Highly active hydrogenation catalyst and process using the same

Abstract

To provide a method for preparing a catalyst.SOLUTION: There is provided a method for preparing a supported catalyst for hydrogen-treating or hydrogen-cracking hydrocarbon feedstocks, wherein the supported catalyst comprises at least one metal from Group 6 and at least one metal from Groups 8, 9, or 10 of the Periodic Table of the Elements, and optionally comprising phosphorous. The Group 6 metal comprises about 30 to about 45 wt.% and the total of Group 6 and Group 8, 9, or 10 or mixtures thereof metal components comprise about 35 to about 55 wt.%, calculated as oxides and based on the total weight of the catalyst composition. The metals, and phosphorous when present, are carried on and / or within a porous inorganic oxide carrier or support, the support prior to incorporation of the metals and phosphorus, has a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g and comprises a defined pore size distribution and wherein the supported catalyst comprises a defined pore size distribution.SELECTED DRAWING: Figure 4A

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 135,167, filed on 8 January 2021, the contents of which are fully incorporated herein by reference. [Background technology]

[0002] In the petroleum industry, it is used when hydrotreating hydrocarbon feedstocks. Therefore, there is a continued need for improved catalyst supports and supported catalysts derived therefrom that exhibit a desirable balance of enhanced activity, improved catalyst lifetime, and morphological properties.

[0003] Granular porous inorganic supports are useful as catalyst supports and for preparing supported catalysts. Such supported catalysts include catalytically active metals, metal oxides, nonmetals, and other metal compounds based on elements from various groups of the periodic table. The concentration and distribution of metals and elements on the support, as well as the properties of the support itself, are representative parameters that influence the complex properties of catalytic activity and catalyst lifetime.

[0004] Regarding the support catalyst used when hydrotreating hydrocarbon feedstocks Therefore, the morphological properties of the support, such as surface area, pore volume, pore size, and the pore size distribution of the pores constituting the total pore volume, are important. Such properties can affect the properties and concentration of the active catalyst site, the diffusion of reactants to the active catalyst site, the diffusion of products from the active site, and the catalyst lifetime. In addition, the support and its dimensions also affect the mechanical strength, density, and reactor packing characteristics, all of which are important in commercial applications.

[0005] Hydroprocessing catalysts in petroleum refining are aluminum in commercial use. It accounts for a large part of supported catalysts such as those based on the use of sodium and silica-alumina. Such hydrotreating applications cover a wide range of feed types and operating conditions, but have one or more common objectives, namely, the removal of heteroatom impurities, for example, sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds (sometimes referred to as sulfur, nitrogen, and metals), asphaltenes, carbon residues, precipitate precursors, and mixtures thereof, and an increase in the hydrogen to carbon (H / C) ratio in the product, as well as a reduction in aromatic compounds, density and / or carbon residue, and a reduction in boiling range and average molecular weight by cracking of carbon bonds, desirably a reduction in product viscosity.

[0006] As refiners increase the proportion of heavier and lower-quality crude oil in the feedstock to be processed, the need for processes and catalysts to treat fractions containing high levels of metals, asphaltenes, aromatics, nitrogen, and sulfur is increasing. When catalysts such as residue hydrodesulfurization catalysts or vacuum gas oil (VGO) hydrocracking pretreatment catalysts are exposed to hydrocarbon fractions containing undesirable metals and aromatics, the catalysts can rapidly deactivate and may be subject to early replacement.

[0007] VGO hydrocracking is a catalytic chemical process that converts high-boiling constituent hydrocarbons in petroleum crude oil into more valuable low-boiling products such as gasoline, kerosene, jet fuel, and diesel oil. Typically, the process is carried out in a hydrogen-rich atmosphere at high temperature (e.g., 260 - 425 °C) and high pressure (35 - 200 bar or 3.5 - 20 MPa). A VGO hydrocracking pretreatment catalyst is typically placed before a hydrocracking catalyst and hydrotreats the VGO by reducing the content of organic nitrogen, organic sulfur, and aromatic compounds. Organic sulfur and aromatic compounds to hydrogenate the VGO.

[0008] Generally, in order to maximize the concentration and activity of catalytic sites, it is desirable to design a hydroprocessing catalyst with a large surface area. However, the surface area and pore diameter These are inversely proportional within the practical limits. As a result, catalyst supports, such as those containing alumina or silica-alumina particles and primarily small pores, exhibit the largest surface area. In contrast, sufficiently large pores are required for the diffusion of feedstock components, especially as the catalyst ages and becomes contaminated, but larger pores result in a lower surface area. More specifically, catalyst compounders or designers and process engineers often face competing considerations that define the balance between the morphological properties of the support and the resulting supporting catalyst.

[0009] Pores with diameters in the range of less than approximately 200 angstroms (Å) (20 nm) have the effect of increasing the number of active sites in alumina or silica-alumina hydrogenation catalysts, but such sites are easily clogged by coke, which can lead to a decrease in catalytic activity. Conversely, if the supporting catalyst has more than approximately 10% of its total pore volume occupied by pores with diameters greater than 1000 Å (100 nm), the mechanical fracturing strength and activity of the supporting catalyst may be adversely affected. Furthermore, for some alumina or silica-alumina catalysts, maximizing the concentration of pores with diameters between 200 Å (20 nm) and less than 1000 Å (100 nm) can provide a balance between activity and catalyst lifetime within a region referred to as the mesopore region, for the purposes of the present invention.

[0010] Therefore, while increasing the surface area of ​​a catalyst can increase the number of active sites, such an increase in surface area leads to an increase in the proportion of smaller pores, which are more susceptible to clogging by coke and other components present in the hydrocarbon feedstock. In other words, increasing the surface area and maximizing the concentration of the supporting catalyst exhibiting pore sizes in the mesopore range are conflicting properties. Furthermore, a large surface area is not only desirable, but it should also remain stable when exposed to petroleum feedstock conversion conditions such as high temperature and humidity. Therefore, catalytically active metals supporting catalysts, particularly for the production of hydroprocessing catalysts, are important. When used for supporting catalysts, stable support particles exhibiting a combination of pore size distribution and total surface area that provides a suitable combination of performance characteristics for use as a catalyst support are still being sought.

