Base oil hydrogenation treatment catalyst and use process

Abstract

An improved hydrotreating catalyst and a process for producing a base oil product, the catalyst comprising a base extrudate comprising amorphous silica alumina (ASA) with a high nano-pore volume and a second amorphous silica alumina. The catalyst and process generally involve using a base extrudate comprising high nano-pore volume ASA and a second ASA in the catalyst and producing a hydrotreated dewaxed base oil product by contacting the catalyst with a hydrocarbon feedstock. The catalyst base extrudate preferably comprises a first amorphous silica alumina having a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm and a second amorphous silica alumina having a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm, and the base extrudate formed from amorphous silica alumina and alumina has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm. The catalyst further comprises at least one modifying element selected from Groups 6 to 10 and Group 14 of the periodic table. The catalyst and process improve aromatic saturation.

Description

Technical Field

[0001] The present invention relates to a hydrotreating catalyst and process for producing base oil from hydrocarbon feedstocks using a catalyst comprising an amorphous silica alumina and a base extrudate comprising amorphous silica alumina having a high nano-pore volume.

Background Art

[0002] In a hydroisomerization dewaxing process for producing base oil from hydrocarbon feedstocks, the feedstock is introduced into a reactor containing a dewaxing catalyst system in the presence of hydrogen. In the reactor, the feedstock contacts a hydroisomerization catalyst under hydroisomerization dewaxing conditions to provide an isomerized stream. Hydroisomerization removes aromatic compounds and residual nitrogen and sulfur and isomerizes normal paraffins to improve low-temperature flow properties. The isomerized stream can be further processed by contacting it with a hydrotreating and / or hydrofinishing catalyst to reduce or remove aromatic compounds and olefins and improve the color and / or other properties of the base oil product. The hydrotreating and / or hydrofinishing catalyst may include a support material and a noble metal, typically palladium, or platinum in combination with palladium.

[0003] The dewaxing of straight-chain paraffins involves various hydroconversion reactions such as hydroisomerization, branch redistribution, and secondary hydroisomerization. The continuous hydroisomerization reaction increases the degree of branching with branch redistribution. The increase in branching generally increases the probability of chain decomposition and results in a greater loss of fuel yield and base oil / lubricating oil yield. Therefore, the base oil / lubricating oil yield can be increased by minimizing such reactions including the formation of transition species in hydroisomerization.

[0004] Typical problems commonly faced in a hydroisomerization catalyst dewaxing process include, among others, providing a product that meets the relevant product specifications such as the cloud point, pour point, viscosity, and / or viscosity index limits of one or more products, while also maintaining a good product yield. Further upgrading can be used, for example, for color and oxidation stability, by saturating aromatic compounds to reduce the aromatic compound content, for example, during hydrotreating / hydrofinishing to further improve product quality. However, the presence of residual organic sulfur, nitrogen, and aromatic compounds from upstream hydrotreating and hydrocracking processes can have a significant impact on the quality of downstream processes and the final base oil product.

[0005] Therefore, a more robust catalyst for base oil / lubricating oil is required to improve the base oil / lubricating oil yield while improving the characteristics of the final product, such as reducing the aromatic compound content of the product.

Summary of the Invention

[0006] The present invention relates to a hydrotreating catalyst and process for converting a wax-containing hydrocarbon feedstock into a high-quality product generally comprising a base oil or lubricating oil with a reduced aromatic compound content. Such a process employs a catalyst system comprising a base extrudate formed from a mixture of a first amorphous silica alumina, which is a high nano-pore volume (HNPV) amorphous silica alumina (ASA1), and a second amorphous silica alumina (ASA2). It has been found that a catalyst formed from the base extrudate of HNPV ASA (ASA1) and amorphous silica alumina (ASA2) advantageously provides a base oil product with a reduced aromatic compound content in the base oil / lubricating oil product as compared to base oil products produced using other catalysts.

[0007] In one aspect, the present invention is directed to a dewaxing product containing a base oil, particularly a hydrogenation treatment catalyst and process useful for making base oil products of one or more product grades through the hydrogenation treatment of a suitable hydrocarbon source. While not necessarily limited thereto, one goal of the present invention is to provide a base oil product having a reduced aromatic compound content and providing a good product yield.

[0008] The catalyst generally comprises a base extrudate containing a first amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2). The amorphous silica alumina ASA1 is a high nanopore volume (HNPV) support material based on the pore volume within a defined pore diameter range. The amorphous silica alumina ASA1 is characterized by having a pore volume of 0.2 to 1.0 cc / g in the pore diameter range of 11 to 20 nm. The second amorphous silica alumina ASA2 may be HNPV ASA, or non-HNPV ASA, or a combination thereof. The amorphous silica alumina ASA2 is characterized by having a pore volume of 0.02 to 0.2 cc / g in the pore diameter range of 11 to 20 nm. The base extrudate containing ASA1 and ASA2 amorphous silica aluminas has a total pore volume of 0.12 to 1.80 cc / g in the pore diameter range of 2 to 50 nm. The catalyst further comprises at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

[0009] The use of a catalyst in a hydrotreating process generally involves contacting a hydrocarbon feedstock with a hydrotreating catalyst under hydrotreating conditions to produce a product or product stream. The hydrotreating catalyst comprises a base extrudate comprising HNPV amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2). The amorphous silica alumina ASA1 has a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm, and the second amorphous silica alumina ASA2 has a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm. The base extrudate has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm. The catalyst comprises at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

Embodiments for Carrying Out the Invention

[0010] Although exemplary embodiments of one or more aspects are shown herein, the disclosed processes can be implemented using any number of techniques. This disclosure is not limited to the exemplary or specific embodiments, drawings, and techniques illustrated herein, including any of the exemplary designs and embodiments illustrated herein, but can be modified within the scope of the appended claims, together with the full scope of equivalents.

[0011] Unless otherwise specified, the following terms, phrases, and definitions apply to this disclosure. If a term is used in this disclosure but not specifically defined herein, the definition from IUPAC Compendium of Chemical Terminology, 2nd ed (1997) may apply, provided that the definition does not conflict with any other disclosure or definition applied herein, or render any claim to which the definition is applied unclear or unacceptable. If any definition or usage shown in any document incorporated herein by reference conflicts with the definition or usage shown herein, the definition or usage shown herein shall apply.

[0012] "API gravity" refers to the specific gravity of petroleum feedstocks or products relative to water, as determined by ASTM D4052-11.

[0013] "Viscosity Index" (VI) represents the temperature dependence of lubricants, as determined by ASTM D2270-10 (E2011).

[0014] "Vacuum Gas Oil" (VGO) is a byproduct of the vacuum distillation of crude oil that can be sent to a hydrotreating unit or an aromatic extraction unit for upgrading to base oil. VGO generally contains hydrocarbons with a boiling range distribution of 343 °C (649 °F) to 593 °C (1100 °F) at 0.101 MPa.

[0015] "Treating", "treated", "upgrading", "upgrade" and "upgraded", when used in combination with a feedstock oil, describe a feedstock, or resulting material or crude product that has been hydrotreated or is a hydrotreated feedstock, and in which the molecular weight of the feedstock has been reduced, the boiling range of the feedstock has been narrowed, 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.

