown to be crucial for achieving high sustained conversion and selectivity.

[0068] Fixed-bed reactor, followed by hydrogenation

[0069] As described in the examples, our catalyst testing experiments were conducted in a laboratory-scale fixed-bed reactor. The setup was equipped with a high-temperature ISCO liquid pump for the feed (heavy) liquid and nitrogen and hydrogen for pretreatment. The reactor (9 mm diameter, 100 mm length tube) was placed in a heated furnace, with thermocouples positioned within the catalyst bed for precise temperature control. All catalysts were pulverized and sieved to 300–600 micrometers, and typically loaded with 1–5 g of catalyst and mixed with SiC to improve heat transfer and reactor flow distribution. All dimerization catalyst testing experiments were conducted in an upflow reactor configuration. C14 linear α-olefin (linear olefin 14, Idemitsu Kosan Co. Ltd.) was used as the feedstock in all experiments, with 1 wt% dodecane (Sigma-Aldrich, >99%) added as an internal standard. Product analysis was performed by online GC using an Agilent 7890A instrument equipped with a 15 m x 250 μm x 0.25 μm RTX-1 (boiling point) column.

[0070] For commercial approaches, adiabatic or isothermal (e.g., boiling water reactor) fixed-bed or continuous stirred-tank reactors may be considered. See U.S. Patent Nos. 5,567,280, 6,884,914 and U.S. Publication 2020 / 0102256 for exemplary process / reactor configuration descriptions.

[0071] Hydrogenation of LAO dimer

[0072] The hydrogenation of the aforementioned linear olefin dimers can be carried out in any suitable manner using various Ni, Pt, or Pd hydrogenation catalysts in slurry or fixed-bed reactor systems. Those skilled in the art will be familiar with suitable hydrogenation conditions, hydrogenation catalysts, reactors, etc. Reactors suitable for the hydrogenation of linear olefin dimers include, but are not limited to, batch reactors, plug-flow reactors, and liquid continuous-mode reactors. When the reactor is a liquid continuous-mode reactor, the hydrogenation product (hydrogenated oligomer) can be recycled along with the fresh feed of the linear olefin dimer and flashed to carry sufficient dissolved hydrogen for the hydrogenation reaction. Such a system configuration simplifies reactor design. See, for example, paragraph

[0065] of US20230127018A1.

[0073] As described in the example, hydrogenation of the central fraction of distilled hydrocarbons was carried out in a fixed-bed catalytic reactor. Two g (g) of a large Ni catalyst (Ni3298, BASF) pre-reduced and passivated with CO2 was activated according to the following procedure: an initial heating ramp of 2 °C min⁻¹ to 100 °C, followed by a ramp of 5 °C min⁻¹ to 200 °C and holding for 6 h, all under a hydrogen flow, then the temperature was lowered (10 °C min⁻¹) to the initial reaction conditions and the feed was introduced. Hydrogenation was performed at a weight hourly space velocity (WHSV) of 10 h⁻¹ and 100 °C at 16 bar pressure and an H₂ to olefin ratio of 2 (assuming an average olefin molar mass of 392 g·mol⁻¹). -1 The initial hydrogenation experiment was conducted under these conditions. After testing showed that a large amount of olefins were not hydrogenated, a second hydrogenation was carried out at 1 h⁻¹ WHSV and 150 °C with a molar ratio of H₂ to olefins of 2 to fully hydrogenate the material.

[0074] WHSV can be used to optimize selectivity for dimers, unreacted olefin recycling (which is diluted with a paraffin feed stream to manage thermal generation / deactivation in the reactor), and selectivity for dimers over a temperature range. These parameters can also be used to optimize the degree of branching of the formed dimers, which is important for the final properties. Other process parameters can be varied, including olefin feedstock, catalyst and catalyst loading, reaction temperature, process time, catalyst removal efficiency, and any fractionation conditions. Each of these parameters can be optimized to meet target molecular properties.

[0075] Optimization of solid acid catalysts

[0076] Zeolite catalysts are used in hydrocarbon processing and chemical conversion processes. The properties that make zeolites a diverse catalytic component are: grain size and shape are variables in catalyst design and are determined by synthesis conditions. Compared to amorphous silica and alumina traditionally used in catalyst preparation, they have a high internal surface area and very high thermal stability. Pores are well-defined and have molecular dimensions, determined by the crystal structure. The pore openings controlling the accessibility of the internal surface can be finely modified (pore size engineering) through ion exchange, post-impregnation, or chemical reactions with specific compounds. Charge-compensating cations can be removed through ion exchange. In most structures, T atoms are highly accessible; their properties determine the surface polarity and its catalytic activity. The chemical composition of the lattice depends on the synthesis conditions. In many cases, the Si / Al ratio can vary within a wide range, and for some structures, the properties of the T atoms are also variable.

