Process and system for base oil production using a bimetallic SSZ-91 catalyst

Abstract

An improved process and catalyst system for producing a base oil product and reducing the aromatics content of the base oil while providing good product yields. The process and catalyst system generally involve the use of a bimetallic SSZ-91 catalyst by contacting the catalyst with a hydrocarbon feed to provide a dewaxed base oil product.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 074,212, filed on 3 September 2020, the entirety of which disclosures are incorporated herein by reference.

[0002] Field of Invention A process and system for producing base oil from hydrocarbon raw materials using a bimetallic SSZ-91 catalyst. [Background technology]

[0003] A hydrogen isomerization catalytic dewaxing process for producing a base oil from hydrocarbon feedstocks involves introducing a feed into a reactor containing a dewaxing catalyst system in the presence of hydrogen. Within the reactor, the feed contacts a hydrogen isomerization catalyst under hydrogen isomerization dewaxing conditions to provide an isomerization stream. Hydrogen isomerization removes aromatics and residual nitrogen and sulfur, and isomerizes normal (linear) paraffins to improve cold flow properties. The isomerization stream may be further contacted in a second reactor with a hydrogenation finishing catalyst to remove trace amounts of aromatics and olefins from the base oil product and to improve color, etc. The hydrogenation finishing unit may include an alumina support and a hydrogenation finishing catalyst containing a precious metal, typically palladium, or platinum in combination with palladium.

[0004] Common challenges in typical hydrogen isomerization catalytic dewaxing processes include, among other things, providing products(s) that meet relevant product specifications such as cloud point, pour point, viscosity, and / or viscosity index limits for one or more products, while simultaneously achieving a good product yield. Furthermore, further upgrades may be used to further improve product quality, for example in hydrogen finishing processes, by saturating aromatics and reducing aromatic content, for example, for color and oxidation stability. However, the presence of residual organic sulfur and nitrogen from upstream hydrogen treatment and hydrocracking processes can have a significant impact on downstream processes and the quality of the final base oil product. Therefore, more robust catalysts for base oil production are needed to isomerize wax molecules and convert aromatics to saturated species. Thus, process and catalyst systems are needed to produce base oil products with reduced aromatic content while simultaneously providing good product yield. [Overview of the project]

[0005] The present invention relates to a process and catalyst system for converting wax-containing hydrocarbon raw materials into high-grade products generally containing base oils with reduced aromatic content. Such a process utilizes a bimetallic catalyst system including a bimetallic SSZ-91 hydrogen isomerization dewax catalyst. The hydrogen isomerization process converts aliphatic, unbranched paraffinic hydrocarbons (n-paraffins) into isoparaffins and cyclic chemical species, thereby lowering the pour point and cloud point of the base oil product compared to the raw material. The bimetallic SSZ-91 catalyst has been found to advantageously provide base oil products with reduced aromatic content compared to base oil products produced using non-bimetallic catalysts.

[0006] In one embodiment, the present invention relates to a hydrogen isomerization process useful for producing a dewaxed product containing a base oil, particularly one or more product grade base oil products, by hydrogenating a suitable hydrocarbon feedstream. Although not necessarily limited thereto, one of the objectives of the present invention is to reduce the aromatic content in the base oil product while providing a good base oil product yield.

[0007] This process generally generally comprises contacting a hydrocarbon feed with a hydroisomerization catalyst under hydroisomerization conditions to produce a product or a product stream; wherein the hydroisomerization catalyst comprises a bimetallic SSZ-91 molecular sieve comprising at least two different modifying metals selected from Groups 7 to 10 and Group 14 of the Periodic Table of the Elements.

[0008] The present invention also relates to a hydroisomerization catalyst system comprising the bimetallic SSZ-91 hydroisomerization catalyst used in the process described herein. Furthermore, [1] to