[0016] "Hydrotreating" refers to a process in which a carbonaceous feedstock is contacted with hydrogen and a catalyst at elevated temperature and pressure for the purpose of removing undesirable impurities and / or converting the feedstock to a desired product. Examples of hydrotreating processes include hydrocracking, hydrotreating, catalytic dewaxing, and hydrofinishing.

[0017] "Hydrocracking" refers to a process involving the cracking / decomposition of hydrocarbons with hydrogenation and dehydrogenation, e.g., converting heavier hydrocarbons to lighter hydrocarbons or converting aromatic compounds and / or cycloparaffins (naphthenes) to acyclic branched paraffins.

[0018] "Hydrotreating" generally refers to a process that, in combination with hydrocracking, converts a sulfur- and / or nitrogen-containing hydrocarbon feedstock into hydrocarbon products with reduced sulfur and / or nitrogen content, producing hydrogen sulfide and / or ammonia as by-products respectively. Such processes or steps carried out in the presence of hydrogen include hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, and / or hydrodearomatization of the components (e.g., impurities) of the hydrocarbon feedstock, and / or hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrotreating and the reaction conditions, the products of the hydrotreating process may exhibit, for example, improved viscosity, viscosity index, saturate content, low-temperature properties, volatility, and depolarization. The terms "guard bed" and "guard layer" are used synonymously and interchangeably herein and may refer to a hydrotreating catalyst or a hydrotreating catalyst bed. The guard bed may be a component of a hydrocarbon dewaxing catalyst system and may be disposed upstream of at least one hydroisomerization catalyst.

[0019] "Catalytic dewaxing" or hydroisomerization refers to a process of isomerizing normal paraffins to more branched counterparts by contacting them with a catalyst in the presence of hydrogen.

[0020] "Hydrofinishing" refers to a process intended to improve the oxidation stability, UV stability, and appearance of a hydrofinished product by removing trace amounts of aromatic compounds, olefins, colored bodies, and solvents. UV stability refers to the stability of the hydrocarbon being tested when exposed to UV light and oxygen. Instability is indicated when visible precipitates, usually regarded as Hoc or cloudiness, are formed, or when a dark color develops upon exposure to ultraviolet light and air. A general description of hydrofinishing can be found in U.S. Patent Nos. 3,852,207 and 4,673,487.

[0021] The term "Hydrogen" or "hydrogen" refers to hydrogen itself and / or the compound(s) that supply a hydrogen source.

[0022] The "BET surface area" is determined by N2 adsorption at its boiling point. The BET surface area is calculated by the five-point method with P / P0 = 0.050, 0.088, 0.125, 0.163, and 0.200. First, the sample is pretreated at 400 °C for 6 hours in the presence of flowing dry N2 to remove adsorbed volatile substances such as water and organic substances.

[0023] The "cut point" refers to the temperature on the true boiling point (TBP) curve that reaches a predetermined degree of separation.

[0024] The "pour point" refers to the temperature at which the oil begins to flow under controlled conditions. The pour point can be measured by ASTM D5950.

[0025] The "cloud point" refers to the temperature at which a lubricating base oil sample begins to become cloudy when cooled under specified conditions. The cloud point of a lubricating base oil is complementary to its pour point. The cloud point can be determined by ASTM D5773.

[0026] The "nanopore diameter" and "nanopore volume" are determined by adsorption at the boiling point of N2 and calculated from the N2 isotherm by the BJH method described in "The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms." by E.P. Barrett, L.G. Joyner, and P.P. Halenda, J. Am. Chem. Soc. 73, 373-380, 1951. First, the sample is pretreated at 400 °C for 6 hours in the presence of flowing dry N2 to remove adsorbed volatile substances such as water and organic substances. The pore diameters corresponding to 10%, 50%, and 90% of the total nanopore volume (referred to as d 10 , d 50 , and d 90 respectively) can also be determined from such N2 adsorption measurements.

[0027] "TBP" refers to the boiling point of a hydrocarbonaceous feedstock or product determined by the simulated distillation method (SimDist) according to ASTM D2887-13.

[0028] "Hydrocarbonaceous", "hydrocarbon" and similar terms refer to compounds containing only carbon and hydrogen atoms. When a specific group is present in a hydrocarbon, other identifying terms can be used to indicate the presence of that specific group (for example, a halogenated hydrocarbon indicates the presence of one or more halogen atoms that have replaced an equal number of hydrogen atoms in the hydrocarbon).

[0029] The "Periodic Table" refers to the IUPAC Periodic Table of the Elements dated Jun.22,2007 edition, and the notation of the group numbers in the periodic table is as described in Chem.Eng.News,63(5),26-27(1985). The "Group 2" refers to the IUPAC Group 2 elements, for example, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and their combinations in any of their elemental, compound, or ionic forms. The "Group 6" refers to the IUPAC Group 6 elements, for example, chromium (Cr), molybdenum (Mo) and tungsten (W). The "Group 7" refers to the IUPAC Group 7 elements, for example, manganese (Mn), rhenium (Re) and their combinations in any of their elemental, compound, or ionic forms. The "Group 8" refers to the IUPAC Group 8 elements, for example, iron (Fe), ruthenium (Ru), osmium (Os) and their combinations in any of their elemental, compound, or ionic forms. The "Group 9" refers to the IUPAC Group 9 elements, for example, cobalt (Co), rhodium (Rh), iridium (Ir) and their combinations in any of their elemental, compound, or ionic forms. The "Group 10" refers to the IUPAC Group 10 elements, for example, nickel (Ni), palladium (Pd), platinum (Pt) and their combinations in any of their elemental, compound, or ionic forms. The "Group 14" refers to the IUPAC Group 14 elements, for example, germanium (Ge), tin (Sn), lead (Pb), and their combinations in any of their elemental, compound, or ionic forms.

[0030] The term "carrier", especially when used in the term "catalyst carrier", refers to a conventional material that is usually a solid with a large surface area and that supports a catalyst material. The carrier material may be inert or may participate 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 silica aluminates, zeolites, alumina-boria, silica-alumina-magnesia, silica-alumina-titania and materials obtained by adding other zeolites and other composite oxides.

[0031] "Molecular sieve" refers to a material having uniformly sized pores of molecular dimensions within its framework structure, such that only certain molecules can reach the pore structure of the molecular sieve depending on the type of molecular sieve, while other molecules are excluded, for example, by the size and / or reactivity of the molecules. 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). The secondary synthesis method enables the synthesis of the target material from an intermediate material by heteroatom lattice substitution or other methods. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatom lattice substitution of B with Al. Such techniques are well known as described, for example, in U.S. Patent No. 6,790,433. Zeolites, crystalline aluminophosphates, and crystalline silicoaluminophosphates are representative examples of molecular sieves.

[0032] In the present disclosure, compositions, and methods or processes are often described in terms of "comprising" various components or steps, but the compositions and methods may, unless otherwise specified, "consist essentially of" or "consist of" those various components or steps.