[0077] Catalyst formulations can be optimized in a wide variety of ways. The percentage of active phase, binder pore size distribution, zeolite crystal size, and Si / Al2 ratio are all example parameters that can be optimized for maximum activity, selectivity, and catalyst lifetime. See, in general, Concepts for Preparation of Zeolite-Based Catalysts, Synthesis of Solid Catalyst, Chapter 12, Wiley Online (2009); also see, Preparation of Zeolite Catalysts Studies in Surface Science and Catalysis, Vol. 137 (2001), pp. 673-706.

[0078] "Active phase" refers to the content of zeolite or heteropolyacid phase in the catalyst material, with the remainder being a binder (Al2O3 or SiO2 in these examples). These are formulated materials in which it is assumed that the active phase participates in the catalytic reaction and that the purpose of the binder is to provide mechanical stability to the catalyst and / or improve the dispersion of the active phase.

[0079] High acid site density refers to the low Si / Al2 ratio of the MCM-49 catalyst. In aluminosilicate zeolites, it is assumed that each framework aluminum atom provides a Brønsted acid site, which is active in acid-catalyzed oligomerization reactions. The lower the Si / Al2 ratio, the higher the acid site density. The Si / Al2 ratio can be quantitatively measured by elemental analysis or by adsorption / desorption of bases (e.g., ammonia, pyridine, etc.), such as inductively coupled plasma-atomic emission spectrometry (“ICP-AES”) provided in the examples. Various probe molecules can also be used to measure accessibility.

[0080] MWW framework materials, including the MCM-49 catalyst, possess 12-membered ring openings (e.g., “cavities”) aligned with the surface of typical thin zeolite grains, offering high accessibility to macromolecules compared to the smaller 10-membered ring openings of the framework. Therefore, the 12-membered ring “cavities” can accommodate catalysis on macromolecules that other porous zeolites (e.g., ZSM-57 and ZSM-23) with more constrained pore channel structures cannot. See Lawton, SL, et al. Twelve-Ring Pockets on the External Surface of MCM-22 Crystals Volume 23, Issues 1-2 (1998), pp. 109-117. ZSM-57 is described in EP 174121 B1, column 2, lines 23-12, line 48, which is incorporated herein by reference. See also Schlenker, JL et al. The Framework Topology of ZSM-57: A New Synthetic Zeolite See also Zeolites, Vol. 10, (1990), pp. 293-296. ZSM-23 is described in U.S. Patent No. 4076842, column 1, lines 60-6, line 44, which is incorporated by reference. See also Schlenker, JL et al. The Framework Topology of ZSM-23: A High Silica Zeolite Zeolites, Vol. 5, (1985), pp. 352-354.

[0081] Catalysis by heteropolyacids (HPAs) and related compounds involves the incorporation of polyoxometalates with metal-oxygen octahedrons as the basic structural unit into anions (heteropolyanions). See Kozhevnikov, Ivan... Heteropoly Acids and Related Compounds as Catalysts for Fine Chemical Synthesis Science and Engineering, Vol. 37, (1995). Keggin series HPAs are used for catalysis and contain heteropoly anions (HPAN). As described in the examples, HPW catalysts, Keggin-type phosphotungstic heteropoly acids (H3PW12P40, HPW) phases are synthesized by acid condensation of sodium tungstate and sodium phosphate. The phosphotungstic acid (HPW) phase is introduced by impregnating silica extrudate (PQ chemicals 1 / 16” extrudate, 229 m2 g⁻¹ surface area and 0.82 cm³ g⁻¹ total pore volume) with an aqueous initial wet impregnation method, which is dried at 110 °C and calcined at 300 °C.

[0082] Zeolite-solid acid catalyst

[0083] Zeolites are classified by the Structure Committee of the International Zeolite Association according to the rules of the IUPAC Zeolite Nomenclature Committee. Framework types describe the topological structure and connectivity of the tetrahedral coordinating atoms that constitute the framework and abstract specific properties of these materials. Zeolites may have internal porous systems, comprising interconnected cage-like voids or one-dimensional, two-dimensional, or three-dimensional channel systems. Three-letter codes are assigned to zeolite adsorbents with established structures, and these are described in the Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (2001), which is incorporated herein by reference in its entirety.

[0084] Molecular sieve materials, whether natural or synthetic, can be used as adsorbents and possess catalytic properties for hydrocarbon conversion reactions. Specific molecular sieves, such as zeolites, AlPO, and mesoporous materials, are ordered, porous crystalline materials with a well-defined crystal structure determined by X-ray diffraction (“XRD”). Molecular sieves can be ordered and produce specific, identifiable XRD patterns. Within specific molecular sieve materials are chambers interconnected by channels or pores. Within certain types of molecular sieves, the pore size is typically uniform. The pore size determines whether molecules can travel within the molecular sieve and be adsorbed or repelled.

[0085] 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.