[19] below all represent one embodiment or aspect of the present invention. [1] A hydrogen isomerization process useful for producing dewaxing products containing a base oil, This includes contacting a hydrocarbon feed with a hydrogen isomerization catalyst under hydrogen isomerization conditions to produce a product; The hydrogen isomerization process wherein the hydrogen isomerization catalyst comprises an SSZ-91 molecular sieve and at least two different reforming metals selected from Groups 7-10 and 14 of the periodic table. [2] The process according to [1], wherein the catalyst comprises a first group 10 metal and a second metal selected from group 7 to 10 and group 14 metals of the periodic table. [3] The process according to [2], wherein the first group 10 metal comprises Pt. [4] The process according to any one of [1] to [3], wherein the Group 7 to 10 and Group 14 metals are selected from Pt, Pd, Ni, Re, Ru, Ir, and Sn. [5] The process according to any one of [2] to [4], wherein the second group 7-10 and group 14 metal is selected from Pd, Ni, Re, Ru, Ir, and Sn. [6] A process according to any one of items [1] to [5], wherein the sieve contains a ZSM-48 type zeolite material, and the molecular sieve is At least 70% of all ZSM-48 type materials are polytype 6; With EUO-type phase in amounts between 0 and 3.5% by weight; The process comprising a polycrystalline aggregate form containing microcrystals having an average aspect ratio between 1 and 8. [7] The process according to any one of [1] to [6], wherein the content of the modified metal is 0.01 to 5.0% by weight, or 0.01 to 2.0% by weight, or 0.1 to 2.0% by weight (based on total catalyst weight). [8] The process according to any one of [1] to [7], wherein the catalyst comprises Pt as one of the reforming metals in amounts of 0.01 to 1.0% by weight and 0.01 to 1.5% by weight of the second metal selected from Groups 7 to 10 and 14, preferably 0.3 to 0.8% by weight of Pt and 0.05 to 0.5% by weight of the second metal. [9] The process according to any one of [2] to [8], wherein the ratio of the first Group 10 metal to the second metal selected from Groups 7 to 10 and 14 is in the range of 5:1 to 1:5, or 3:1 to 1:3, or 1:1 to 1:2, or 5:1 to 2:1, or 5:1 to 3:1, or 1:1 to 1:3, or 1:1 to 1:4.

[10] The process according to any one of [1] to [9], wherein the catalyst comprises 0.01 to 1.0 wt% or 0.3 to 0.8 wt% of Pt as a Group 10 metal, and 0.01 to 1.5 wt% or 0.05 to 0.5 wt% of a second metal selected from Pd, Ni, Re, Ru, Ir, and Sn as a Group 7 to 10 and Group 14 metal.

[11] The process according to any one of [1] to

[10] , wherein the molar ratio of silicon oxide to aluminum oxide in the sieve is in the range of 40 to 220, or 50 to 220, or 40 to 200.

[12] A process described in any one of items [1] to

[12] , wherein the sieve is: At least 80% or 90% of all ZSM-48 type materials are polytype 6; 0.1-2% by weight of EU-1; Microcrystals having an average aspect ratio between 1 and 5, or between 1 and 3; Or a combination thereof, the process comprising one or more of the above.

[13] The process according to any one of [1] to

[12] , wherein the catalyst further comprises a matrix material selected from alumina, amorphous silica-alumina (ASA), or a combination thereof.

[14] The process according to

[13] , wherein the catalyst comprises 0.01 to 5.0 wt% of the modified metal, 1 to 99 wt% of the matrix material, and 0.1 to 99 wt% of the SSZ-91 molecular sieve.

[15] The process according to any one of [1] to

[14] , wherein the hydrocarbon feed includes diesel fuel; vacuum diesel fuel; long residue; vacuum residue; atmospheric distillates; heavy oils; oils; waxes and paraffins; spent oils; de-asphalt residues or crude oils; charges resulting from thermal or catalytic conversion processes; shale oil; circulating oils; fats, oils and waxes of animal and plant origin; petroleum and slack waxes; or combinations thereof.

[16] A hydrogen isomerization catalyst for use in the process described in [1], wherein the catalyst comprises 0.01 to 5.0 wt% of the modified metal, 1 to 99 wt% of the matrix material, and 0.1 to 99 wt% of the SSZ-91 molecular sieve.

[17] A process for producing a base oil product having reduced aromatic content, comprising subjecting a hydrocarbon feed to the method described in [1].

[18] The process according to

[17] , wherein the hydrocarbon feed is a neutral heavy base oil and the catalyst comprises a combination of reforming metals selected from Pt / Pd and Pt / Re.

[19] The process according to

[18] , wherein the aromatic conversion rate is increased by at least about 1.5 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt%, or 6.0 wt%, compared to the same process using an SSZ-91 catalyst containing only Pt as the modifying metal. [Modes for carrying out the invention]

[0009] While this specification illustrates exemplary embodiments of one or more aspects, the disclosed processes can be carried out using a number of techniques. This disclosure, including any exemplary designs and embodiments illustrated and described herein, is not limited to the exemplary or specific embodiments, drawings and techniques illustrated herein, and may be modified within the scope of the appended claims, along with the entire range of equivalents.