[0033] The terms "a", "an", and "the" are intended to include a plurality of alternatives, e.g., at least one. For example, the disclosed "transition metal" or "alkali metal" means, unless otherwise specified, one or a mixture or combination of one or more transition metals or alkali metals.

[0034] All numerical values within the detailed description and claims of this specification are modified by the term "about" or "approximately" to account for experimental error and variations that would be expected by one of ordinary skill in the art.

[0035] In one aspect, the present invention is a hydrotreating catalyst useful for producing a dewaxing product comprising a base oil / lubricating oil having a reduced aromatic compound content, the catalyst comprising a base extrudate formed from high nanopore volume (HNPV) amorphous silica alumina (ASA1) and a second amorphous silica alumina, wherein the amorphous silica alumina ASA1 has a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm, and the second amorphous silica alumina ASA2 has a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm. The base extrudate has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm. The catalyst comprises at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

[0036] In another aspect, the present invention is a hydrotreating catalyst useful for producing a dewaxing product containing a base oil / lubricating oil with a reduced aromatic compound content. The catalyst comprises a base extrudate formed from high nanopore volume (HNPV) amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2), where the HNPV ASA1 amorphous silica alumina has a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm, and the second amorphous silica alumina ASA2 has a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm. The base extrudate has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm. The catalyst comprises at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

[0037] In a further aspect, the present invention relates to a hydrotreating process useful for producing a dewaxing product containing a base oil with a reduced aromatic compound content, the process comprising contacting a hydrocarbon feedstock with a hydrotreating catalyst under hydrotreating conditions to produce a product or product stream, the hydrotreating catalyst comprising a base extrudate formed from high nanopore volume (HNPV) amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2), where the HNPV ASA1 has a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm, and the second amorphous silica alumina ASA2 has a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm. The base extrudate has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm. The catalyst comprises at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

[0038] The first amorphous silica alumina (ASA1) used in the hydrogenation treatment catalyst and process is generally referred to as "high nanopore volume" amorphous silica alumina (ASA) and is abbreviated herein as "HNPV" amorphous silica alumina or "HNPV" ASA1. HNP ASA1 can be conveniently characterized according to its pore volume within the range of average pore diameter. The term "nanopore volume", abbreviated herein as "NPV", provides a convenient label for defining the NPV pore volume within those ranges of pore volume and values of ASA1, for example, in the pore diameter ranges of 2 - 6 nm, 6 - 11 nm, 11 - 20 nm, and 20 - 50 nm. Generally, HNPV ASA1 has a pore volume of 0.2 - 1.0 cc / g in the pore diameter range of 11 - 20 nm, more specifically, a pore volume of 0.24 - 0.85 cc / g in the pore diameter range of 11 - 20 nm, or a pore volume of 0.28 - 0.7 cc / g in the pore diameter range of 11 - 20 nm. Independently, or in addition to the aforementioned 11 - 20 nm range, the first amorphous silica alumina ASA1 has a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.06 - 0.8 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.07 - 0.6 cc / g in the pore diameter range of 2 - 6 nm. Independently, or in addition to the aforementioned 2 - 6 nm and 11 - 20 nm ranges, ASA1 has a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.06 - 0.8 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.07 - 0.6 cc / g in the pore diameter range of 6 - 11 nm. Independently, or in addition to the aforementioned 2 - 6 nm, 6 - 11 nm, and 11 - 20 nm ranges, ASA1 has a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 20 - 50 nm, or a pore volume in the pore diameter range of 0.07 - 0.8 cc / g at 20 - 50 nm, or a pore volume of 0.09 - 0.6 cc / g in the pore diameter range of 20 - 50 nm.

[0039] HNPV ASA1 can also be characterized in terms of total pore volume in the pore size range. For example, in addition to, or separately and independently of, the aforementioned NPV pore volume, HNPV ASA1 may have a total pore volume of 0.3 to 2.0 cc / g in the pore size range of 2 to 50 nm, or a total pore volume of 0.5 to 1.9 cc / g in the pore size range of 2 to 50 nm, or a total pore volume of 0.7 to 1.8 cc / g in the pore size range of 2 to 50 nm.

[0040] In comparison, non-HNPV amorphous silica alumina generally has a pore size distribution biased towards a larger pore volume content in a smaller pore size range. For example, such non-HNPV ASA may typically have a pore volume of less than about 0.2 cc / g, or less than about 0.18 cc / g, in the pore size range of 11 to 20 nm, and / or a pore volume of less than about 0.15 cc / g, or less than about 0.1 cc / g, in the pore size range of 20 to 50 nm.

[0041] The second amorphous silica alumina ASA2 used in the hydrogenation treatment catalyst and process can be conveniently characterized according to its pore volume within the average pore diameter range. As used herein, the term "nanopore volume", abbreviated as "NPV", provides a convenient label for defining the pore volume ranges and values within those ranges of amorphous silica alumina ASA2, for example, the NPV pore volume in the pore diameter ranges of 2 - 6 nm, 6 - 11 nm, 11 - 20 nm, and 20 - 50 nm. Generally, amorphous silica alumina ASA2 has a pore volume of 0.02 - 0.2 cc / g in the pore diameter range of 11 - 20 nm, more specifically, a pore volume of 0.03 - 0.18 cc / g in the pore diameter range of 11 - 20 nm, or a pore volume of 0.04 - 0.16 cc / g in the pore diameter range of 11 - 20 nm. Independently, or in addition to the aforementioned 11 - 20 nm range, amorphous silica alumina ASA2 may have a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.06 - 0.9 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.07 - 0.8 cc / g in the pore diameter range of 2 - 6 nm. Independently, or in addition to the aforementioned 2 - 6 nm and 11 - 20 nm ranges, amorphous silica alumina ASA2 may have a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.06 - 0.8 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.07 - 0.6 cc / g in the pore diameter range of 6 - 11 nm. Independently, or in addition to the aforementioned 2 - 6 nm, 6 - 11 nm, and 11 - 20 nm ranges, amorphous silica alumina ASA2 may have a pore volume of 0.01 - 0.2 cc / g in the pore diameter range of 20 - 50 nm, or a pore volume of 0.015 - 0.15 cc / g in the pore diameter range of 20 - 50 nm, or a pore volume of 0.02 - 0.1 cc / g in the pore diameter range of 20 - 50 nm.

[0042] The second amorphous silica alumina ASA2 can also be characterized in terms of its total pore volume over a pore diameter range. For example, in addition to or separately and independently of the aforementioned NPV pore volume, the amorphous silica alumina ASA2 may have a total pore volume of 0.3 to 2.0 cc / g in the pore diameter range of 2 to 50 nm, or a total pore volume of 0.4 to 1.8 cc / g in the pore diameter range of 2 to 50 nm, or a total pore volume of 0.5 to 1.6 cc / g in the pore diameter range of 2 to 50 nm.