[0011] Furthermore, the physical and chemical properties of porous supports may depend on the procedures followed during their preparation, and many processes have been developed in attempts to optimize their properties for use as catalyst supports. Examples of suitable porous support materials and preparation methods are described below. Generally, alumina supports can be prepared by combining a water-soluble acidic aluminum-containing compound or aluminum salt, such as aluminum sulfate, aluminum nitrate, or aluminum chloride, with an alkali metal aluminate, such as sodium aluminate or potassium aluminate, to form a precipitate, which is then further dried and typically calcined. Thus, catalyst supports containing alumina supports are known, but further improvements are needed to provide supports with even better properties. [Overview of the project]

[0012] A supported catalyst comprising at least one metal from Group 6 of the periodic table (or referred to as Group VIB) and at least one metal from Group 8, Group 9, or Group 10 of the periodic table (or referred to as Group VIIIB), optionally comprising phosphorus, and calculated as an oxide and based on the total weight of the catalyst composition, the Group 6 metal constitutes about 30 to about 45% by weight, and the sum of the metal components of Group 6 and Group 8, Group 9, or Group 10 or mixtures thereof constitutes about 35 to about 55% by weight, and the metals, and phosphorus, if present, are supported on and / or within a porous inorganic oxide carrier or support, and the metals and present In this case, the support before phosphorus is incorporated has a total pore volume (TPV) of approximately 0.8 cc / g to approximately 1.5 cc / g, and (a) 100 angstroms (Å) (b) TPV of approximately 25% to approximately 45% in pores with a diameter of ~200 angstroms (Å) (20 nm), (c) TPV of more than approximately 15% to less than approximately 30% in pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), (d) TPV of 10% to less than 30% in pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), (d) TPV of 100 Å (10 nm) to 200 Å (2 A supporting catalyst containing (e) TPV of approximately 35% to approximately 60% in pores with a diameter of (0 nm), (f) TPV of more than approximately 15% to approximately 30% in pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (g) TPV of 10% to less than 30% in pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), wherein the pore characteristics and content are measured using mercury porosimetry.

[0013] Another embodiment includes a porous inorganic oxide carrier or support having a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, and comprising (a) about 25% to about 45% of TPV in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), (b) about 15% to less than 30% of TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (c) 10% to less than 30% of TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[0014] Further embodiments include a process for processing a hydrocarbon feedstock containing at least one of paraffin, aromatic, and naphthenic components to produce a processed product, the process comprising: (I) hydrodemetallation, hydrodenitrification, hydrodesulfurization, hydrodearomatherapy, and hydrocracking, wherein the process contacts the feedstock in at least one reactor with hydrogen under hydroprocessing or hydrocracking conditions using the above-mentioned supporting catalyst. Hydrotreating a hydrocarbon feed containing (II) a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof, wherein the feed is, Under isothermal or substantially isothermal hydrotreating conditions, hydrogen and the above-mentioned supporting catalyst are subjected to hydrogen treatment. (III) Hydrotreating a hydrocarbon feed having components with a boiling point higher than 600°F (315.6°C) to form a product in which the proportion of components with a boiling point lower than approximately 600°F (315.6°C) is increased, wherein the feed is subjected to isothermal or substantially isothermal hydrotreating conditions. (iv) Forming, comprising contacting the feed with hydrogen and the above-mentioned supporting catalyst and recovering the product; and Hydrogenating the feed, comprising contacting the feed containing hydrocarbon oil with hydrogen and the above-mentioned supporting catalyst under conditions of a high temperature exceeding about 600°F (315.6°C) and a pressure exceeding about 500 p.sig (3.44 MPa) and recovering the product.

[0015] Further embodiments include a method for preparing a catalyst for use in at least one petroleum hydrocarbon processing process, the method of impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the periodic table, at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9 or Group 10 (or Group VIII) of the periodic table, and optionally a phosphorus-containing compound and at least one organic chelate compound, wherein the Group VIB and Group VIIIB compounds and the phosphorus compounds are thermally decomposable or thermally heated to their corresponding oxides in the presence of an oxygen-containing atmosphere. An oxidizable impregnation, followed by drying and calcining of the resulting impregnated support, wherein the support is formed by (A) mixing alumina-containing powder with water and optionally nitric acid to form a wet mixture, and (B) shaping the wet mixture to form support particles suitable for use in a hydroprocessing reactor. The support is prepared by drying and calcining, and comprises a porous inorganic oxide having a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, and the following pore size distribution and pore content corresponding to values ​​measured using mercury porosimetry, namely, (i) 25% to 45% TPV in pores with a diameter of 100 Å (10 nm) to 200 Å (20 nm), (ii) more than 15% to less than 30% TPV in pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (iii) 10% to less than 30% pore volume in pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm). [Brief explanation of the drawing]

[0016] [Figure 1A] The typical pore size distributions, measured using a nitrogen desorption method, are shown for a comparative catalyst support or support particle and for a catalyst support or support particle prepared according to the present invention. [Figure 1B] The typical pore size distributions, measured using the mercury intrusion method, are shown for comparative catalyst support or support particles and catalyst support or support particles prepared according to the present invention. [Figure 1C] The typical pore size distributions, measured using the mercury intrusion method, for comparative catalyst support or support particles and catalyst support or support particles prepared according to the present invention are shown on a logarithmic scale. [Figure 2A] This shows a typical pore size distribution measured using a nitrogen desorption method for supported catalysts with and without added fine powder, prepared according to the present invention. [Figure 2B] This shows typical pore size distributions measured using the mercury intrusion method with and without the addition of fine powder, prepared according to the present invention. [Figure 2C] Typical pore size distributions, measured using the mercury intrusion method with and without the fine powder added to the supported catalyst prepared according to the present invention, are shown on a logarithmic scale. [Figure 3] This is a simplified flow diagram of the bench scale unit (BSU) used to test the petroleum hydrotreating performance of the support catalysts prepared in the examples. [Figure 4A] This is a plot of the reaction rate (kHDN) of hydrogenation denitrification as a function of the operating temperature of the catalyst or bench-scale unit for comparative and exemplary catalysts. [Figure 4B] This is a plot of the reaction rate (kHDS) of hydrogenodesulfurization as a function of the operating temperature of the catalyst or bench-scale unit for comparative and exemplary catalysts. [Figure 4C] This is a plot of the apparent conversion rate of hydrogenodesulfurization as a function of catalyst temperature in bench-scale units for comparative and exemplary catalysts. [Figure 5A]This is a plot of the volume percentage of aromatics in the stripper bottom (STB) of bench-scale units for performance evaluation of comparative and exemplary catalyst A as a function of apparent conversion rate. [Figure 5B] This is a plot of the volume percentage of naphthenes in the stripper bottom (STB) of bench-scale units for performance evaluation of comparative and exemplary catalyst A as a function of apparent conversion rate. [Figure 5C] This is a plot of the volume percentage of paraffin in the stripper bottom (STB) of bench-scale units for performance evaluation of comparative and exemplary catalyst A as a function of apparent conversion rate. [Modes for carrying out the invention]

[0017] definition When used herein, the following terms or phrases have the meanings expressed:

[0018] The use of the term "alumina" is a convenient and concise expression intended to encompass, individually and in combination, any and all of the inorganic oxides further disclosed below as useful herein. This includes the powder form of the inorganic oxides, as well as their subsequent processing to form supports for use in preparing support catalysts.

[0019] The terms "catalyst" and "catalytic system" are used interchangeably herein.

[0020] When the term “about” is used as a modifier to a variable, feature, or condition, or in conjunction with a variable, feature, or condition, it is intended to convey that the number, scope, features, and conditions disclosed herein are flexible, and that the implementation of the invention by a person skilled in the art using properties such as temperature, rate, time, concentration, amount, content, pore size, pore volume, and surface area, which are outside the scope described or different from a single described value, will achieve the desired or multiple results described in this application, namely, the preparation of porous catalyst support particles having defined features, and their use in the preparation of active catalysts, and processes using such catalysts.

[0021] "Apparent conversion rate" = 100, for example, ASTM D2887 "Gas chromatograph" after hydroprocessing including HDA, HCR, HDN and / or HDS Based on SimDist (simulated distillation) tests following the "Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography" by [translator name], subtract the percentage of hydrocarbons that boil above 700°F (371.1°C).