[0086] Zeolites and their isotypes are classified by the Structural Committee of the International Zeolite Association according to the rules of the IUPAC Zeolite Nomenclature Committee. Based on this classification, three-letter codes are assigned to framework types of zeolites with established structures and other crystalline microporous molecular sieves, and are described in “Atlas of Zeolite Framework Types,” edited by Ch. Baerlocher, LB McCusker, and D. Holson, Elsevier, 6th edition, 2007, which is incorporated herein by reference.

[0087] Specific zeolites contain an inorganic framework type in which silicon tetrahedral atoms are connected to four next-nearest neighbor tetrahedral atoms via oxygen atoms. The term "silicate," as used herein, refers to a substance containing silicon and oxygen atoms alternately bonded to each other (i.e., -O-Si-O-Si-), and optionally contains other types of atoms within the inorganic framework type, including boron, gallium, aluminum, or other metals (e.g., transition metals such as titanium, vanadium, or zinc). 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 "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 mentioned 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 suitable for a given zeolite. Currently, the International Zeolite Association’s Structural Committee has identified more than 200 known zeolite framework silicates, providing a range of defined pore geometries and orientations.

[0088] Zeolite framework silicates are typically characterized by the term ring size, which refers to the number of silicon atoms (or substitute atoms, such as those listed above) tetrahedral coordinated with oxygen atoms in the ring, defining pores or channels within the zeolite. For example, an "8-membered ring" zeolite is a zeolite having 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.

[0089] Zeolites can be classified into small, medium, large, and supermacroporous structures, corresponding to pore windows defined 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 approximately 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, omega, ZSM-2, ZSM-12, zeolite T, Beta, and SSZ-56. Macroporous zeolites typically have a free pore size of 0.6 to 0.8 nm. Mesoporous (or intermediate) pore size zeolites (10R) include, for example, MFI, MEL, Mesopore-sized zeolites include 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. These zeolites typically have a free pore size of 0.45 to 0.6 nm. Small-pore-sized zeolites (8R) include framework zeolites such as CHA, RTH, ERI, KFI, LEV, and LTA, 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. These zeolites typically have a free pore size of 0.3 to 0.45 nm.

[0090] 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) (e.g., sources of silica, but also alumina, etc.). In many cases, a structure-directing agent (“SDA”) is also present. A SDA is a compound believed to promote the formation of molecular sieves and is thought to act as a template (around which a specific molecular sieve structure can be formed), thereby facilitating the formation of the desired molecular sieve. Various compounds have been used as SDAs, including various types of quaternary ammonium cations. Typically, molecular sieve (zeolite) crystals form around the SDA, and once crystallization is complete, the SDA occupies the pores in the molecular sieve. Therefore, the “synthetic state” (or “prepared state”) molecular sieve will contain the SDA in its pores, and after crystallization, the “synthetic state” molecular sieve undergoes processing steps such as calcination to remove the SDA.

[0091] MWW framework-type crystalline microporous materials include those molecular sieves with X-ray diffraction patterns having maxima of d-spacing at 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 associated computer as the collection system.

[0092] Examples of crystalline microporous materials of MWW framework type I or synthetic MWW type zeolites 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), and MCM-49 (described in U.S. Patent No. 5,236,575). The following are also mentioned: 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. in Chem. Sci., 2015, 6, 6320-6324), and mixtures thereof.

[0093] In the implementation, the MWW framework-type crystalline microporous material can be an aluminosilicate material having a silica to alumina (Si / Al2) molar ratio of at least 10, for example, at least 10 to less than 50.

[0094] As described in this article, MWW-based crystalline microporous materials may be contaminated by other crystalline materials, such as magnesium alkali zeolite or quartz. These contaminants may be present in amounts of <10% by weight, typically <5% by weight.

[0095] Zeolite MCM-49

[0096] As described in U.S. Patent No. 5,236,575, 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, from about 2 to about 35, from about 10 to about 35, from about 15 to about 31. U.S. Patent No. 5,236,575, column 2, lines 67-68. In its synthetic form, based on anhydrous form and in terms of the number of moles of oxide per n moles of YO₂, the material has the following formula: (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 easily removed by the post-crystallization method described in column 3, lines 1-20 of U.S. Patent No. 5,236,575.

[0097] Crystallizable materials can be prepared from a reaction mixture containing the following sources: alkali metal or alkaline earth metal (M); cation; oxide of trivalent element X; oxide of tetravalent element Y; directing agent (R); and water. The composition of the reaction mixture, based on the molar ratio of oxides, is provided in Table 2 below within the following ranges:

[0098] Table 2

[0099] Reactants for preparing MCM-49 zeolite

[0100]

[0101] In this synthesis method, if more than one component X is present, at least one must be present such that its 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.