[0043] The pore size distribution of a suitable non-HNPV ASA generally favors a larger pore volume content in a smaller pore diameter range. For example, such a non-HNPV ASA may typically have a pore volume of less than about 0.2 cc / g, or less than about 0.18 cc / g, in the pore diameter range of 11 to 20 nm, and / or a pore volume of less than about 0.15 cc / g, or less than about 0.1 cc / g, in the pore diameter range of 20 to 50 nm.

[0044] The HNPV amorphous silica alumina ASA1 and the second amorphous silica alumina ASA 2 may be commercially available materials from Sasol, JGC Catalysts and Chemicals, and PIDC (Pacific Industrial Development Corporation). Suitable HNPV ASA and non-HNPV ASA are commercially available and are known, for example, from patent documents including US10,183,282. One such family of ASA includes, for example, Sasol's SIRAL® ASA (Table 1).

Table 1

[0045] The silica content of the first amorphous silica alumina and the second amorphous silica alumina generally differs. For example, the silica content of the first amorphous silica alumina may range from 0.5 to 15 wt%, or 1 to 10 wt%, or 1.5 to 8 wt%. The silica content of the second amorphous silica alumina may range from 15 to 90 wt%, or 20 to 85 wt%, or 25 to 80 wt%.

[0046] The relative content of each of the first and second ASAs in the base extrudate may also usually vary in the ratio range of 4:1 to 1:4. In some cases, a narrower range may be more suitable. For example, the ratio of ASA 1 to ASA 2 is from 4:1 to 1:2, or from 4:1 to 1:1, or from 4:1 to 2:1, or from 2:1 to 1:4, or from 2:1 to 1:2, or from 2:1 to 1:1, or from 1:2 to 1:1, or from 1:4 to 1:2, or from 1:4 to 1:1. Generally, the total amount of the first amorphous silica alumina and the second amorphous silica alumina in the base extrudate is in the range of 10 to 95% by weight, or 20 to 90% by weight, or 25 to 85% by weight.

[0047] Catalysts comprising a base extrudate formed from HNPV ASA1 and a second amorphous silica alumina ASA2 generally also contain at least one modifier selected from Groups 6 - 10 and 14 of the Periodic Table (IUPAC). Suitable Group 6 modifiers include Group 6 elements such as chromium (Cr), molybdenum (Mo), and tungsten (W), and any combination of these elements, compounds, or ionic forms. Suitable Group 7 modifiers include Group 7 elements such as manganese (Mn), rhenium (Re), and combinations thereof in any of their elemental, compound, or ionic forms. Suitable Group 8 modifiers include Group 8 elements such as iron (Fe), ruthenium (Ru), osmium (Os), and combinations thereof in any of their elemental, compound, or ionic forms. Suitable Group 9 modifiers include Group 9 elements such as cobalt (Co), rhodium (Rh), iridium (Ir), and combinations thereof in any of their elemental, compound, or ionic forms. Suitable Group 10 modifiers include Group 10 elements such as nickel (Ni), palladium (Pd), platinum (Pt), and combinations thereof in any of their elemental, compound, or ionic forms. Suitable Group 14 modifiers include Group 14 elements such as germanium (Ge), tin (Sn), lead (Pb), and combinations thereof in any of their elemental, compound, or ionic forms. Additionally, any Group 2 modifiers may be present, such as Group 2 elements like magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof in any of their elemental, compound, or ionic forms.

[0048] The modifier advantageously contains one or more Group 10 metals. The Group 10 metal may be, for example, platinum, palladium, or a combination thereof. Platinum is, in some embodiments, a suitable Group 10 metal together with another Group 6 - 10 and Group 14 metal. The Group 6 - 10 and Group 14 metals may be more narrowly selected from, but are not limited to, Pt, Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof. In relation to Pt as the first metal in the catalyst, any second metal in the catalyst may be more narrowly selected from the second Group 6 - 10 and Group 14 metals and may be selected from Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof. In more specific examples, the catalyst may contain Pt as the Group 10 metal in an amount of 0.01 - 5.0 wt% or 0.01 - 2.0 wt%, or 0.1 - 2.0 wt%, more specifically 0.01 - 1.0 wt% or 0.3 - 0.8 wt%. Any second metal selected from Pd, Ni, Re, Ru, Ir, Sn, or combinations thereof as the Group 6 - 10 and Group 14 metals may be present in an amount of 0.01 - 5.0 wt% or 0.01 - 2.0 wt% or 0.1 - 2.0 wt%, more particularly 0.01 - 1.0 wt% and 0.01 - 1.5 wt%.

[0049] The metal content in the catalyst may vary within a useful range. For example, the total modifier metal content in the catalyst may be 0.01 - 5.0 wt%, or 0.01 - 2.0 wt%, or 0.1 - 2.0 wt% (based on the total catalyst weight). In some cases, the catalyst contains 0.1 - 2.0 wt% of Pt as one of the modifier metals and 0.01 - 1.5 wt% of a second metal selected from the Group 6 - 10 and Group 14, or 0.3 - 1.0 wt% of Pt and 0.03 - 1.0 wt% of the second metal, or 0.3 - 1.0 wt% of Pt and 0.03 - 0.8 wt% of the second metal. Optionally, the ratio of the first Group 10 metal to any second metal selected from the Group 6 - 10 and Group 14 may range from 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.

[0050] The catalyst may further comprise an additional matrix material selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, or combinations thereof. In more specific cases, the first catalyst comprises 0.01 to 5.0 wt% of a modifying metal, 1 to 99 wt% of a matrix material, and 0.1 to 99 wt% of a base extrudate comprising HNPVASA1 and ASA2. The catalyst can also be described more narrowly. For example, the catalyst may comprise 0.01 to 5.0 wt% of a modifier, 15 to 85 wt% of a matrix material, and 15 to 85 wt% of an HNPV ASA1 and ASA2 base extrudate. Two or more matrix materials may be used. For example, the matrix material may comprise about 15 to 65 wt% of a first matrix material and about 15 to 65 wt% of a second matrix material. In such cases, the first and second matrix materials generally differ in one or more characteristics such as the type of material or pore volume and pore distribution characteristics. When one or more matrix materials are used, the first, second (and any other) matrix materials may also be of the same type of matrix material. For example, the matrix material may comprise one or more aluminas.

[0051] Suitable HNPV and non-HNPV aluminas are commercially available and are known, for example, from patent documents including US10,183,282. One such family of aluminas includes, for example, CATAPAL® alumina from Sasol (Table 2). Sasol's PURAL® alumina may also be suitable.

Table 2

[0052] The catalyst-based extrudate is also preferably characterized by pore volume, both in terms of total pore volume and pore volume within a specific average pore diameter range. Similar to the HNPV ASA1 and ASA2 components, the base extrudate can be characterized according to the pore volume in the pore diameter ranges of 2 - 6 nm, 6 - 11 nm, 11 - 20 nm, and 20 - 50 nm. Generally, the base extrudate has a total pore volume of 0.12 - 1.80 cc / g in the pore diameter range of 2 - 50 nm, or more specifically, a total pore volume of 0.20 - 1.65 cc / g in the pore diameter range of 2 - 50 nm, or a total pore volume of 0.25 - 1.50 cc / g in the pore diameter range of 2 - 50 nm.