[0022] For example, the term "component" applied to the metal in the catalyst impregnation solution or to the catalyst itself refers to any compound or complex containing salts, oxides, sulfides, or any intermediate forms between oxides and sulfides of the metal in question.

[0023] "comprise" or "comprising": Throughout this Spec., including the claims, the terms "comprising" and "comprises" are used, as well as "comprise" or "comprising". "to have", "to possess", "includes", "include ) and "including", and variations thereof such as "comprise The term "and variations thereof" means that the specified steps, elements, components, or materials referred to therein are essential, but other steps, elements, components, or materials may be added, and still form a component within the scope of the claims or disclosure. When described in the description and claims of the present invention, it means that the present invention and claims are considered to be the following and potentially more. These terms are comprehensive or open-ended and do not exclude elements, components, or method steps that are not additionally described, especially when applied to the claims.

[0024] "Feedback" or petroleum feedbacks typically processed using processes containing the catalyst of the present invention are often described in terms of being "heavy" or "light." The terms "light" and "heavy" in relation to petroleum fractions are used herein in their usual sense within the refining industry to refer to relatively low and high boiling point ranges, respectively. Heavy fuel oil (HFO) includes both the final product (residual fuel) and the primary refinery stream into which they are blended. Members of the heavy fuel oil category have a wide range of molecular weights and carbon numbers (typically about C7 to about C7). 50 ) and boiling point (approximately 250°F to approximately 1112°F) This is a diverse group of substances encompassing hydrocarbons having a boiling point of F (approximately 121°C to 600°C). In addition to petroleum hydrocarbons, the feedstock may contain one or more heterocyclic compounds containing sulfur, nitrogen, and oxygen, as well as organometallic or metallic compounds. The final heavy fuel (residual fuel) is a product mainly consisting of the residues of the refining process after substantially all high-quality hydrocarbons have been removed from the crude oil feedstock by distillation, cracking, or catalytic means. Substantially all (at least 90 vol%) of the hydrocarbon feedstock stream or feedstock falls within a boiling point range of approximately 300°F to 1050°F (approximately 148.9°C to 565.6°C), preferably approximately 600°F to 1000°F (approximately 315.6°C to 537.8°C). The feedstock may include mixtures of petroleum fractions such as atmospheric and vacuum diesel (AGO and VGO). Preferred feedstocks include heavy hydrocarbon minerals or synthetic oils, or mixtures of one or more fractions thereof. Therefore, known feedstocks such as straight-run diesel, vacuum diesel, demetallated oil, deasphalt vacuum residue, coker distillate, catalytic cracking distillate, shale oil, tar sands oil, and liquefied coal oil are possible. Preferred feedstocks have a boiling point range that begins at temperatures above approximately 260°C (above approximately 500°F). Hydrocracking feedstocks may typically contain nitrogen present in amounts of 1 ppm to 1.0 wt% as organic nitrogen compounds. Feedstocks also typically contain sulfur-containing compounds sufficient to provide a sulfur content of more than 0.15 wt%. The boiling point ranges of the various product fractions recovered at any particular refinery vary depending on factors such as the characteristics of the crude oil source, the refinery's regional market, and product prices. The American Petroleum Institute (API) recommended to the Environmental Protection Agency (EPA) a list of common names for refinery streams that are consistent with industry operations and cover all known processes used by refiners. The list, which includes the common name, Chemical Abstracts Service (CAS) number, and definition of each stream, is titled "A The definitions of these streams were published by the EPA as "ddendum I, Generic Terms Covering Petroleum Refinery Process Streams." "High Production" submitted by HPV Testing Group (June 17, 2004), Appendix A, pages 38-42 It can also be found in the Volume (HPV) Chemical Challenge Program, Test Plan, Heavy Fuel Oils Category. Suitable petroleum streams for treatment using the catalyst of the present invention are identified in EPA documents, the contents of which are incorporated herein by reference to the extent permitted.

[0025] "Group" or "Groups": Any reference to a group or group in the periodic table of elements preferably refers to a group or group that is reflected in the periodic table of elements using the IUPAC system for numbering the groups of elements as groups 1 through 18. However, insofar as a group is identified by Roman numerals according to the periodic table of elements published, for example, in "Hawley's Condensed Chemical Dictionary" (2001) ("CAS" system), one or more elements in that group are further identified to avoid confusion and to provide a cross-reference to the numerical IUPAC identifier.

[0026] The median pore diameter (MPD) can be calculated, for example, based on volume, surface area, or pore size distribution data. The median pore diameter calculated by volume represents the pore diameter where half of the total pore volume resides, and the median pore diameter calculated by surface area represents the pore diameter where half of the total pore surface area resides. In addition, the median pore diameter calculated based on pore size distribution represents the pore diameter where half of the pores have a larger diameter, according to the pore size distribution determined, for example, using the mercury intrusion method, as described elsewhere in this specification.

[0027] "Micropores" are typically understood to refer to pores present in a supporting catalyst or catalyst support that have a diameter of less than 20 Å (2 nm).

[0028] "Mesopores" are typically understood to refer to pores present in a supporting catalyst or catalyst support having a diameter of less than 20 Å (2 nm) to 1000 Å (100 nm). However, this broader range also includes "sub-ranges" of mesopores that are important to the inventions disclosed herein, including the ranges of 100 Å (10 nm) to 200 Å (20 nm) and 200 Å (20 nm) to 1000 Å (100 nm).

[0029] "Macropores" are typically understood to refer to pores present in a supporting catalyst or catalyst support having a diameter of 1,000 Å (100 nm) or more, for example, 1,000 Å (100 nm) to 30,000 Å (3,000 nm).

[0030] Each of the above definitions of micropores, mesopores, mesopore sub-ranges, and macropores is unique and clear enough that a pore is not counted twice when summing percentages or values ​​in the pore size distribution for any given sample.

[0031] "d50" means the median pore diameter measured by mercury porosimetry for the purposes of this invention. Therefore, d50 corresponds to the median pore diameter calculated based on the pore size distribution, and beyond that, half of the pores have a larger diameter.

[0032] As used herein, "total pore volume" penetration refers to penetration by either nitrogen desorption or mercury penetration, also known as porosimetry. This refers to the cumulative volume in cc / g of all possible pores. For catalyst supports or support particles, for example, alumina powder and alumina or silica-alumina powder or support particles, the pore size distribution and pore volume can be calculated by referring to nitrogen desorption isotherms (assuming cylindrical pores) using the BET (or BET) technique described by S. Brunauer, P. Emmett, and E. Teller in the Journal of American Chemical Society, 60, pp209-31.9 (1939), and also refer to ASTM D3037, which identifies the procedure for determining surface area using the nitrogen BET method. It is generally recognized that the nitrogen desorption method is particularly useful for smaller pore sizes, while the mercury intrusion method is well suited for larger pore sizes. Unless otherwise specified, the mercury intrusion method is used for convenience to measure and express values ​​and ranges over the entire range of pore sizes present in the powders, supports, catalyst supports or supports, and supporting catalysts disclosed herein.