[0010] Unless otherwise indicated, the following terms, technical terms, and definitions apply to this disclosure. Where a term is used in this disclosure but is not specifically defined herein, the definition in IUPAC Compendium of Chemical Terminology, 2nd ed (1997) may be applied, provided that such definition does not conflict with any other disclosure or applicable definition herein, or make any claim to which such definition applies unclear or unenforceable. To the extent that any definition or usage provided in any document incorporated herein by reference conflicts with any definition or usage provided herein, the definition or usage provided herein shall apply.

[0011] "API specific gravity" refers to the specific gravity of petroleum raw materials or products relative to water, as determined by ASTM D4052-11.

[0012] The "viscosity index" (VI) is determined by ASTM D2270-10 (E2011) and represents the temperature dependence of a lubricant.

[0013] Vacuum gasoline (VGO) is a byproduct of the vacuum distillation of crude oil and can be sent to a hydrotreatment or aromatic extraction process to be upgraded to a base oil. VGO generally contains hydrocarbons with a boiling point range of 343°C (649°F) to 593°C (1100°F) at 0.101 MPa.

[0014] "Processed," "processed," "upgraded," and "upgraded" refer to materials or crude products that, when used in conjunction with oil raw materials, have been hydrogenated, or have been hydrogenated raw materials, or have been obtained in which the molecular weight of the raw material has been reduced, the boiling point range of the raw material has been reduced, the concentration of asphaltenes has been reduced, the concentration of hydrocarbon free radicals has been reduced, and / or the amount of impurities such as sulfur, nitrogen, oxygen, halides and metals has been reduced.

[0015] Hydroprocessing refers to the process of contacting a carbonous raw material with hydrogen and a catalyst at high temperatures and pressures for the purpose of removing undesirable impurities and / or converting the carbonous raw material into a desired product. Examples of hydroprocessing processes include hydrocracking, hydrogenation, catalytic dewaxing, and hydrogenation finishing.

[0016] Hydrocracking refers to a process in which hydrogenation and dehydrogenation are accompanied by the cracking / fragmentation of hydrocarbons, such as converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatic compounds and / or cycloparaffins (naphthenes) into acyclic branched paraffins.

[0017] "Hydrotherming" typically refers to a process, usually in conjunction with hydrocracking, that converts a sulfur and / or nitrogen-containing hydrocarbon feed into hydrocarbon products with reduced sulfur and / or nitrogen content, producing hydrogen sulfide and / or ammonia (respectively) as byproducts. Such processes or steps carried out in the presence of hydrogen include hydrodesulfurization, hydrodenitrification, hydrodemetallation, and / or hydrodesaromatization of components (e.g., impurities) of the hydrocarbon feedstock, and / or hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrogenotherming and reaction conditions, the products of the hydrogenotherming process may exhibit improvements, for example, in viscosity, viscosity index, saturation content, low-temperature properties, volatility, and reduced polarity. The terms "guard layer" and "guard bed" may be used synonymously and interchangeably herein to refer to a hydrogenotherming catalyst or hydrogenotherming catalyst layer. The guard layer may be a component of a hydrocarbon dewaxing catalyst system and may be located upstream of at least one hydrogen isomerization catalyst.

[0018] "Contact dewaxing," or hydrogen isomerization, refers to the process of isomerizing normal paraffins into more branched counterparts by contacting them with a catalyst in the presence of hydrogen.

[0019] Hydrofinishing refers to a process aimed at improving the oxidative stability, UV stability, and appearance of a hydrofinished product by removing trace amounts of aromatics, olefins, colorants, and solvents. UV stability refers to the stability of the hydrocarbon under test when exposed to UV light and oxygen. Instability is indicated by the formation of visible precipitates, usually seen as hoc or cloudiness, or by the development of a darker color when exposed to ultraviolet light and air. General descriptions of hydrofinishing can be found in U.S. Patents 3,852,207 and 4,673,487.

[0020] The term "hydrogen" refers to hydrogen itself and / or the compound(s) that supply a hydrogen source.

[0021] "Aromatic content" refers to the aromatic content in the dewaxing product, calculated using the following formula for the conversion rate of aromatics (X): X = (C フィード -C 生成物 ) / C フィード *100 (Here C フィード and C 生成物 (This refers to the aromatic content in the feed and the product.)