[0053] Independently, or in addition to the aforementioned total pore volume of 2 - 50 nm, the base extrudate may have a pore volume of 0.05 - 0.8 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.08 - 0.6 cc / g in the pore diameter range of 2 - 6 nm, or a pore volume of 0.1 - 0.5 cc / g in the pore diameter range of 2 - 6 nm. Independently, or in addition to the pore volume of 2 - 6 nm and the pore volume range of 2 - 50 nm mentioned above, the base extrudate may have a pore volume of 0.05 - 1.0 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.08 - 0.9 cc / g in the pore diameter range of 6 - 11 nm, or a pore volume of 0.1 - 0.8 cc / g in the pore diameter range of 6 - 11 nm. Independently, or in addition to the pore volume of 2 - 6 nm, the pore volume of 6 - 11 nm, and the total pore volume range of 2 - 50 nm mentioned above, the base extrudate may have a pore volume of 0.02 - 0.3 cc / g in the pore diameter range of 11 - 20 nm, or a pore volume of 0.03 - 0.25 cc / g in the pore diameter range of 11 - 20 nm, or a pore volume of 0.04 - 0.2 cc / g in the pore diameter range of 11 - 20 nm. Independently, or in addition to the pore volume of 2 - 6 nm, the pore volume of 6 - 11 nm, the pore volume of 11 - 20 nm, and the total pore volume range of 2 - 50 nm mentioned above, the base extrudate may have a pore volume of 0.01 - 0.3 cc / g in the pore diameter range of 20 - 50 nm, or a pore volume of 0.012 - 0.25 cc / g in the pore diameter range of 20 - 50 nm, or a pore volume of 0.015 - 0.2 cc / g in the pore diameter range of 20 - 50 nm.

[0054] The base extrudate can be manufactured according to any suitable method. For example, the base extrudate may be conveniently manufactured by mixing the components together and extruding the well-mixed HNPV ASA1 and ASA2 components to form the base extrudate. Next, the extrudate is dried and calcined, and subsequently any modifier is loaded onto the base extrudate. The modifier can be dispersed onto the base extrudate using a suitable impregnation method. However, the method for manufacturing the base extrudate is not intended to be particularly limited according to specific process conditions or techniques.

[0055] The hydrocarbon feedstock may generally be selected from various base oil feedstock materials and advantageously includes gas oil, vacuum gas oil, long residue, vacuum residue, atmospheric distillate, heavy fuel, oil, wax and paraffin, used oil, deasphalted residue or crude oil, charge obtained from a thermal conversion or catalytic conversion process, shale oil, cycle oil, animal and plant-derived fats, oils and waxes, petroleum and slack wax, or combinations thereof. The hydrocarbon feedstock may also include a feedstock hydrocarbon fraction having a distillation range of 400 to 1300°F, or 500 to 1100°F, or 600 to 1050°F, and / or the hydrocarbon feedstock has a KV100 (kinematic viscosity at 100°C) in the range of about 3 to 30 cSt or about 3.5 to 15 cSt.

[0056] The hydrocarbon feedstock may undergo an initial hydrotreating step before being subjected to this hydrotreating process. Such an initial hydrotreating step, although not limited or necessary, may include hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, and / or hydrodearomatization of the components (e.g., impurities) of the hydrocarbon feedstock. It is also possible to subject the hydrocarbon feedstock to an initial hydrotreating to improve certain properties of the hydrocarbon feedstock, such as viscosity characteristics. In some cases, the hydrotreating process may be advantageously used in combination with (e.g., subsequent to) a hydroisomerization process for a light or heavy neutral base oil feedstock such as vacuum gas oil (VGO). The hydrotreating process can then be carried out subsequent to such an initial hydrotreating by contacting the hydrocarbon feedstock with a catalyst formed from an ASA1 / ASA2-based extrudate.

[0057] The product(s) or product stream can be used in the manufacture of one or more base oil products, e.g., the manufacture of multiple grades having a KV100 in the range of about 2 to 30 cSt. In some cases, such base oil products can have a pour point of about -5°C, or -12°C, or -14°C or lower.

[0058] The process and system may also be combined with additional process steps or system components. For example, the feedstock may be further exposed to other hydrotreating conditions using a hydrotreating catalyst before contacting the hydrocarbon feedstock with the hydrotreating catalyst. Any additional layered catalysts can also be used. For example, the hydrotreating catalyst includes a guard bed catalyst comprising a refractory inorganic oxide material containing about 0.1 to 1 wt% of Pt and about 0.2 to 1.5 wt% of Pd.

[0059] Among the advantages provided by the present process and catalyst system is the improvement of base oil product properties (e.g., reduction in aromatic content) using the catalyst system of the present invention that includes HNPV ASA1 and a second amorphous silica alumina ASA2, compared to the same process using a similar catalyst that does not include a combination of HNPV ASA1 and ASA2 components in the base extrudate. In some cases, when the hydrotreating catalyst of the present invention that includes a base extrudate formed from both amorphous silica aluminas of ASA1 and ASA2 is used, compared to the case of being used in the same process of a similar catalyst that does not include both ASAs in the base extrudate, the aromatic content of the base oil product is significantly reduced by at least about 0.5 wt%, or 1.0 wt%, or 1.5 wt%, or 2.0 wt%. The aromatic content of the base oil product can also be characterized in terms of an increase in the aromatic saturation conversion rate, where the aromatic saturation conversion rate of the base oil product is significantly increased by at least about 0.5 wt%, or 1.0 wt%, or 1.5 wt%, or 2.0 wt% when the hydrotreating catalyst of the present invention is used, compared to the case of being used in the same process of a similar catalyst that does not include both ASA1 and ASA2 in the catalyst base extrudate.

[0060] In practice, hydrodewaxing is mainly used to lower the pour point of the base oil by removing wax from the base oil and / or to lower the cloud point of the base oil. Dewaxing usually uses a catalytic process to treat the wax, and the dewaxing agent feedstock is generally reformed before dewaxing to increase the viscosity index, reduce the aromatic and heteroatom content, and reduce the amount of low-boiling components in the dewaxing agent feedstock. Some dewaxing catalysts effect a wax conversion reaction by cracking wax-like molecules into lower molecular weight molecules. Other dewaxing processes can convert the wax contained in the hydrocarbon feedstock into a process by wax isomerization to produce isomerized molecules having a lower pour point than the corresponding non-isomerized molecules. As used herein, isomerization includes a hydroisomerization method for using hydrogen for the isomerization of wax molecules under catalytic hydroisomerization conditions.