[0033] ASTM D4284-07, "A Standard Test Method for Determining Pore Volume Distribution of Catalysts by Mercury Intrusion Porosimetry," is a generally accepted test used to measure the pore volume distribution in catalysts and catalyst supports or support particles with respect to the apparent diameter or size of the pore inlet. As discussed above, both the size and volume of pores in a catalyst generally affect its performance. Therefore, pore volume distribution is useful for understanding catalytic performance and may be one of the characteristics identified for a catalyst that can be expected to function in a desired manner. Values ​​of pore volume, including total pore volume or total intrusion volume, such as the percentage of pores in various size ranges, and various attributes of pore volume distribution are based on the mercury intrusion method unless otherwise disclosed.

[0034] The pore size distribution using the mercury intrusion method is given by the following formula:

[0035]

number

[0036] The total N2 pore volume of the sample is the sum of the nitrogen pore volumes determined by the nitrogen desorption method described above. Similarly, the total mercury pore volume of the sample is the sum of the mercury pore volumes determined by the mercury osmosis method described above, using, for example, a contact angle of 130°, a surface tension of 485 dynes / cm, and an Hg density of 13.5335 gm / cc.

[0037] In this specification, "surface area" refers to the specific surface area determined by nitrogen adsorption using the BET technique described above, whether in powder or aggregate form.

[0038] Pore ​​volume, PV (cc / g), or surface area (SA) (m²) 2 All morphological properties related to weight, such as ( / g), can be normalized to a "metal-free standard" according to procedures known in the art. However, the morphological properties reported herein are "as-measured" standards that have not been corrected for metal content.

[0039] "Periodic Table": All references to the periodic table of elements in this specification are as defined by the International Union of Pure and Applied Chemistry (IUPAC). This refers to the publicly available periodic table of elements, with the version dated February 19, 2010, available online at http: / / old.iupac.org / reports / periodic_table / .

[0040] Where used herein in relation to numerical ranges, the terms “approximately,” “about,” “substantially,” and similar terms are understood by those skilled in the art. The interpretation will vary to some extent depending on the context in which it is used. Where there is a use of terminology that is not obvious to those skilled in the art, the term will be plus or minus 10% of the disclosed value, considering the context in which it is used. "Approximately," "about," "substantially," and similar terms are used when applied to structural features. For example, to describe its shape, size, orientation, direction, etc., these terms are intended to have a broad meaning that is consistent with the common and acceptable usage by those skilled in the art to which the subject matter of this disclosure relates, and to encompass minor structural deformations that may result from the manufacturing or assembly process. Accordingly, these terms should be interpreted as indicating that any substantial or insignificant modification or alteration of the subject matter described and claimed is deemed to fall within the scope of this disclosure as described in the appended claims. Unless otherwise defined with respect to a specific characteristic, feature, or variable, the term “substantially” applied to any criterion such as a characteristic, feature, or variable is the criterion described in such a measure that a person skilled in the art would understand that the benefits to be achieved, or the desired conditions or characteristic values, are met. This means that the following conditions are met. For example, see below for the use of the term "substantially" in relation to the description of substantially isothermal.

[0041] When used in reference to various processes for processing hydrocarbon feedstocks, the phrase “substantially isothermal” is typically understood to mean that the process is operated such that the temperature typically fluctuates only about 50°F, preferably less than about 40°F, more preferably less than about 30°F, for example less than about 20°F, for example near 0°F, and only about 20°F, 30°F, 40°F, or 50°F across the entire catalyst bed. Alternatively, such a process may be described as operating isothermally, even while exhibiting the temperature fluctuations described above.

[0042] In the context of describing elements (particularly in the context of the following claims), “a,” “an,” and “the,” as well as similar references, should be interpreted as encompassing both singular and plural forms unless otherwise indicated herein or unless there is a clear contradiction. The enumeration of value ranges herein is intended merely as a concise way of referring individually to each distinct value belonging to that range unless otherwise indicated herein, and each distinct value is incorporated herein as if it were individually listed herein. All methods described herein may be performed in any preferred order unless otherwise indicated herein or unless there is a clear contradiction. The use of any and all examples or exemplary language (e.g., “etc.”) provided herein is intended merely to better illustrate embodiments and does not, unless otherwise indicated, impose any limitation on the claims. The language herein should not be interpreted as indicating any unclaimed element as essential.

[0043] Embodiments of the present invention relate to catalyst supports and methods for preparing supported catalysts using such supports, as well as hydroprocessing, hydrocracking (HCR), and de-aromaticing. This includes the use of a support catalyst for fragrant group (HDA), hydrodesulfurization (HDS), hydrodenitrification (HDN), hydrometallation (HDM), and hydrodemicrocarbon residue (HDMCR) or microcarbon reduction activity. The supports or carriers disclosed herein are also useful for preparing other catalysts useful in various processes. More specifically, embodiments also relate to porous catalyst supports or carriers and methods for preparing a support catalyst using such a support, wherein the support catalyst has preferred defined pore properties, including pore size and pore size distribution, and contains at least one metal and / or metal compound from Group 6 (also known as Group VIB) and Groups 8, 9 and 10 (also known as Group VIIIB) of the periodic table of elements, and optionally contains phosphorus.

[0044] Exemplary carriers or supports are generally identified as inorganic oxide porous carriers, and such carriers will generally be understood to have many pores, perforations, and / or porosity. Examples of suitable porous carrier materials include silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed in alumina, alumina-coated silica, silica-coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, and magnesium carbonate. Examples of porous carrier materials include magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, cationic clay or anionic clay, such as saponite, bentonite, kaolin, sepiolite or hydrotalcite, and mixtures thereof. Preferred porous carrier materials are silica, silica-alumina, alumina, titania, titania-alumina, zirconia, bentonite, boria, and mixtures thereof, with silica, silica-alumina, alumina, and mixtures thereof being particularly preferred, with a maximum of about 20% by weight of silica, preferably a maximum of about 12% by weight of silica, and similarly alumina containing, for example, a maximum of about 10% by weight of silica.

[0045] Examples of silica-alumina compositions suitable for use in the present invention exhibit the following properties.

[0046] [Table 1]

[0047] Alumina for use as a carrier can be prepared, for example, by converting an alumina precursor in the form of pseudoboehmite into a preferred form for use as a carrier material, such as gamma-alumina, typically using calcination.

[0048] Preparation of alumina-containing powder As disclosed above, the following disclosures, which specifically refer to alumina-containing compositions, also apply to other inorganic oxides, specifically silica-alumina, and combinations thereof, that are identified herein as useful, with appropriate modifications known to those skilled in the art.

[0049] In embodiments of the present invention, the alumina-containing composition is typically prepared by a batch process in which alumina and / or the alumina-containing composition are precipitated under controlled reactant concentrations and reaction conditions, including temperature, time, pH, reactant flow rate, etc. Such processes are generally known in the art (see, for example, U.S. Patent No. 4,154,812 by Sanchez et al., U.S. Patent No. 6,403,526 by Lussier et al., and the patents cited herein; these disclosures are incorporated herein by reference). Related alumina preparation methods are disclosed herein. The preparation of silica-alumina compositions is specifically disclosed by Lussier et al. (this disclosure is incorporated herein by reference to the extent permitted).