[0102] Furthermore, the source of YO2 is primarily solid YO2, for example, at least about 30% by weight of solid YO2, in order to obtain a crystalline product containing at least about 30% by weight of solid silica (e.g., Ultrasil, precipitated, spray-dried silica containing about 90% by weight of silica, or HiSil, precipitated hydrated SiO2 containing about 87% by weight of silica), about 6% by weight of free H2O, and about 4.5% by weight of bound H2O, and having a particle size of about 0.02 micrometers that is conducive to the formation of crystallized MCM-49.

[0103] The directing agent R is selected from cycloalkylamines, azacycloalkanes, diazacycloalkanes, and mixtures thereof, wherein the alkyl group comprises 5 to 8 carbon atoms. Non-limiting examples of R include cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethyleneimine, heptamethyleneimine, piperazine, and combinations thereof. (See U.S. Patent 5,236,575, column 6, lines 24-68, column 7, lines 1-2.)

[0104] The synthesis of MCM-49 is facilitated by the presence of at least 0.01%, 0.10%, and % of 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). ​​Alternatively, MCM-49 can be converted to another form by heat treatment, typically performed by heating at a temperature of at least about 370°C for at least 1 minute and no longer than 20 hours. While heat treatment can be performed at pressures below atmospheric pressure, atmospheric pressure is preferred for convenience. The heat treatment can be performed at temperatures up to about 925°C. (US Patent No. 5, column 5, lines 59-67). When used as an adsorbent or as a catalyst in the conversion of organic compounds, MCM-49 should be dehydrated, at least partially dehydrated. This can be achieved by heating to a temperature ranging from 200°C to approximately 370°C for 30 minutes to 48 hours in an atmosphere such as air or nitrogen, and at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. Dehydration can also be achieved at room temperature simply by placing MCM-49 in a vacuum, but this requires a longer time. (See U.S. Patent No. 5,236,575, column 6, lines 13-23).

[0105] base oils

[0106] Base oils are typically distinguished by viscosity and produced to specific viscosity specifications. Since viscosity is roughly related to molecular weight, the first step in manufacturing any base oil is to separate lubricating precursor molecules from feedstocks with the correct molecular weight range through distillation in a coarse fractionation system. This distillation removes low-viscosity, low-volatility, low-boiling-point fuel products that are not used in lubricants. Higher molecular weight feedstocks that do not evaporate at atmospheric pressure can be fractionated by distillation under reduced pressure from about 10 mmHg to about 50 mmHg.

[0107] As described above, higher molecular weight feedstocks can then be fed into a vacuum column, where intermediate product streams are generated, such as light vacuum gas oil (“LVGO”) and heavy vacuum gas oil (“HVGO”). These intermediate product streams can be narrow fractions with specific viscosities intended for solvent refining steps, or they can be broader fractions intended for hydrocracking into lubricants and fuels.

[0108] Conversely, as described herein, the method of the present invention enables C 14+ LAO dimerizes on a solid acid catalyst in an isothermal fixed-bed reactor to provide Group II+ or Group III base oils.

[0109] As shown in Table 3, base oils are classified according to the American Petroleum Institute (API) classification based on saturated hydrocarbon content, sulfur level, and viscosity index. Typically, Group I, II, and III base oils are derived from crude oils that have undergone extensive processing (e.g., fractionation, solvent extraction, solvent dewaxing, and hydroisomerization). Group III base oils can also be produced from synthetic hydrocarbons derived from natural gas, coal, or other fossil resources. Group IV base oils include polyalphaolefins (“PAOs”) produced through oligomerization of alpha-olefins. Group V base oils include all base oils not belonging to Groups I-IV, such as cycloalkanes, polyalkylene glycols (“PAGs”), and esters.

[0110] In addition, there are informal classifications of base oils, known as "Group II+" and "Group III+", which are generally considered in the lubricant industry to correspond to base oils that exceed the minimum classification requirements of the formal groups. For example, "Group II+" base oils can have a viscosity index (VI) higher than 110, and "Group III+" base oils can have a viscosity index (VI) of 130 to 150. Group III+ base oils have properties specifically tailored for specific applications. In addition to the viscosity index, properties such as CCS (Cold Start Simulator according to ASTM D5293-20) and Noack (ASTM D5800-18) are also controlled.

[0111] Table 3

[0112] American Petroleum Institute Group I-V classification

[0113]

[0114] The aromatic content of base oils, paraffinic diesels, and waxes is measured using various methods, including chromatography and ultraviolet spectroscopy, such as those described in U.S. Publication No. 2013 / 0179092, published July 11, 2013, which is incorporated herein by reference. Furthermore, techniques such as mass spectrometry and NMR spectroscopy are used to establish the detailed composition of crude oils. The empirical ndM method (ASTM D3238-17) can also be used to determine the distribution of carbon types (paraffinic carbons, cycloalkanes, and aromatic carbons) in sample oils through relatively simple measurements of physical parameters such as refractive index (n), density (d), and molecular weight (M).