[0061] Suitable hydrodewaxing and / or hydrogenation treatment conditions generally depend on the feedstock used, the catalyst used, the desired yield, and the desired properties of the base oil. Typical conditions include temperatures of 500°F to 775°F (260°C to 413°C), pressures of 15 psig to 3000 psig (0.10 MPa to 20.68 MPa gauge), a LHSV of 0.25 hours -1 to 20 hours -1 and a hydrogen / feedstock ratio of 2000 SCF / bbl to 30,000 SCF / bbl (356 to 5340 m 3 H2 / m 3 feedstock). Generally, hydrogen is separated from the product and recycled to the isomerization zone. The dewaxing process that can be used with the present invention is carried out in the presence of hydrogen, and the ratio of hydrogen to hydrocarbon is typically in the range of about 2000 to about 10,000 standard cubic feet of H2 per barrel of hydrocarbon, and usually in the range of about 2500 to about 5000 standard cubic feet of H2 per barrel of hydrocarbon. Such conditions can be applied to the hydrogenation treatment conditions of the hydrogenation treatment zone (including, for example, the guard bed upstream of the hydroisomerization catalyst), as well as the hydroisomerization conditions that can be used upstream of the present hydrogenation treatment process. Suitable dewaxing conditions and processes are described, for example, in U.S. Patent Nos. 5,135,638, 5,282,958, and 7,282,134.

[0062] A suitable catalyst system generally includes the hydrogenation treatment catalyst described herein, which includes a base extrudate formed from ASA1 and ASA2, arranged such that the feedstock contacts the hydrogenation treatment catalyst. The present hydrogenation treatment process and catalyst are generally used according to the hydrodewaxing / hydroisomerization process steps. The hydrogenation treatment catalyst may be used by itself, in combination with other catalysts, and / or in a layered catalyst system. Additional treatment steps and catalysts may be used in combination with the present hydrogenation treatment process, including, for example, additional hydrogenation treatment catalyst(s) / steps, guard beds, and / or hydrofinishing catalyst(s) / steps as noted.

Examples

[0063] The HNPV amorphous silica alumina ASA1 and the second amorphous silica alumina ASA2 used in the following examples were provided as commercially available materials according to the foregoing description. Comparative catalysts containing only one ASA component, i.e., ASA1 or ASA2, in the base extrudate were formed by combining the respective ASA components with commercially available alumina. The properties of these materials used in the examples are shown in Table 3. ASA1 contains 5 wt% silica and has large pores and a high nanopore volume, while ASA2 contains 70 wt% silica and has smaller pores and a lower nanopore volume.

Table 3

[0064] The metal dispersion of the PtPd bimetallic particles was determined by hydrogen chemisorption. The measurement included the following steps. After reduction, the sample was continuously evacuated until the total H2 chemisorption was measured at 110 °C at the following pressures: 20, 50, 80, 110, 140, 170, 200, 240, 280, 320, 360 torr. After measuring the total chemisorption, the catalyst was evacuated for 10 minutes and isothermal H2 chemisorption was repeated to determine the weak and strong H2 chemisorption components. The metal dispersion was calculated by strongly adsorbing hydrogen per PtPd atom.

[0065] The S / C surface center ratio, i.e., the Pt or Pd distribution in the extrudate, was determined by measuring the Pt or Pd concentration in the cross-sectional catalyst pellet by electron probe microanalysis (EPMA). After collecting the metal profile, the S / C ratio was calculated by dividing the surface concentration by the central concentration of the measured pellet of Pt or Pd.

[0066] Example 1 - Preparation of Hydrogenation Catalyst A The comparative hydrogenation catalyst A was prepared as follows. 80 wt% of the amorphous silica alumina ASA1 was composited with conventional alumina, and the mixture was extruded, dried, and calcined. The dried and calcined extrudate was impregnated with a solution containing platinum and palladium. The total noble metal load was 0.54 wt%.

[0067] Example 2 - Preparation of Hydrogenation Catalyst B The comparative hydrogenation catalyst B was prepared as described for catalyst A, except that ASA2 was used instead of ASA1, providing a mixture containing 80 wt% amorphous silica alumina ASA2 and 20 wt% alumina. The dried and calcined extrudates were impregnated with platinum and palladium, and the total noble metal load was 0.54 wt%.

[0068] Example 3 - Preparation of Hydrogenation Catalyst C The hydrogenation catalyst C was prepared as described for catalyst A, except that a 50 wt% / 50 wt% combination of ASA1 and ASA2 was used, providing a mixture containing 80 wt% amorphous silica alumina and 20 wt% alumina. The dried and calcined extrudates were impregnated with platinum and palladium, and the total noble metal load was 0.54 wt%.

[0069] The catalyst characteristics are shown in Table 4 (relative to the base catalyst A). [Table 4]

[0070] From Table 4, the relative metal dispersion and distribution in each catalyst can be noted. Catalyst A contained ASA1 in the base extrudate support and showed good metal dispersion and poor metal distribution. Catalyst B contained ASA2 in the base extrudate support and showed poor metal dispersion and good metal distribution. In contrast, catalyst C used a combination of ASA1 and ASA2 in the base extrudate support and showed both good metal dispersion and good metal distribution.

[0071] Example 4 - Hydrogenation Performance of Catalysts A, B, and C Catalysts A, B, and C were used to hydrogenate a dewaxed heavy neutral feedstock having the characteristics shown in Table 5. [Table 5]

[0072] The hydrotreating reaction was carried out in a micro-unit equipped with a downflow reactor. The experiment was carried out under a total pressure of 2100 psig. Prior to the introduction of the raw materials, the catalyst was activated by a standard reduction procedure. The raw materials passed through the reactor at a liquid hourly space velocity (LHSV) of 1.2. The ratio of hydrogen to oil was about 3000 scfb. The hydrotreating reaction temperature was adjusted in the range of 350 - 550°F. The results of the aromatic compound conversion for each of Catalysts A, B, and C are shown in Table 6.

Table 6

[0073] Compared with Catalyst A (having ASA A (ASA1) on a base extrudate support) and Catalyst B (having ASA2 on a base extrudate support), Catalyst C (having both ASA1 and ASA2 on a base extrudate support) showed an increased aromatic compound saturation conversion rate of about 4% compared to Catalyst B and 16% relative to Catalyst A.