[0050] In a preferred embodiment for preparing alumina or silica-alumina, the filter cake produced during the synthesis process is dried to produce a powder that can be easily stored for long periods without decomposition before use in further processing. Drying of the filter cake can be carried out by several methods, such as tray drying, belt drying, spray drying, or a combination thereof. The drying conditions are typically adjusted to partially remove water to a level of volatile matter of about 20% to about 35% by weight, preferably about 22% to about 30% by weight, for example, about 23, 24, 25, 26, 27, 28, or 29% by weight, for volatile matter.

[0051] Dry alumina and / or silica-alumina powder and water are mixed or combined to provide a wet or moist mixture or dough. Optionally, an acidic or basic aqueous medium, such as an aqueous solution of an acid or acidic salt, may also be added to the mixture. If an acid is present, preferably, an aqueous solution of a monobasic mineral acid is mixed with water and alumina to provide the mixture. Hydrochloric acid and other strong monobasic acids, including nitric acid, may be used. Nitric acid is preferred. Other useful acids include organic acids such as acetic acid, formic acid, and propionic acid. Alternatively, aqueous bases such as ammonium hydroxide can be used. In addition, as disclosed in the art, a recirculation calcination product of up to about 25% by weight of the total alumina may be added. The powder can be added advantageously during this process.

[0052] The mixture obtained from the previous step is referred to as the wet mixture. This mixture is formed on a carrier, for example, in the form of a pill or other shape, as described elsewhere in this specification. This step is carried out simply by extruding the wet mixture, which is typically followed by drying and calcining of the pill.

[0053] Firing can be carried out in batches or continuously by bringing the formed alumina support product into contact with a hot gas, which may be either an indirectly heated gas or the combustion product of a conventional fuel and air. Regardless of the specific method used, the product is typically preheated for a limited time at a temperature below the target firing temperature, and then fired at a temperature of about 1000°F (537.8°C) to about 2000°F (1093.3°C), or about 1200°F (648.9°C) to about 1900°F (1037.8°C), for example, about 1400°F (760°C) to about 1800°F (982.2°C), for about 30 minutes to about 3 hours, preferably about 30 minutes to about 2 hours. Alternatively, the pills can be heated and fired to achieve a desired target level of ignition loss, as described elsewhere in this specification.

[0054] Properties of silica-alumina supports As described above, the powder is then mixed with water and optionally with recycled fine powder (catalyst powder and / or catalyst support powder) and an acid such as nitric acid, extruded to produce support particles such as pills, which are then dried and preferably calcined. The recycled fine powder typically contains the inorganic oxide itself or the pulverized catalyst or its corresponding support or carrier, and typically exhibits a particle size in the range of 10 to 100 micrometers. In the following description, the products generated at this stage of the process will be referred to as "alumina support particles," catalyst support particles, or "catalyst carrier particles," or simply "support" or "carrier" particles.

[0055] The support particles are typically heat-treated or calcined at a temperature in the range of about 450 to about 1100°C, preferably about 550 to about 1000°C, most preferably about 600 to about 900°C (in °C) for typically about 0.2 to about 3 hours, preferably about 0.3 to about 2 hours, most preferably about 0.5 to about 1.5 hours. The atmosphere in which the activation takes place is typically air, but may include an inert gas such as nitrogen, or may be carried out exclusively in an inert atmosphere.

[0056] Some properties of alumina support particles produced according to the synthesis method described above are typically measured and generally represent the characteristics of the particles. Various properties and test methods are defined above and also mentioned in the following examples. Typical values ​​for some of the properties are summarized below.

[0057] The total mercury pore volume of the sample is the sum of the mercury pore volumes determined by the mercury osmosis method described above.

[0058] The support particles or carrier particles of the present invention have a total pore volume (TPV) before incorporating the catalytic metal and other catalyst components, which is sometimes also referred to as the total intrusion volume TIV or total mercury pore volume, referring to measurements performed using, for example, mercury intrusion porosimetry. Typically, it is from about 0.8 to about 1.5 cc / g, or about 0.85 or about 0.9 or about 0.95 or about 1.0 or about 1.05 or about 1.10 or about 1.15 cc / g, up to about 1.45 or about 1.40 or about 1.35 or about 1.30 or about 1.25 or about 1.20 cc / g in cc / g.

[0059] On the other hand, the "as-measured" total pore volume of the supported catalyst according to the present invention, which contains the catalytic metal and other catalyst components, such as a chelating agent or a chelating agent residue after drying and / or calcination, is typically significantly lower, for example, about half of the values listed above for the support itself. The TPV value measured for the supported catalysts of the examples herein was about 0.45 cc / g, which is partly due to the high content of the catalytic metal.

[0060] The silica-alumina support particles or carrier particles produced according to the present invention have a total surface area in m 2 / g determined by nitrogen adsorption using the BET technique, that is, at least about 185, or at least about 195, or at least about 205 m 2 / g, and for each of the values listed, has a maximum total nitrogen surface area of about 425 m 2 / g, or about 400 m 2 / g, or about 375 m 2 / g, or about 350 m 2 / g, or about 325 m 2 / g, or about 300 m 2 / g, or about 275 m 2 / g.

[0061] The content of pore sizes between 1,000 Å and 30,000 Å (3,000 nm), as measured using mercury osmosis, is typically between 10% and 30% of the total pore volume, for example, 12%, 14%, 16%, 18%, 20%, 22%, 24%, or 26% or more, and 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, or 20% or less. Furthermore, for each of the ranges resulting from the listed lower and upper limits, the “greater than” and “less than” amounts include values ​​expressed as tenths of a percent and unit percentage values.

[0062] The pore content in the carrier particles useful in the present invention, i.e., the content of pores having a diameter of 200 Å (20 nm) or more and less than 1000 Å (100 nm) as measured using mercury osmosis, is typically in the range of about 15% or more and about 30% or less of the total pore volume, for example, 16%, or 17%, or 18%, or 19%, or 20%, or 21%, or 22%, or 23%, and 29%, or 28%, or 27%, or 26%, or 25%, or 24%, or 23%, or 22%, or 21%, or 20% or less. Furthermore, for each of the ranges resulting from the listed lower and upper limits, the amounts "greater than" and "less than" include values ​​expressed as one-tenth of a percent.

[0063] The pore content of carrier particles measured using mercury osmosis, i.e., the pore content of carrier particles exhibiting pores with a diameter of less than 200 Å (20 nm), is typically greater than approximately 55% to approximately 75%, or greater than 57%, 59%, 61%, 63%, 65%, 67%, or 69%, and less than or equal to approximately 74%, 73%, 72%, 71%, 70%, 69%, 68%, 67%, or 65%. Furthermore, for each of the ranges resulting from the listed lower and upper limits, the amounts “greater” and “less” (or their values) include values ​​expressed as tenths of a percent and unit percentage values.