[0115] This document describes a method for producing base oils. According to embodiments, the hydrocarbons produced by the method of the present invention contain less than 0.03% by weight sulfur, a pour point below -60°C, less than 30% by weight Noack volatility, and a CCS value of less than 600 cP at -35°C according to ASTM D5293. The base oils produced according to this disclosure have a KV100 of about 2.7 cSt to about 3.5 cSt.

[0116] As described herein, the base oils produced by the method of the present invention have a kinematic viscosity at 100°C of about 3.5 cSt to about 2.7 cSt, about 3.4 cSt to about 2.8 cSt, or about 3.3 cSt to about 2.9 cSt as measured according to ASTM D-445 (“KV100”). In various embodiments of the present invention, the base oils have a kinematic viscosity at 40°C of about 12 cSt to about 15 cSt, about 11 cSt to about 14 cSt, or about 12 cSt to about 13 cSt as measured according to ASTM D-445 (“KV40”). The base oils or base oil blends may have a viscosity index greater than about 100, about 105, about 110, or about 115 as calculated according to ASTM D-2270.

[0117] The base oil has a Noack volatility of not less than about 30%, preferably not less than about 25%. According to various embodiments of the invention, the base oil has a Noack volatility of about 30.0 wt% to about 20.0 wt% or about 21.0 wt% to about 24.0 wt%. As used herein, Noack volatility is determined by ASTM D-5800.

[0118] Additionally or alternatively, according to various embodiments of the invention, the base oil has a pour point below about -60°C, below about -63°C, below about -64°C, and below about -70°C. According to various embodiments of the invention, the base oil has a pour point from about -70°C to -60°C. Furthermore, in embodiments, the base oil has a flash point above 200°C.

[0119] Example

[0120] Features of this disclosure are described in the following non-limiting embodiments.

[0121] Example 1

[0122] ZSM-57, ZSM-23, MCM-49, and HPW catalysts were used for screening C14 LAO dimerization.

[0123] To demonstrate the superior activity and selectivity of MCM-49 compared to other solid acid catalysts (e.g., ZSM-57, ZSM-23, and HPW), 2 g (2 grams) of the solid acid catalyst was pulverized and sieved to approximately 300 to approximately 600 micrometers. The pulverized solid acid catalyst was then supported on SiC (50% / 50% blend) and the C... 14 The LAO feedstock was contacted with a solid acid catalyst. The C14LAO feedstock was not dried prior to testing. The test was conducted in an upflow reactor configuration under liquid phase conditions at 5 bar back pressure and at 120°C, 160°C, and 200°C for 3 hours. -1 and 1.5h -1 The weight time air velocity (WHSV) was tested.

[0124] like Figure 1A , 1B As shown in Figures 1C and 1D, the MWW framework-type MCM-49 catalyst exhibits significantly greater activity and selectivity in dimer formation compared to other oligomerizing catalysts (e.g., ZSM-57 and ZSM-23). ​​The data also demonstrate superior performance compared to supported heteropolyacid (HPW) catalysts.

[0125] Figure 1A , 1B 1C and 1D are plots showing the observed selectivity of these four different solid acid catalysts for the production of linear and / or branched hydrocarbons (excluding C). 14 (Isoselectivity), and also showed the total C of each solid acid catalyst at three different process temperatures and two different feed flow rates (in terms of heavy space-time velocity). 14 Conversion rate.

[0126] Table 3 below provides the properties of the solid acid catalyst used in Example 1.

[0127] Table 3

[0128]

[0129] [[ID=...]] Further summary of C 14 Testing of solid acid catalysts for LAO dimerization. ​ The reported conversions, selectivity, and yields are averages over approximately 10 hours under conditions where the solid acid catalyst exhibits the highest overall dimer yield. The active phase is the catalytically active component of the catalyst.

[0130] The high activity and selectivity observed in MCM-49 appear to be due to the high acid site density and accessibility (external cavities) of the MWW skeleton. Accessibility and high acid site density lead to high activity at a mild temperature (160°C), which further results in fewer cracking, (skeleton) isomerization, and coking side reactions.

[0131] Example 2

[0132] Sample production run using MCM-49

[0133] Using the self-bonding MCM-49 catalyst confirmed in Example 1, solid acid catalyst screening, and C 14 The LAO feedstock was used for sample production runs, with the goal of producing approximately 500 mL of the C14 dimer center fraction for application testing and benchmarking against Group II / III / III+ base oils.

[0134] Two grams (2g) of MCM-49 catalyst (crushed and sieved to 300-600 micrometers) were loaded onto SiC (50%-50% blend). Prior to operation, C... 14 The LAO feedstock was not pre-dried. Operating conditions were initially set at WHSV = 3 h⁻¹ and 160 °C. The system was maintained at a back pressure of 5 bar (full liquid phase conditions) in an upflow reactor configuration.