[0022] A "cut point" refers to the temperature on the true boiling point (TBP) curve at which a certain degree of separation is reached.

[0023] The "pour point" refers to the temperature at which oil begins to flow under controlled conditions. The pour point can be determined, for example, by ASTM D5950.

[0024] The "cloud point" refers to the temperature at which a lubricating oil base oil sample begins to produce haze when cooled under specific conditions. The cloud point of a lubricating oil complements its pour point. The cloud point can be determined, for example, by ASTM D5773.

[0025] "TBP" refers to the boiling point of a hydrocarbon feed or product determined by SimDist according to ASTM D2887-13.

[0026] The terms "hydrocarbonaceous," "hydrocarbon," and similar terms refer to compounds containing only carbon and hydrogen atoms. If a specific group is present in the hydrocarbon, other identifiers can be used to indicate the presence of that group (for example, halogenated hydrocarbons indicate the presence of one or more halogen atoms that replace an equal number of hydrogen atoms in the hydrocarbon).

[0027] The term “periodic table” refers to the IUPAC periodic table version dated June 22, 2007, and the numbering scheme for the periodic table families is as described in Chem.Eng.News, 63(5), 26-27(1985). “Group 2” refers to the IUPAC Group 2 elements, in elemental, compound, or ionic form, e.g., magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof. “Group 7” refers to the IUPAC Group 7 elements, in elemental, compound, or ionic form, e.g., manganese (Mn), rhenium (Re), and combinations thereof. “Group 8” refers to the IUPAC Group 8 elements, in elemental, compound, or ionic form, e.g., iron (Fe), ruthenium (Ru), osmium (Os), and combinations thereof. "Group 9" refers to the IUPAC Group 9 elements, whether in elemental, compound, or ionic form, such as cobalt (Co), rhodium (Rh), iridium (Ir), and combinations thereof. "Group 10" refers to the IUPAC Group 10 elements, whether in elemental, compound, or ionic form, such as nickel (Ni), palladium (Pd), platinum (Pt), and combinations thereof. "Group 14" refers to the IUPAC Group 14 elements, whether in elemental, compound, or ionic form, such as germanium (Ge), tin (Sn), lead (Pb), and combinations thereof.

[0028] The term "carrier," especially when used in the context of "catalyst carrier," typically refers to a conventional material that supports a catalytic material, which is a solid with a large surface area. The carrier material may be inert or involved in the catalytic reaction, and may be porous or non-porous. Typical catalyst carriers include various types of carbon, alumina, silica, and silica-alumina, such as amorphous silicaaluminate, zeolites, alumina-boria, silica-alumina-magnesia, silica-alumina-titania, and materials obtained by adding other zeolites and other composite oxides to them.

[0029] A "molecular sieve" refers to a material that has a framework structure with uniform molecular dimensions of pores, and depending on the type of molecular sieve, only certain molecules can reach the pore structure of that molecular sieve, while other molecules are excluded, for example, due to their size and / or reactivity. The terms "molecular sieve" and "zeolite" are synonymous and include (a) intermediates and (b) final or target molecular sieves, and molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary modification). Secondary synthesis techniques enable the synthesis of target materials from intermediate materials by heteroatomic lattice substitution or other techniques. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatomic lattice substitution of Al for B. Such techniques are known, for example, as described in U.S. Patent No. 6,790,433. Zeolites, crystalline aluminophosphates, and crystalline silicoaluminophosphates are typical examples of molecular sieves.

[0030] In this disclosure, compositions and methods or processes are often described in terms of "including" various components or steps, but unless otherwise stated, such compositions and methods may "essentially consist of" or "consist of" such components or steps.

[0031] The terms “a,” “an,” and “the” are intended to include plural forms, for example, at least one. For example, the disclosure of a transition metal or an alkali metal, unless otherwise specified, is intended to include one transition metal or alkali metal, a mixture of two or more transition metals or alkali metals, or a combination of two or more transition metals or alkali metals.

[0032] In the detailed descriptions and claims herein, all numerical values ​​are modified by "about" or "approximately," taking into account experimental errors and variations that a person skilled in the art would anticipate.