[0064] The carrier particles suitable for use in the present invention may also contain pores within a pore size range of about 100 Å (10 nm) to about 200 Å (20 nm), which are also measured and reported using the mercury osmosis method described above. The content of pores in the range of about 100 Å (10 nm) to about 200 Å (20 nm) is typically about 25% to about 45% or more, or more than 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%, and less than or equal to about 44%, 43%, 42%, 41%, 40%, 39%, or 38%. Furthermore, for each of the ranges resulting from the listed lower and upper limits, the quantities “greater than” and “less than” (or their values) include values ​​expressed as one-tenth of a percent and unit percentage values.

[0065] Typically, catalyst carriers or support particles prepared according to the present invention exhibit a pore size distribution (PSD) with major or significant peaks located at lower pore diameters, as observed on the pore size distribution plot, and the differential mercury intrusion volume is plotted as a function of the log derivative of the pore diameter (dV / dlogD) according to the porosimetry method, ASTM D4284-07. For the purposes of the present invention, particles containing carriers or supports, and supported catalysts prepared using the supports, may also exhibit one or more additional peaks larger than the peaks located at lower pore diameters described above. Pore size distribution plots including such smaller diameter peaks are shown in Figures 1 and 2.

[0066] The carrier particles or support particles are typically characterized by exhibiting a d50 (measured similarly using mercury osmosis) that is greater than about 110 Å (11 nm) and less than about 170 Å (17 nm), or greater than about 120 Å (12 nm) and less than about 160 Å (16 nm), for example, greater than about 125 Å (12.5 nm) and less than about 135 Å (13.5 nm). On the other hand, the supported catalyst of the present invention is typically characterized by exhibiting a d50 (measured similarly using mercury osmosis) that is greater than about 125 Å (12.5 nm) and less than about 210 Å (21 nm), or greater than about 130 Å (13 nm) and less than about 200 Å (20 nm), for example, greater than about 135 Å (13.5 nm) and less than about 200 Å (20.5 nm). Referring to Figures 1A to 1C, it can be observed that when measurements are taken using nitrogen, an initial peak appears at approximately 80 Å (8 nm), while when measurements are taken using mercury osmosis, an initial peak appears at approximately 90 Å to 100 Å (9 to 10 nm).

[0067] Figures 2A and 2C show typical pore size distributions of supported catalysts with and without added fine powder, prepared according to the present invention. The initial peaks located at smaller pore diameters were observed to be in the range of 50 Å (5 nm) to 100 Å (10 nm). Based on nitrogen measurements, these peaks are estimated to be approximately 65 Å (6.5 nm) and 75 Å (7.5 nm) from Figures 2A and 2C, and approximately 110 Å (11.0 nm) based on the mercury intrusion method.

[0068] Supported catalysts prepared according to the present invention as disclosed herein exhibit a pore size distribution measured using the mercury porosimetry method similarly disclosed herein, including the following properties: (A) For pores with a diameter of less than 200 angstroms (Å) (20 nm), the TPV is approximately 50% or more and up to approximately 75%, or 51% or more, or 52% or more, or 53% or more, or 54% or more, or 55% or more, or 56% or more, or 57% or more, or 58% or more, or 59% or more, or 60% or more, or 62% or more, or 64% or more, and up to approximately 73%, or approximately 71%, or approximately 69%, or approximately 67%, or approximately 65%, or 63%. (B) Pore sizes of approximately 100 Å (10 nm) to approximately 200 Å (20 nm) as similarly measured and reported using mercury osmosis, and typically having a pore content of approximately 35% to approximately 60%, or exceeding 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, or 52%, and having a pore content of approximately 59%, 58%, 57%, 56%, 55%, 54%, 53%, 52%, 51%, or 50% or less. Furthermore, for each of the ranges resulting from the listed lower and upper limits, the “greater” and “less” amounts include values ​​expressed as tenths of a percent and unit percentage values. (C) Pores within the size range of pores generally identified as having a pore diameter greater than 0 Å (0 nm) or greater than 20 Å (2 nm) to about 100 Å (10 nm), and which have also been measured and reported using mercury osmosis, typically have a pore content of more than about 4% to about 14%, or greater than 5%, 6%, 7%, 8%, 9%, or 10%, and Pore ​​content of approximately 13%, 12%, 11%, or 10% or less. Furthermore, for each range resulting from the listed lower and upper limits, the amounts "greater than" and "less than" include values ​​expressed as tenths of a percent and unit percentage values. (D) For pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), the TPV is greater than approximately 15% and less than a maximum of approximately 30%, or greater than approximately 17%, or greater than approximately 20%, or greater than approximately 22% and less than a maximum of approximately 28%, or less than approximately 25%, or less than approximately 23%. (E) For pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), the TPV is 10% or more and less than 30%, or 12% or more, or 15% or more, or 17% or more, or 20% or more and less than 28% at most, or less than 25% at most, or less than 23% at most.

[0069] Catalyst preparation Generally, hydrogenation catalysts can be manufactured using alternative methods. In the impregnation method (note that pre-impregnation and post-impregnation methods will be described further below), an alumina-containing powder such as silica-alumina is mixed with water and then extruded to form a pellet-shaped catalyst support. The support is dried and calcined to impregnate the support with a Group 6 (e.g., Mo) metal compound or precursor and a Group 8, 9, or 10 (e.g., Ni) metal compound or precursor. The impregnated wet pellet is then dried and calcined to obtain a supported catalyst. In another preparation method, an alumina-containing powder, such as silica-alumina, a catalyst metal precursor, water, and additives, such as extrusion aids and papillogenic chemicals, are combined, mixed, and extruded into pellets. The metal-containing wet pellet is then dried and calcined to produce a supported catalyst.

[0070] Suitable catalysts can be prepared by impregnating a catalyst support exhibiting the properties described herein, preferably an alumina-containing support such as silica-alumina, using the stabilized aqueous compositions and methods described in U.S. Patents No. 7,390,766, No. 7,560,407 and No. 7,642,212 (assigned to DPKlein, Advanced Refining Technologies), and the disclosures of the above U.S. patents are incorporated herein to the extent permitted. A preferred method and composition comprises adding to a suitable amount of water (A) at least one substantially water-insoluble Group 8, Group 9 or Group 10 metal component, (B) at least one substantially water-soluble phosphorus-containing acidic component in an amount insufficient to cause dissolution of at least one Group 8, Group 9 or Group 10 metal component, typically to produce a slurry at ambient temperature, (C) combining the slurry with at least one Group 6 metal component, (D) mixing the combination of (A), (B) and (C), and heating the mixture to a time and temperature sufficient for (A), (B) and (C) to form a solution, and (E) adding additional amounts of water as needed to obtain a solution concentration of at least one Group 8, Group 9 or Group 10 metal, at least one Group 6 metal, and phosphorus useful for impregnating a carrier, where Group 6, as well as Groups 8, 9 and 10, refer to the groups of the periodic table of elements. In various preferred embodiments, the molar ratio of at least one group 8, group 9, or group 10 metal to the group 6 metal is about 0.05 to about 0.45, provided that the amount of at least one group 8, group 9, or group 10 metal is sufficient to promote the catalytic effect of the group 6 metal, the concentration of the group 6 metal expressed as an oxide is at least about 3 to about 50% by weight, based on the weight of the composition, and the amount of phosphorus-containing acidic component is sufficient to provide a molar ratio of phosphorus to the group 6 metal of about 0.05 to less than about 0.25. In further embodiments, the process includes a step of separating the volatile portion of the solution from the impregnated uncalcined carrier to obtain a dry catalyst having a desired water content.