[0074] This application is to be understood as being directed to the entire scope of the main claims described in the following paragraphs P1 to P30. P1. A hydrotreating catalyst useful for the production of a hydrotreated dewaxed product containing a base oil with improved aromatic compound saturation conversion rate, a base extrudate containing a first amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2), wherein the first amorphous silica alumina has a pore volume of 0.2 - 1.0 cc / g in a pore diameter range of 11 - 20 nm, the second amorphous silica alumina has a pore volume of 0.02 - 0.2 cc / g in a pore diameter range of 11 - 20 nm, and the base extrudate has a total pore volume of 0.12 - 1.80 cc / g in a pore diameter range of 2 - 50 nm, said base extrudate, and at least one modifier selected from Groups 6 - 10 and Group 14 of the Periodic Table. The hydrotreating catalyst. P2. The catalyst according to paragraph P1, wherein the modifier contains a metal of Groups 8 to 10 of the periodic table. P3. The catalyst according to paragraph P2, wherein the modifier is a Group 10 metal containing Pt, Pd, or a combination thereof. P4. The catalyst according to any one of paragraphs P1 to P3, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 2 to 6 nm. P5. The catalyst according to any one of paragraphs P1 to P4, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 6 to 11 nm. P6. The catalyst according to any one of paragraphs P1 to P5, wherein the first amorphous silica alumina has a pore volume of 0.24 to 0.85 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.28 to 0.7 cc / g in a pore diameter range of 11 to 20 nm. P7. The catalyst according to any one of paragraphs P1 to P6, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.07 to 0.8 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.09 to 0.6 cc / g in a pore diameter range of 20 to 50 nm. P8. The catalyst according to any one of paragraphs P1 to P7, wherein the first amorphous silica alumina has a total pore volume of 0.3 to 2.0 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.5 to 1.9 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.7 to 1.8 cc / g in a pore diameter range of 2 to 50 nm. P9. The catalyst according to any one of paragraphs P1 to P8, wherein the second amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.06 to 0.9 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.07 to 0.8 cc / g in a pore diameter range of 2 to 6 nm. P10. The catalyst according to any one of paragraphs P1 to P9, wherein the second amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 6 to 11 nm. P11. The catalyst according to any one of paragraphs P1 to P10, wherein the second amorphous silica alumina has a pore volume of 0.03 to 0.18 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.04 to 0.16 cc / g in a pore diameter range of 11 to 20 nm. P12. The catalyst according to any one of paragraphs P1 to 11, wherein the second amorphous silica alumina has a pore volume of 0.01 to 0.2 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.015 to 0.15 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.02 to 0.1 cc / g in a pore diameter range of 20 to 50 nm. P13. The catalyst according to any one of paragraphs P1 to P12, wherein the second amorphous silica alumina has a total pore volume of 0.3 to 2.0 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.4 to 1.8 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.5 to 1.6 cc / g in a pore diameter range of 2 to 50 nm. P14. The catalyst according to paragraphs P1 to P13, wherein the base extrudate has a pore volume of 0.05 to 0.80 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.08 to 0.60 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.10 to 0.50 cc / g in a pore diameter range of 2 to 6 nm. P15. The catalyst according to any one of paragraphs P1 to P14, wherein the base extrudate has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.08 to 0.90 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.10 to 0.80 cc / g in a pore diameter range of 6 to 11 nm. P16. The catalyst according to any one of paragraphs P1 to P15, wherein the base extrudate has a pore volume of 0.02 to 0.3 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.03 to 0.25 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.04 to 0.2 cc / g in a pore diameter range of 11 to 20 nm. P17. The catalyst according to any one of paragraphs P1 to P16, wherein the base extrudate has a pore volume of 0.01 to 0.3 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.012 to 0.25 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.015 to 0.2 cc / g in a pore diameter range of 20 to 50 nm. P18. The catalyst according to any one of paragraphs P1 to P17, wherein the base extrudate has a total pore volume of 0.20 to 1.65 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.25 to 1.50 cc / g in a pore diameter range of 2 to 50 nm. P19. The catalyst according to any one of paragraphs P1 to P18, wherein the modifier content is 0.01 to 5.0 wt% or 0.01 to 2.0 wt%, or 0.1 to 2.0 wt% (based on the total catalyst weight). P20. The catalyst according to any one of paragraphs P1 to P19, wherein the catalyst contains Pt, Pd, or a combination of Pt and Pd as a modifier in an amount of 0.01 to 1.0 wt%, or 0.3 to 0.8 wt% of Pt. P21. The catalyst according to any one of paragraphs P1 to P20, wherein the silica content of the first amorphous silica alumina is in the range of 0.5 to 15 wt%, or 1 to 10 wt%, or 1.5 to 8 wt%. P22. The catalyst according to any one of paragraphs P1 to P21, wherein the silica content of the second amorphous silica alumina is in the range of 15 to 90 wt%, 20 to 85 wt%, or 25 to 80 wt%. P23. The ratio of the first amorphous silica alumina to the second amorphous silica alumina is in the range of 4:1 to 1:4, or 4:1 to 1:2, or 4:1 to 1:1, or 4:1 to 2:1, or 2:1 to 1:4, or 2:1 to 1:2, or 2:1 to 1:1, or 1:2 to 1:1, or 1:4 to 1:2, or 1:4 to 1:1, and the catalyst according to any one of paragraphs P1 to P22. P24. The catalyst according to any one of paragraphs P1 to P23, further comprising a matrix material selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, or a combination thereof. P25. The catalyst according to any one of paragraphs P1 to P24, comprising 0.01 to 5.0% by weight of the modifier, 0 to 99% by weight of the matrix material, and 0.1 to 99% by weight of the base extrudate. P26. The catalyst according to any one of paragraphs P1 to P25, wherein the total amount of the first and second amorphous silica aluminas in the base extrudate is in the range of 10 to 95% by weight, 20 to 90% by weight, or 25 to 85% by weight. P27. A process for producing a hydrotreated base oil product with improved aromatic compound saturation conversion rate, comprising contacting a hydrocarbon raw material with the hydrotreating catalyst according to any one of P1 to P26 under hydrotreating conditions to produce a base oil product. P28. The hydrocarbon raw material includes light oil, vacuum gas oil, long residue, vacuum residue, atmospheric distillate, heavy fuel, oil, wax and paraffin, used oil, deasphalted residue oil or crude oil, charge obtained from a thermal conversion or catalytic conversion process, shale oil, cycle oil, fats, oils and waxes derived from animals and plants, petroleum and slack wax, or a combination thereof, and the process according to paragraph P27. P29. Compared with the same process using a comparative hydrotreating catalyst, which differs only in that the hydrotreating catalyst does not contain both the first amorphous silica alumina and the second amorphous silica alumina, when using the catalyst according to any one of claims 1 to 26, the aromatic compound saturation conversion rate increases, and the process according to any one of paragraphs P27 to P28. The process according to paragraph P29, wherein the increase in the saturation conversion rate of the aromatic compound is at least about 2.0 wt%, or 5.0 wt%, or 10 wt%, or 15 wt%.

[0075] The disclosure of the present application is not limited to the specific embodiments described in the present application, which are for the purpose of exemplifying different aspects. Obviously, many modifications and changes can be made without departing from the spirit and scope thereof. In addition to those listed herein, functionally equivalent methods and systems within the scope of the present disclosure will be apparent from the foregoing representative description. Such modifications and changes are intended to be included within the scope of the appended representative claims. The present disclosure should be limited only by the literal language of the appended representative claims, together with the full scope of equivalents to which such representative claims are entitled. It should also be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to limit the same.

[0076] The foregoing description, together with its associated embodiments, is presented for purposes of illustration only. The description is not exhaustive and does not limit the invention to the precise form disclosed. Those skilled in the art will recognize from the above description that modifications and changes are possible in light of the above teachings, or that modifications and changes can be made by practicing the disclosed embodiments. For example, in some cases, each step described need not be performed in the same order or at the same intervals as described. Similarly, different steps can be omitted, repeated, or combined as necessary to achieve the same or similar objectives. Accordingly, the invention is not limited to the embodiments described above, but instead is defined by the appended claims in light of the full scope of equivalents.

[0077] For the purposes of the practice of U.S. patents and, where recognized, in other patent offices, any patents and publications cited in the above description of the invention are hereby incorporated by reference into this specification to the extent that any information contained therein is consistent with and / or supplements the above disclosure.