[0033] In one embodiment, the present invention relates to a hydrogen isomerization process useful for producing a dewaxing product containing a base oil, the process comprising contacting a hydrocarbon feed with a hydrogen isomerization catalyst under hydrogen isomerization conditions to produce a product or product stream, wherein the hydrogen isomerization catalyst comprises a bimetallic SSZ-91 molecular sieve containing at least two reforming metals selected from groups 7-10 and 14 of the periodic table.

[0034] SSZ-91 molecular sieves used in hydrogen isomerization catalysts are described, for example, in U.S. Patent Nos. 9,802,830; 9,920,260; 10,618,816; and WO2017 / 034823. SSZ-91 molecular sieves generally comprise a ZSM-48 type zeolite material, which has a polycrystalline aggregate form containing at least 70% polytype 6 of the total ZSM-48 type material; 0–3.5 weight percent of EUO type phase; and microcrystals having an average aspect ratio of 1–8. The silicon oxide to aluminum oxide molar ratio of the SSZ-91 molecular sieve may be in the range of 40–220 or 50–220 or 40–200. The aforementioned patents provide additional details relating to SSZ-91 sieves, methods for their preparation, and catalysts formed therefrom.

[0035] The bimetallic SSZ-91 catalyst may be advantageous in comprising a Group 10 metal and, optionally, a second metal selected from Groups 7-10 and 14 of the periodic table. The Group 10 metal may be, for example, platinum, palladium, or a combination thereof, and optionally comprises a Group 2 metal. Platinum is, in some embodiments, a suitable Group 10 metal, alongside other Groups 7-10 and 14 metals. The Groups 7-10 and 14 metals may be more narrowly selected from Pt, Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof, but are not limited to these. Along with Pt as the first metal of the SSZ-91 catalyst, the second metal of the bimetallic SSZ-91 catalyst may also be more narrowly selected from a second Group 7-10, and the Group 14 metal may be selected from Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof. In a more specific example, the bimetallic SSZ-91 catalyst may contain Pt as a Group 10 metal in amounts of 0.01 to 5.0 wt%, or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt%, more specifically 0.01 to 1.0 wt% and 0.01 to 1.5 wt%, and a second metal selected from Groups 7 through 10 and 14, such as Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof, in amounts of 0.01 to 5.0 wt%, or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt%, more specifically 0.01 to 1.0 wt% and 0.01 to 1.5 wt%. In another example, the catalyst comprises Pt as one of the reforming metals, in amounts of 0.01–1.0 wt% and 0.01–1.5 wt% of a second metal selected from groups 7–10 and 14, or more specifically, 0.3–0.8 wt% of Pt and 0.05–0.5 wt% of the second metal.

[0036] The metal content in the bimetallic SSZ-91 catalyst can vary over a typically useful range, for example, the total reformed metal content of the catalyst may be 0.01–5.0 wt%, 0.01–2.0 wt%, or 0.1–2.0 wt% (based on total catalyst weight). In some cases, the catalyst may contain 0.01–1.0 wt% of Pt and 0.01–1.5 wt% of a second metal selected from groups 7–10 and 14 as one of the reformed metals, or 0.3–1.0 wt% of Pt and 0.03–1.0 wt% of a second metal, or 0.3–1.0 wt% of Pt and 0.03–0.8 wt% of a second metal. In some cases, the ratio of a Group 10 metal to any second metal selected from Groups 7-10 and 14 may be in the range of 5:1-1:5, or 3:1-1:3, or 1:1-1:2, or 5:1-2:1, or 5:1-3:1, or 1:1-1:3, or 1:1-1:4.

[0037] The bimetallic SSZ-91 catalyst may further contain a matrix material selected from alumina, silica, titania, or a combination thereof. In more specific cases, the first catalyst comprises 0.01 to 5.0 wt% of the modified metal, 1 to 99 wt% of the matrix material, and 0.1 to 99 wt% of the SSZ-91 molecular sieve.

[0038] Hydrocarbon feeds may generally be selected from a variety of base oil raw materials and may be advantageous to include diesel fuel; vacuum diesel fuel; long residue; vacuum residue; atmospheric distillates; heavy oils; oils; waxes and paraffins; spent oils; de-asphalt residues or crude oils; charges resulting from thermal or catalytic conversion processes; shale oil; cycle oils; fats, oils and waxes of animal and plant origin; petroleum and slack waxes; or combinations thereof. Hydrocarbon feeds may also include feed hydrocarbon cuts with distillation ranges of 400–1300°F, or 500–1100°F, or 600–1050°F, and / or hydrocarbon feeds with a KV100 (kinematic viscosity at 100°C) range of about 3–30 cSt or about 3.5–15 cSt.