[0135] ​ A summary of the sample production run is provided, and C using MCM-49 is shown. 14+ Conversion and selectivity curves for the dimer sample were obtained. At the beginning of the operating conditions (WHSV = 3 h⁻¹ and 160 °C), C 14 The LAO conversion rate was 65% by weight, and the selectivity for the dimer was approximately 65% ​​by weight. 14 The selectivity for olefin isomers was approximately 30% by weight, with the remainder being cracking products (<C14), mildly cracked products (C15-C24), and heavier products (>C29). The apparent deactivation rate increased to an average of 1.8 x 10⁻⁶. -6 mol C 14+ Dimer h -1 g feed -1 Compared to the initial catalyst activity of 2.8 x 10⁻⁶, -3 mol C 14+ Dimer h -1 g catalyst -1 Therefore, we can estimate that under constant operating conditions, 1T of catalyst will be "completely" deactivated after exposure to approximately 1600T of feed, or in other words, the expected final catalyst lifetime will be 1600T. 进料 / T 催化剂 .

[0136] After approximately 350 hours on the feed stream, 1500 grams of reactor effluent were collected (final catalyst lifetime: 226 g). C14+二聚体 / g 催化剂 and 1500 g 进料 / g 催化剂And then terminate the operation.

[0137] Reactor product distillation was performed on an Iludest DN50 laboratory vacuum batch distillation apparatus. A six-liter (6L) round-bottom flask was used for distilling the total reactor effluent, which was compared with the high-boiling bottom fraction of Primol 542 (~C). 36 Average carbon number, containing <0.5% C by weight 14+ (Dimer) combination.

[0138] ​ It consists of the raw materials, collected fractions, and C from the effluent of the main reactor. 14+ Summary of the composition (bars, left axis) and weight (black squares, right axis) of the final central fraction obtained by distillation of LAO dimer. ​ It is a reconstructed distillation profile of the method described herein, including (hollow circle) added Primol 542 substrate and excluding (solid circle) added Primol 542 substrate.

[0139] Example 3

[0140] Hydrogenation of the central fraction

[0141] like ​ As shown, fractions 7 to 16 (380°C to 415°C) were selected as the center fractions for subsequent hydrogenation. Hydrogenation was carried out on 2 g of bulk Ni catalyst (Ni3298, BASF). The hydrogenation was carried out at 16 bar pressure and an H2 to olefin + n ratio of 2 at LHSV for 10 h. -1 The initial hydrogenation experiment was conducted at 100°C, assuming an average olefin molar mass of 392 g mol. -1 (C28H56). However, the bromination test after hydrogenation showed 8285 mg bromine / 100 g. 样品 The rather high value indicates that a significant amount of olefins were not hydrogenated. Therefore, at LHSV 1h -1 The second hydrogenation was carried out at 150°C and a molar ratio of H2 to olefin of 2. The bromination test after hydrogenation showed 236 mg bromine / 100 g. 样品 It has a low bromine index value.

[0142] The central fraction produced (C 14+ LAO dimers exhibit properties of Group II+ and / or Group III base oils. However, compared to the reported distributions of Group II / III base oils, hydrogenated oligomers (multi-synthetic hydrocarbons) show a narrower carbon number distribution and a narrower branching distribution. (Lee, S. et al.) ​ ​ ​Energy Fuels 2007, 21, 6, 3477-3483, incorporated by reference. The skeletal isomerization of the produced dimers affects the properties of the synthesized hydrocarbons. For example, the degree of branching of hydrocarbons depends on process conditions, including average operating temperature and catalyst.

[0143] Hydrogenated C produced 14+ The properties of LAO dimers are shown in Table 4 below. Furthermore, in Table 4, C... 14 The properties of the LAO dimer were compared with those of Group III base oils, GTL 3 (Fischer-Tropsch technology), Group II+ base oils, and Yubase™ 3 base oils. Additionally, the produced C... 14+ The properties of LAO dimer and Chevron 100R (Group II base oil) and SpectraSyn TM The properties of 3.5 Max (Group IV base oils) were compared.

[0144] As shown, the viscosity index is slightly lower than any base oil, while the flash point properties (Cleveland open cup (“COC”)) are substantially the same between the test samples and each base oil. Although not tested at the same temperature, the cold start simulator (“CCS”) results are slightly favorable compared to the GTL 3 base oil, while the hydrogenated C… 14 The pour point and Noack volatility of the LAO dimer sample were superior to those of the Group II+ and Group III base oils.

[0145] Compared to the typical 4cP II group base oil reference Chevron 100R, C 14 LAO dimer exhibited superior performance in most properties, including cold start simulator testing, pour point, and Noack volatility. The viscosity index and flash point of the experimental samples were similar to those of the slightly higher viscosity Chevron 100R reference.