[0071] A “pre-impregnated” catalyst refers to a catalyst to which a metal-containing solution (one or more) is added before the porous catalyst support is calcined. The metal-containing solution (one or more) can be added before or after the formation of the catalyst particles, but in important embodiments, the metal-containing solution (one or more) is added before the support material is calcined. However, there is a significant advantage in obtaining the uncalcined support by forming it after impregnation (contact) with an aqueous solution containing one or more catalyst metals. These advantages are observed in the form of a more desirable distribution of metal throughout the support in the final catalyst. Therefore, a “pre-impregnated” catalyst can be prepared as follows: Uncalcined alumina-containing silica-alumina powder is thoroughly mixed with water, or optionally with a diluted aqueous solution of nitric acid, and the mixture is combined with a suitable amount of a stable metal solution. Such a solution typically contains at least one Group 6 and at least one Group 8, Group 9, or Group 10 metal compound or precursor, optionally but preferably phosphorus, e.g., molybdenum, nickel, and phosphorus compounds, and optionally additional amounts of one or more Group 8, Group 9, and Group 10 metal solutions, to provide the desired amount of metal on the final catalyst, if necessary. The one or more Group 8, Group 9, or Group 10 metals used to achieve the optionally additional amounts of one or more Group 8, Group 9, or Group 10 metals are typically selected to be water-soluble under the temperature conditions encountered. Furthermore, as described elsewhere in this specification, chelating agents or compounds may optionally but preferably be included in the impregnation solution.

[0072] A metal-containing mixture typically containing about 50 to about 65 weight percent moisture is preferably formed into catalyst particles of a desired size by extrusion. The formed catalyst particles are dried using alternative or combined heating methods, including high-temperature drying and combinations of high and moderate firing temperatures. For example, wet-impregnated catalyst particles can be subjected to high-temperature drying conditions of about 375°F (190.6°C) to about 425°F (218.3°C), for example 400°F (204.4°C), for about 30 to 60 minutes, for example 40 minutes, or for the entire time, to achieve the desired target LOI level disclosed elsewhere in this specification. Alternatively, the wet-impregnated catalyst particles can be subjected to an initial high-temperature drying temperature of approximately 300°F (148.9°C) to approximately 340°F (171.1°C), for example 320°F (160°C), for a limited time, for example about 8 to 12 minutes, for example 10 minutes; then the temperature can be increased to a milder firing temperature of approximately 650°F (343.3°C) to approximately 690°F (365.6°C), for example 670°F (354.4°C), for about 30 to 60 minutes, for example 40 minutes; and then the catalyst particles can be held at the final lamp temperature for approximately 8 to 12 minutes, for example about 10 minutes, or for the entire time, to achieve the desired target LOI level disclosed elsewhere in this specification. Regardless of the drying method used, careful consideration must be given to whether or not the impregnation solution contains a chelating agent, and if one or more drying methods are used, the overall drying conditions should be selected to preserve at least a portion of the chelating agent or its complex with the catalytic metal. Analytical methods known to those skilled in the art are available to measure the residual levels of chelating agents, complexes, or thermal by-products in the dried supporting catalyst.

[0073] A "post-impregnation" catalyst refers to a catalyst to which a metal-containing solution (one or more) is added after the porous catalyst support has been calcined. Preferred calcination conditions for the support itself are described above. While the porous catalyst support can be calcined before or after the formation of catalyst support particles, a key aspect of post-impregnation is the addition of a metal-containing solution (one or more) after the support material has been calcined. Therefore, a "post-impregnation" catalyst can be prepared as follows: Uncalcined alumina-containing or silica-alumina powder is thoroughly mixed with water, or optionally with a diluted aqueous solution of nitric acid, and the alumina mixture containing about 50-75% by weight of water is then formed into catalyst particles of the desired size and shape, preferably by extrusion. The formed particles are dried at a temperature of about 110-150°C and then dried at about 400°C. The particles are calcined at a temperature of approximately 750°C for approximately 1 to 2 hours. The dried and calcined particles are then brought into contact with a suitable amount of a stable metal solution. For example, such a solution may contain molybdenum, nickel, and phosphorus, in addition to optionally an additional amount of a solution of one or more metals from Group 8, Group 9, or Group 10 (also identified as Group VIIIB according to CAS designation), in order to provide the desired amount of metal on the final catalyst while substantially and uniformly filling the pores. After a suitable contact time, the formed catalyst particles are dried according to one of the alternative conditions described above.

[0074] A significant difference between pre-impregnated and post-impregnated catalysts is that post-impregnated catalysts undergo two calcination steps, typically the first of which involves calcining an essentially porous support, followed by a second step in which the calcined support is impregnated with catalytically active metal components and optionally phosphorus components. In contrast, pre-calcined catalysts undergo a single calcination step, as described above.

[0075] Suitable catalytically active metals from Groups 8, 9, and 10 present in the components of the present invention include suitable compounds such as Fe, Co, Ni, Pd, and Pt, and mixtures thereof. Of these, Co and Ni are the most preferred. Suitable Group VIB elements or metals include Cr, Mo, W, and mixtures thereof, with Mo and W being the most preferred. Preferred combinations of metal components include, for example, nickel and molybdenum, cobalt and molybdenum, tungsten and nickel or cobalt, a combination of molybdenum, cobalt and nickel, a combination of tungsten, nickel and cobalt, and a combination of molybdenum, chromium and nickel, with the combination of molybdenum and nickel being particularly preferred.

[0076] A suitable overall process for preparing a stable impregnation solution can be described as follows: Basic nickel- and molybdenum-containing solutions can be prepared by combining water, a molybdenum source, a nickel source, and aqueous ammonia in appropriate proportions. Various molybdenum and nickel sources can be used. For molybdenum, these include, but are not limited to, molybdenum trioxide, ammonium dimolybdate, and ammonium heptamolybdate. For nickel, these include, but are not limited to, nickel carbonate and nickel nitrate. The weights of the components can be varied to ensure solution stability and appropriate concentrations and ratios of the metals. The required weights of the components, the order of addition, the temperature, and the reaction time are known to those skilled in the art.

[0077] Optionally, but preferably, the impregnation solution contains at least one chelating agent, such as an organic compound known to chelate when combined with one or more catalytically active metal components. Suitable compounds or chelating agents include organic additives such as (i) organic compounds selected from the group consisting of compounds containing at least two oxygen atoms and 2 to 10 carbon atoms, and compounds composed of or derived from these compounds, or (ii) organic compounds containing at least one covalently bonded nitrogen atom and at least one carbonyl moiety, or both of (i) and (ii). The organic compounds according to (i) above are preferably selected from the group consisting of compounds containing at least two oxygen-containing moieties, such as carboxyl, carbonyl, or hydroxyl moieties, and 2 to 10 carbon atoms, and compounds composed of or derived from these compounds. Compounds composed of or derived from organic compounds may be, for example, ethers, esters, acetals, acid chlorides, acid amides, oligomers, or polymers of organic compounds. Examples of suitable organic compounds include carboxylic acids such as citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, and malic acid; as well as butanediol, pyruvate aldehyde, glycolaldehyde, and acetaldol. Organic compounds selected from the group of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule, and compounds composed of these compounds, are further... The following are preferred. Preferred compounds include, for example, tartaric acid, or aliphatic alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, and trimethylolpropane. Compounds composed of these organic compounds include oligomers and polymers, such as diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, and tetrapentylene glycol. This range can be extrapolated to include polyethers such as polyethylene glycol. With respect to polyethylene glycol, polyethylene glycol having a molecular weight of 200 to 8,000 is preferred. Other compounds composed of these organic compounds are ethers such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. Preferred organic compounds are, in particular, ethylene glycol, diethylene glycol, polyethylene glycol, or mixtures thereof. Another group of organic compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule are formed by monosaccharides such as glucose and fructose. Compounds composed of these organic compounds include oligomers and polymers, such as disaccharides like lactose, maltose, and saccharose, as well as polysaccharides. Citric acid is a particularly preferred organic compound or chelating agent.