[0039] In some cases, the SSZ-91 catalyst can be advantageously used for heavy neutral base oils as a hydrocarbon feed containing a combination of reforming metals selected from Pt / Pd and Pt / Re.

[0040] The product(s) or product stream may be used to produce one or more base oil products, for example, to produce multiple grades having a KV100 in the range of about 2 to 30 cSt. Such base oil products may, in some cases, have a pour point of about -5°C, or -12°C, or -14°C or lower.

[0041] The process and system may also be combined with additional process steps or system components, for example, the raw materials may be further subjected to hydrogen treatment conditions using a hydrogen treatment catalyst before contacting the hydrocarbon feed with the SSZ-91 hydrogen isomerization catalyst, and optionally the hydrogen treatment catalyst includes a guard layer catalyst containing a refractory inorganic oxide material comprising about 0.1 to 1% by weight of Pt and about 0.2 to 1.5% by weight of Pd.

[0042] Among the advantages provided by this process and catalyst system is a reduction in the aromatic content of base oil products produced using the bimetallic SSZ-91 catalyst system compared to the same process using a non-bimetallic SSZ-91 catalyst. Of the advantages provided by the process and system, the aromatic conversion rate is significantly increased by at least about 1.5 wt%, or 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt%, or 6.0 wt%, when using the bimetallic SSZ-91 catalyst, compared to when using a non-bimetallic SSZ-91 catalyst that contains only the same Group 10 metal, e.g., Pt, but does not contain the second metal of the bimetallic SSZ-91 catalyst.

[0043] In practice, hydrodewaxing is primarily used to reduce the pour point of a base oil by removing wax from the base oil and / or to reduce the cloud point of the base oil. Typically, dewaxing employs a catalytic process to treat wax, and generally, the dewaxing feed is upgraded prior to dewaxing to increase the viscosity index, reduce the content of aromatics and heteroatoms, and decrease the amount of low-boiling components in the dewaxing feed. Some dewaxing catalysts achieve the wax conversion reaction by cracking wax molecules into low molecular weight molecules. Other dewaxing processes convert wax contained in a hydrocarbon feed through a process involving wax isomerization, which can produce isomerized molecules having a lower pour point than their non-isomerized molecular counterparts. As used herein, isomerization includes hydroisomerization processes that use hydrogen in the isomerization of wax molecules under catalytic hydroisomerization conditions.

[0044] Appropriate hydrodewaxing conditions generally depend on the feed used, the catalyst employed, the desired yield, and the desired properties of the base oil. Typical conditions include: a temperature of from 500°F to 775°F (260°C to 413°C); a pressure of from 15 psig to 3000 psig (0.10 MPa to 20.68 MPa gauge); a LHSV of 0.25 hour -1 to 20 hour -1 ; and a hydrogen to feed ratio of from 2000 SCF / bbl to 30,000 SCF / bbl (356 to 5340 m 3 H2 / m 3 feed). Generally, hydrogen is separated from the product and recycled to the isomerization zone. Generally, the dewaxing process of the present invention is carried out in the presence of hydrogen. Typically, the ratio of hydrogen to hydrocarbon may range from about 2000 to about 10,000 standard cubic feet of H2 per barrel of hydrocarbon, and usually may be from about 2500 to about 5000 standard cubic feet of H2 per barrel of hydrocarbon. The above conditions may be applied to the hydroprocessing conditions in the hydroprocessing zone, as well as the hydroisomerization conditions for the first and second catalysts. Suitable dewaxing conditions and processes are described, for example, in U.S. Patent Nos. 5,135,638; 5,282,958; and 7,282,134.

[0045] The catalyst system generally includes a catalyst containing a bimetallic SSZ-91 catalyst, and the raw materials are arranged to come into contact with the SSZ-91 catalyst before a further hydrogenation finishing step. The bimetallic SSZ-91 catalyst may be on its own, in combination with other catalysts, and / or in a layered catalyst system. Additional processing steps and catalysts may be included, for example, a hydrogenation catalyst / step, a guard layer, and / or a hydrogenation finishing catalyst / step, as described above. [Examples]

[0046] Example 1 - Preparation of a hydrogen isomerization catalyst Hydrogen isomerization catalyst A was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65% by weight of zeolite, which was then extruded, dried, and calcined. The dried and calcined extruded material was impregnated with a platinum-containing solution, and the impregnated catalyst was subsequently dried and calcined. The overall platinum load was 0.6% by weight.