[0146] Table 4

[0147]

[0148] Overall, even compared to Group IV base oils with slightly higher viscosity (Spectrasyn™ 3.5 MaX), the properties of the produced synthetic hydrocarbons are comparable in performance. The resulting C 14+ LAO hydrogenated oligomers demonstrate that the method described in this paper provides a lower-cost production route (method) for Group II+ / III base oils—even when the solid acid catalyst and process conditions used for the sample production run are not optimized. Using a mixture of C 14 C 16 and C 18The process of LAO feedstock and the adjustment and conversion of solid acid catalysts can allow for the adjustment of viscosity and other product properties for specific applications.

[0149] Additional implementation plan

[0150] Additionally or alternatively, the present invention relates to:

[0151] Implementation Plan 1: A method for producing base oils, comprising the following steps:

[0152] We provide LAO raw materials containing C14+LAO;

[0153] The LAO raw material is contacted with a solid acid catalyst to produce an oligomer mixture containing C14+LAO dimers and monomers, wherein the solid acid catalyst is an MWW framework catalyst.

[0154] The C14+LAO dimer in the oligomer mixture is separated from the monomer during distillation; and

[0155] The C14+LAO dimer is hydrogenated to produce a base oil having a KV100 of 2.7–3.5 and a KV40 of 12 cSt–15 cSt as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

[0156] Implementation Scheme 2: The method for producing base oils according to Implementation Scheme 1, wherein the oligomer mixture is not cooled prior to the step of separating the dimer from the monomer.

[0157] Implementation Scheme 3: A method for producing base oils according to Implementation Scheme 1, wherein the monomer is recycled and provided as a raw material.

[0158] Implementation Scheme 4: A method for producing base oils according to Implementation Scheme 1, wherein the MWW skeleton catalyst is not separated from the oligomer mixture prior to hydrogenation of the C14+LAO dimer.

[0159] Implementation Scheme 5: The method for producing base oils according to Implementation Scheme 1 further includes a second distillation of the hydrogenated oligomer mixture.

[0160] Implementation Scheme 6: The method for producing base oils according to Implementation Scheme 1, wherein 45%-80% by weight of C14+LAO is converted into C14+LAO dimer.

[0161] Implementation Scheme 7: The method for producing base oils according to Implementation Scheme 1, wherein the base oils contain more than 80% of the generated branched synthetic hydrocarbons.

[0162] Implementation Scheme 8: A method for producing various synthetic hydrocarbons, comprising the following steps:

[0163] Provides LAO feedstock comprising LAO and mixtures thereof, wherein the LAO has 10 or more carbon atoms; and

[0164] The LAO raw material is contacted with a solid acid catalyst to produce an oligomer mixture containing at least one LAO dimer and monomer, wherein the LAO is in the liquid phase and the solid acid catalyst is an MWW type zeolite.

[0165] Separate the LAO dimer from the monomer, and

[0166] Hydrogenation of the dimer of LAO produces a variety of synthetic hydrocarbons having a KV100 of 2.7 to 3.5 and a KV40 of 12 cSt to 15 cSt as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

[0167] Implementation Scheme 9: The method according to Implementation Scheme 1 or 8, wherein the base oil has a KV100 of 2.7 to 3.25, a KV40 of 12 to 14, and a viscosity index of 100 to 115.

[0168] Implementation Scheme 10: The method according to Implementation Scheme 1 or 8, wherein the oligomer mixture comprises 30% to 90% by weight of the dimer of the LAO.

[0169] Implementation Scheme 11: The method according to Implementation Scheme 1 or 8, wherein the catalyst is MCM-49.

[0170] Implementation Scheme 12: The method according to Implementation Scheme 1 or 8, wherein the catalyst Si / Al2 ratio is 10 to 50.

[0171] Implementation Scheme 13: The method according to Implementation Scheme 1 or 8, wherein the specific surface area of ​​the catalyst is greater than 400 m2 / g.

[0172] Implementation Scheme 14: The method according to Implementation Scheme 1 or 8, wherein the catalyst can absorb more than 75 micromoles / gram.

[0173] Implementation Scheme 15: The method according to Implementation Scheme 1 or 8, wherein the method is carried out in an isothermal fixed-bed reactor.

[0174] Implementation Scheme 16: The method according to Implementation Scheme 1 or 8, wherein the method is operated at a temperature of 120°C to 200°C.

[0175] Implementation Scheme 17: The method according to Implementation Scheme 1 or 8, wherein the method takes 1.5 to 3.0 hours. -1 WHSV operation.

[0176] Implementation Scheme 18: The method according to Implementation Scheme 1 or 8, wherein the solid acid catalyst has a final catalyst lifetime of greater than 1500T feed / T catalyst.