Claims

1. A hydrotreating catalyst useful for the production of a hydrotreated dewaxing product containing a base oil with an improved aromatic compound saturation conversion rate, which is a base extrudate containing a first amorphous silica alumina (ASA1) and a second amorphous silica alumina (ASA2), wherein the first amorphous silica alumina has a pore volume of 0.2 to 1.0 cc / g in a pore diameter range of 11 to 20 nm, the second amorphous silica alumina has a pore volume of 0.02 to 0.2 cc / g in a pore diameter range of 11 to 20 nm, the base extrudate has a total pore volume of 0.12 to 1.80 cc / g in a pore diameter range of 2 to 50 nm, and the base extrudate, and at least one modifier selected from Groups 6 to 10 and Group 14 of the periodic table.

2. The catalyst according to claim 1, wherein the modifier contains a metal of Groups 8 to 10 of the periodic table.

3. The catalyst according to claim 2, wherein the modifier is a Group 10 metal containing Pt, Pd, or a combination thereof.

4. The catalyst according to claim 1, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 2 to 6 nm.

5. The catalyst according to claim 1, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 6 to 11 nm.

6. The catalyst according to claim 1, wherein the first amorphous silica alumina has a pore volume of 0.24 to 0.85 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.28 to 0.7 cc / g in a pore diameter range of 11 to 20 nm.

7. The catalyst according to claim 1, wherein the first amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.07 to 0.8 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.09 to 0.6 cc / g in a pore diameter range of 20 to 50 nm.

8. The catalyst according to claim 1, wherein the first amorphous silica alumina has a total pore volume of 0.3 to 2.0 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.5 to 1.9 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.7 to 1.8 cc / g in a pore diameter range of 2 to 50 nm.

9. The catalyst according to claim 1, wherein the second amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 2 to 6 nm, a pore volume of 0.06 to 0.9 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.07 to 0.8 cc / g in a pore diameter range of 2 to 6 nm.

10. The catalyst according to claim 1, wherein the second amorphous silica alumina has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.06 to 0.8 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.07 to 0.6 cc / g in a pore diameter range of 6 to 11 nm.

11. The catalyst according to claim 1, wherein the second amorphous silica alumina has a pore volume of 0.03 to 0.18 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.04 to 0.16 cc / g in a pore diameter range of 11 to 20 nm.

12. The catalyst according to claim 1, wherein the second amorphous silica alumina has a pore volume of 0.01 to 0.2 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.015 to 0.15 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.02 to 0.1 cc / g in a pore diameter range of 20 to 50 nm.

13. The catalyst according to claim 1, wherein the second amorphous silica alumina has a total pore volume of 0.3 to 2.0 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.4 to 1.8 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.5 to 1.6 cc / g in a pore diameter range of 2 to 50 nm.

14. The catalyst according to claim 1, wherein the base extrudate has a pore volume of 0.05 to 0.80 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.08 to 0.60 cc / g in a pore diameter range of 2 to 6 nm, or a pore volume of 0.10 to 0.50 cc / g in a pore diameter range of 2 to 6 nm.

15. The catalyst according to claim 1, wherein the base extrudate has a pore volume of 0.05 to 1.0 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.08 to 0.90 cc / g in a pore diameter range of 6 to 11 nm, or a pore volume of 0.10 to 0.80 cc / g in a pore diameter range of 6 to 11 nm.

16. The catalyst according to claim 1, wherein the base extrudate has a pore volume of 0.02 to 0.3 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.03 to 0.25 cc / g in a pore diameter range of 11 to 20 nm, or a pore volume of 0.04 to 0.2 cc / g in a pore diameter range of 11 to 20 nm.

17. The catalyst according to claim 1, wherein the base extrudate has a pore volume of 0.01 to 0.3 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.012 to 0.25 cc / g in a pore diameter range of 20 to 50 nm, or a pore volume of 0.015 to 0.2 cc / g in a pore diameter range of 20 to 50 nm.

18. The catalyst according to claim 1, wherein the base extrudate has a total pore volume of 0.20 to 1.65 cc / g in a pore diameter range of 2 to 50 nm, or a total pore volume of 0.25 to 1.50 cc / g in a pore diameter range of 2 to 50 nm.

19. The catalyst according to claim 1, wherein the content of the modifier 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 the total catalyst weight).

20. The catalyst according to claim 1, wherein the catalyst contains Pt, Pd, or a combination of Pt and Pd as a modifier in an amount of 0.01 to 1.0% by weight, or 0.3 to 0.8% by weight of Pt.

21. The catalyst according to claim 1, wherein the silica content of the first amorphous silica alumina is in the range of 0.5 to 15% by weight, or 1 to 10% by weight, or 1.5 to 8% by weight.

22. The catalyst according to claim 1, wherein the silica content of the second amorphous silica alumina is in the range of 15 to 90% by weight, or 20 to 85% by weight, or 25 to 80% by weight.

23. The ratio of the first amorphous silica alumina to the second amorphous silica alumina is in the range of 4:1 to 1:4, or 4:1 to 1:2, or 4:1 to 1:1, or 4:1 to 2:1, or 2:1 to 1:4, or 2:1 to 1:2, or 2:1 to 1:1, or 1:2 to 1:1, or 1:4 to 1:2, or 1:4 to 1:1, the catalyst according to claim 1.

24. The catalyst according to claim 1, further comprising a matrix material selected from alumina, silica, ceria, titania, tungsten oxide, zirconia, or combinations thereof.

25. The catalyst according to claim 24, wherein the catalyst comprises 0.01 to 5.0% by weight of the modifier, 0 to 99% by weight of the matrix material, and 0.1 to 99% by weight of the base extrudate.

26. The catalyst according to claim 1, wherein the total amount of the first and second amorphous silica aluminas in the base extrudate is in the range of 10 to 95% by weight, 20 to 90% by weight, or 25 to 85% by weight.

27. A process for producing a hydrotreated base oil product with improved aromatic compound saturation conversion rate, comprising contacting a hydrocarbon feedstock with the hydrotreating catalyst according to claim 1 under hydrotreating conditions to produce a base oil product.

28. The hydrocarbon feedstock includes gas oil, vacuum gas oil, long residue, vacuum residue, atmospheric distillate, heavy fuel, oil, wax and paraffin, used oil, deasphalted residue or crude oil, charge obtained from a thermal conversion or catalytic conversion process, shale oil, cycle oil, fats, oils and waxes derived from animals and plants, petroleum and slack wax, or combinations thereof, the process according to claim 27.

29. When compared with the same process using a comparative hydrotreating catalyst, which differs only in that the hydrotreating catalyst does not contain both the first amorphous silica alumina and the second amorphous silica alumina, using the hydrotreating catalyst results in an increase in the aromatic compound saturation conversion rate, the process according to claim 27.

30. The increase in the aromatic compound saturation conversion rate is at least about 2.0% by weight, or 5.0% by weight, or 10% by weight, or 15% by weight, the process according to claim 29.

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