[0047] Hydrogen isomerization catalyst B was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65% by weight of zeolite, which was then extruded, dried, and calcined. The dried and calcined extruded material was impregnated with a palladium-containing solution, and the impregnated catalyst was subsequently dried and calcined. The metal load was 0.46% by weight of Pd.

[0048] Hydrogen isomerization catalyst C was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65% by weight of zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was impregnated with a solution containing platinum and palladium, and the impregnated catalyst was then dried and calcined. The metal loads were 0.67% by weight of Pt and 0.09% by weight of Pd.

[0049] Hydrogen isomerization catalyst D was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was impregnated with a solution containing platinum and palladium, and this co-impregnated catalyst was then dried and calcined. The metal loads were 0.42 wt% Pt and 0.23 wt% Pd.

[0050] Hydrogen isomerization catalyst E was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was impregnated with a solution containing platinum and iridium, and this co-impregnated catalyst was then dried and calcined. The metal loads were 0.6 wt% Pt and 0.2 wt% Ir.

[0051] Hydrogen isomerization catalyst F was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was first impregnated with a rhenium-containing solution, and the impregnated catalyst was then dried and calcined. The dried and calcined extruded material was second-time impregnated with a platinum-containing solution, and the impregnated catalyst was then dried and calcined. The metal loads were 0.6 wt% Pt and 0.2 wt% Re.

[0052] Hydrogen isomerization catalyst G was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was first impregnated with a ruthenium-containing solution, and this impregnated catalyst was then dried and calcined. The dried and calcined extruded material was secondarily impregnated with a platinum-containing solution, and this impregnated catalyst was then dried and calcined. The metal loads were 0.6 wt% Pt and 0.2 wt% Ru.

[0053] The hydrogen isomerization catalyst H was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was first impregnated with a tin-containing solution, and the impregnated catalyst was then dried and calcined. The dried and calcined extruded material was second-time impregnated with a platinum-containing solution, and the impregnated catalyst was then dried and calcined. The metal loads were 0.6 wt% Pt and 0.4 wt% Sn.

[0054] Hydrogen isomerization catalyst I was prepared as follows: Microcrystalline SSZ-91 was compounded with alumina to provide a mixture containing 65 wt% zeolite, which was extruded, dried, and calcined. The dried and calcined extruded material was first impregnated with a nickel-containing solution, and this impregnated catalyst was then dried and calcined. The dried and calcined extruded material was second-time impregnated with a platinum-containing solution, and this impregnated catalyst was then dried and calcined. The metal loads were 0.6 wt% Pt and 0.2 wt% Ni.

[0055] Table 1 summarizes the metal content of the bimetallic SSZ-91 catalysts used in the examples. Catalysts A and B are non-bimetallic catalysts containing only one reforming metal. [Table 1] Example 2 - Hydrogen isomerization performance

[0056] The hydrogen isomerization performance of catalysts A to I in Example 1 was evaluated using the feed and reaction conditions described in WO2012 / 005980. A waxy heavy neutral hydrogen decomposition product (hydrodecomposition product, 600N) feed having the characteristics shown in Table 2 was used. [Table 2]

[0057] The reaction was carried out in a microunit, and the experiment was operated at a total pressure of 1500–2300 psig (e.g., 2100 psig in some cases) and a temperature in the range of 580–650°F. The catalyst was activated before introducing the feed. The heavy neutral feed was introduced for 0.5–3 hours. -1 The mixture was passed through a hydrogen isomerization reactor at LHSV in the range of and a hydrogen-to-oil ratio of approximately 3000 scfb. The unfinished base oil was separated from the fuel via a distillation section. The aromatic content was determined by using the aromatic content in the dewaxed product. The aromatic conversion rate was calculated using the following formula: X=(C フィード -C 生成物 ) / C フィード *100 (Here, C フィード and C 生成物 (This represents the aromatic content in the feed and product). The results for the evaluated catalysts are shown in Table 3. [Table 3]

[0058] Compared to reference catalyst A (Pt only), Examples C (Pt / Pd), D (Pt / Pd), and F (Pt / Re) show significantly improved aromatic conversion rates, i.e., the quality of the base oil products produced using these bimetallic catalysts is improved compared to the non-bimetallic SSZ-91 catalyst containing only Pt as the modifying metal.