[0177] Implementation Scheme 19: A method for producing hydrogenated oligomers that can be used as base oils, comprising the following steps:

[0178] Provides C 14+ LAO raw materials;

[0179] The LAO feedstock is contacted with the MCM-49 catalyst to produce a product containing C. 14+ Oligomeric mixtures of LAO dimers and monomers;

[0180] C 14+ The LAO dimer separates from the monomer, and

[0181] Hydrogenation of the C 14+ LAO dimers are used to produce hydrogenated oligomers having a viscosity of 2.7 to 3.5 KV100 and 12 cSt to 15 cSt KV40 as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

[0182] Implementation Scheme 20: The method according to Implementation Scheme 1, 8 or 19, wherein the base oil has a Noack volatility of less than 30% by weight as measured by ASTM test method D5800 and a pour point of less than -60°C as measured by ASTM test method D5950.

[0183] Based on the foregoing description, many changes, modifications and variations will be readily 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 considered.

Claims

1. A method for producing base oils, comprising the following steps: Provides C 14+ LAO raw materials; The LAO feedstock is contacted with a solid acid catalyst to produce a product containing C. 14+ Oligomeric mixtures of LAO dimers and monomers, wherein the solid acid catalyst is an MWW framework catalyst; During the distillation process, the C in the oligomer mixture is... 14+ LAO dimer and monomer separation; and Hydrogenation of the C 14+ LAO dimers are used to produce base oils with viscosities of 2.7–3.5 KV100 and 12 cSt–15 cSt KV40 as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

2. The method for producing base oils according to claim 1, wherein the oligomer mixture is not cooled prior to the step of separating the dimer from the monomer.

3. The method for producing base oils according to claim 1, wherein the monomer is recycled and provided as a raw material.

4. The method for producing base oils according to claim 1, wherein during the hydrogenation of the C 14+ Previously, the MWW framework catalyst had not been separated from the oligomer mixture using LAO dimer.

5. The method for producing base oils according to claim 1 further includes a second distillation of the hydrogenated oligomer mixture.

6. The method for producing base oils according to claim 1, wherein 45%-80% by weight of C 14+ LAO is converted to C 14+ LAO dimer.

7. The method for producing base oils according to claim 1, wherein the base oils contain more than 80% by weight of C 14+ LAO dimer.

8. A method for producing a variety of synthetic hydrocarbons, comprising the following steps: Provide LAO raw materials comprising LAO and mixtures thereof, wherein the LAO has 10 or more carbon atoms; The LAO raw material is contacted with a solid acid catalyst to produce an oligomer mixture containing at least one LAO dimer and monomer, wherein the LAO is in the liquid phase and the solid acid catalyst is an MWW type zeolite. Separate the LAO dimer from the monomer, and Hydrogenation of the dimer of LAO produces a variety of synthetic hydrocarbons having a KV100 of 2.7 to 3.5 and a KV40 of 12 cSt to 15 cSt as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

9. The method according to claim 1 or 8, wherein the base oil has a KV100 of 2.7 to 3.25, a KV40 of 12 to 14, and a viscosity index of 100 to 115.

10. The method according to claim 1 or 8, wherein the oligomer mixture comprises 30% to 90% by weight of the dimer of the LAO.

11. The method according to claim 1 or 8, wherein the catalyst is MCM-49.

12. The method according to claim 1 or 8, wherein the catalyst Si / Al2 ratio is 10 to 50.

13. The method according to claim 1 or 8, wherein the catalyst has a specific surface area greater than 400 m². 2 / g.

14. The method according to claim 1 or 8, wherein the catalyst can absorb more than 75 micromoles / gram.

15. The method according to claim 1 or 8, wherein the method is carried out in an isothermal fixed-bed reactor.

16. The method according to claim 1 or 8, wherein the method is operated at a temperature of 120°C to 200°C.

17. The method according to claim 1 or 8, wherein the method is performed over a period of 1.5 to 3.0 hours. -1 WHSV operation.

18. The method according to claim 1 or 8, wherein the solid acid catalyst has a content greater than 1500T. 进料 / T 催化剂 The final catalyst lifetime.

19. A method for producing hydrogenated oligomers that can be used as base oils, comprising the following steps: Provides C 14+ LAO raw materials; and The LAO feedstock is contacted with the MCM-49 catalyst to produce a product containing C. 14+ Oligomeric mixtures of LAO dimers and monomers; C 14+ The LAO dimer separates from the monomer, and Hydrogenation of the C 14+ LAO dimers are used to produce hydrogenated oligomers having a viscosity of 2.7 to 3.5 KV100 and 12 cSt to 15 cSt KV40 as measured by ASTM test method D445, and a viscosity index greater than 100 as measured by ASTM test method D2270.

20. The method according to claim 1, 8 or 19, wherein the base oil has a Noack volatility of less than 30% by weight as measured by ASTM test method D5800 and a pour point of less than -60°C as measured by ASTM test method D5950.

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