[0059] The above description of one or more embodiments of the present invention is primarily illustrative and may include variations, which are recognized to be incorporated into the essence of the invention. In determining the scope of the invention, refer to the following claims.

[0060] For the purposes of U.S. patent practice and, where permitted, in other patent offices, any patents and publications referenced in the above description of the present invention are incorporated herein by reference to the extent that any information contained herein is consistent with and / or supplements the above disclosures.

Claims

1. A hydrogen isomerization process useful for producing dewaxing products containing a base oil, This includes contacting a hydrocarbon feed with a hydrogen isomerization catalyst under hydrogen isomerization conditions to produce a product; The hydrogen isomerization process wherein the hydrogen isomerization catalyst comprises an SSZ-91 molecular sieve and at least two different modified metals selected from Pt / Pd and Pt / Re.

2. The process according to claim 1, wherein the sieve comprises a ZSM-48 type zeolite material, and the molecular sieve is At least 70% of all ZSM-48 type materials are polytype 6; EUO-type phase in weight percentage amounts between 0 and 3.5; The process comprising a polycrystalline aggregate form containing microcrystals having an average aspect ratio between 1 and 8.

3. The process according to claim 1 or 2, wherein the content of the modified metal is 0.01 to 5.0% by weight, or 0.01 to 2.0% by weight, or 0.1 to 2.0% by weight (based on total catalyst weight).

4. The process according to any one of claims 1 to 3, wherein the catalyst comprises Pt as one of the reforming metals in an amount of 0.01 to 1.0% by weight, and a second metal selected from Pd and Re in an amount of 0.01 to 1.5% by weight.

5. The process according to claim 4, wherein the ratio of Pt to the second metal selected from Pd and Re is in the range of 5:1 to 1:5, or 3:1 to 1:3, or 1:1 to 1:2, or 5:1 to 2:1, or 5:1 to 3:1, or 1:1 to 1:3, or 1:1 to 1:

4.

6. The process according to claim 4 or 5, wherein the catalyst comprises 0.01 to 1.0% by weight or 0.3 to 0.8% by weight of Pt and 0.01 to 1.5% by weight or 0.05 to 0.5% by weight of a second metal selected from Pd and Re.

7. The process according to any one of claims 1 to 6, wherein the molar ratio of silicon oxide to aluminum oxide in the sieve is in the range of 40 to 220, or 50 to 220, or 40 to 200.

8. A process according to any one of claims 1 to 7, wherein the sieve is: At least 80% or 90% of the total ZSM-48 type material is polytype 6; EU-1 at 0.1–2% by weight; Microcrystals having an average aspect ratio between 1 and 5, or between 1 and 3; Or a combination thereof, the process comprising one or more of the above.

9. The process according to any one of claims 1 to 8, wherein the catalyst further comprises a matrix material selected from alumina, amorphous silica-alumina (ASA), or a combination thereof.

10. The process according to claim 9, wherein the catalyst comprises 0.01 to 5.0% by weight of the modified metal, 1 to 99% by weight of the matrix material, and 0.1 to 99% by weight of the SSZ-91 molecular sieve.

11. The process according to any one of claims 1 to 10, wherein the hydrocarbon feed comprises diesel fuel; vacuum diesel fuel; long residue; vacuum residue; atmospheric distillate; heavy oil; oil; wax and paraffin; spent oil; de-asphalt residue or crude oil; charge resulting from a thermal or catalytic conversion process; shale oil; circulating oil; fats, oils and waxes of animal and plant origin; petroleum and slack wax; or a combination thereof.

12. A hydrogen isomerization catalyst for use in the process according to claim 1, wherein the catalyst comprises 0.01 to 5.0 wt% of the modified metal, 1 to 99 wt% of a matrix material selected from alumina, amorphous silica-alumina (ASA), or a combination thereof, and 0.1 to 99 wt% of the SSZ-91 molecular sieve.

13. A process for producing a base oil product having a reduced aromatic content, comprising subjecting a hydrocarbon feed to the method according to claim 1.

14. The process according to claim 13, wherein the hydrocarbon feed is a neutral heavy base oil.

15. The process according to claim 14, wherein the aromatic conversion rate is increased by at least about 1.5% by weight, or 2.0% by weight, or 3.0% by weight, or 4.0% by weight, or 5.0% by weight, or 6.0% by weight, compared to the same process using an SSZ-91 catalyst containing only Pt as the modifying metal.

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