[0078] The organic compound according to (ii) preferably contains at least two carbonyl moieties. It is preferable that at least one carbonyl moiety is present on the carboxyl group. It is even more preferable that at least one nitrogen atom is covalently bonded to at least two carbon atoms. Preferred organic compounds satisfy formula (I) or (II), (R 1 R)NR 3 -N(R 1 'R 2 ')(I) N(R 1 R 2 R 1 ')(II) In the formula, R 1 , R 2 , R 1 'and R 2 ' is independently selected from alkyl, alkenyl, and allyl groups having up to 10 carbon atoms, optionally substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. 3 -O- or -NR 4 - An alkylene group having up to 10 carbon atoms that can be interrupted by R. 4 R 1 The same groups as those shown above are selected for R. 3 The alkylene group may be substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. As described above, it is essential that the organic compound of formula (I) or (II) contains at least one carbonyl moiety. Preferably, R 1 , R 2 , R 1 'and R 2 'At least two of (Equation (I)), and R 1 , R 2 , and R 1 At least two of (Equation (II)) are Equation -R 5 -C(O)OX is present in the formula, where R 5X is an alkylene group having 1 to 4 carbon atoms, and X is hydrogen, or another cation such as ammonium, sodium, potassium, and / or lithium cations. If X is a polyvalent cation, one X has two or more -R 5 It can be bonded to a -C(O)O- group. Typical examples of compounds of formula (I) are ethylene diamine(tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. A typical example of a compound of formula (II) is nitrilotriacetic acid (NTA).

[0079] The catalyst composition typically contains approximately 30 to 45% by weight of at least one metallic component from Group 6 of the periodic table (or referred to as Group VIB) and at least one metallic component from Group 8, 9, or 10 of the periodic table (or referred to as Group VIIIB), or a mixture thereof, with the Group VIB and VIIIB metallic components calculated as oxides based on the total weight of the catalyst composition. Furthermore, the total weight of the Group 6 metallic component and the Group 8, 9, or 10 metallic component, calculated as oxides, constitutes approximately 35 to 55% by weight based on the total weight of the catalyst composition. Alternatively, it may contain Group 6 metallic oxides. The total weight of the content and the content of Group 8, Group 9, or Group 10 metal oxides ranges from approximately 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45% by weight to approximately 55, 54, 53, 52, 50, 49, 48, 47, 46, or 45% by weight.

[0080] Specifically, the amount of at least one group 6 metal component, when calculated as an oxide, constitutes approximately 30 to approximately 45% by weight, or approximately 31, 32, 33, 34, 35, 36, 37, or 38% by weight, or approximately 45, 44, 43, 42, 41, 40, 39, 38, 37, or 36% by weight.

[0081] Group VIIIB metals, when calculated as oxides, are typically present in amounts of 3 to about 15% by weight, or in amounts ranging from about 3.5, 4, 5, 6, 7, 8, 9, or 10% by weight to about 15, 14, 13, 12, 11, 10, 9, 8, or 7% by weight. Phosphorus, if present, is typically present in amounts of about 1 to about 10% by weight, when calculated as P2O5, or in amounts ranging from about 1.5, 2.5, 3, 4, or 5% by weight to about 6, 7, 8, 9, or 10% by weight. The amounts of Group VIB and Group VIIIB metals present in the catalyst composition can be measured using atomic absorption spectrometry (AAS), inductively coupled plasma spectrometer (ICP) analysis, and / or X-ray fluorescence (XRF).

[0082] The supporting catalyst composition after impregnation, drying, and calcination exhibits the above properties, i.e., the metal-containing components and phosphorus (if present) exist as their oxides, and preferably, before the sulfidation step if one is present.

[0083] The term "aggregate" refers to a product formed by combining particles held together by various physicochemical bonds, while the term "forming" and its grammatical variations refer to the process of forming aggregates. More specifically, each aggregate consists of multiple adjacent constituent primary porous carrier particles, preferably joined and connected at their contact points. Thus, aggregate particles typically exhibit a higher macropore content than the primary particles that make up the aggregate particles due to interparticle voids between the constituent composite particles. These larger voids are not included as part of the characteristic properties of the primary porous carrier particles, e.g., specific pore size or range and pore size distribution characteristics.

[0084] Aggregation of porous carriers, such as alumina and composites, is carried out according to methods known in the art, particularly by methods such as pelletizing, extrusion, and forming into beads in a rotating coating drum. Modularization techniques can be used to aggregate composite particles having a diameter of about 0.1 mm or less into particles having a diameter of at least about 0.8 mm using a granulation solution. As is known to those skilled in the art, aggregation can be optionally carried out in the presence of additional amorphous or crystalline binders, and pore-forming agents can be added to the mixture to be aggregated. Conventional binders include other forms of alumina, silica, silica-alumina, clay, zirconia, silica-zirconia, magnesia, and silica-boria. Conventional pore-forming agents can be used, and examples of suitable reagents include wood flour, charcoal, cellulose, starch, naphthalene, and organic compounds that generally promote pore formation and can be removed by calcination. However, the addition of pore-forming agents is not necessary or desirable.

[0085] Catalyst compositions may have different forms selected for their suitability to the process and / or apparatus in which they are used. For example, when catalyst compositions are used in slurry reactors, fluidized beds, moving beds, or expanding beds, spray drying or beading is generally applied. In fixed-bed or boiling-bed applications, catalyst compositions are generally extruded, pelletized, and / or beaded. In the latter case, at any stage before or during the molding process, Any additives commonly used to facilitate molding may be added. These additives may include aluminum stearate, surfactants, graphite, starch, methylcellulose, bentonite, polyethylene glycol, polyethylene oxide, or mixtures thereof. Furthermore, as discussed elsewhere, when alumina is used as a carrier, nitric acid may be added before the molding process, for example, to increase the mechanical strength of the aggregates. In the present invention, the molding process is carried out in the presence of water. For extrusion and beading, the amount of water in the molding mixture, expressed as LOI, is preferably in the range of 20-80%. Additional water may be added if required by the molding operation, or if the amount of water is too high, it can be reduced, for example, by solid-liquid separation by filtration, decantation, or evaporation. Appropriately controlling the amount of water is within the scope of those skilled in the art.

[0086] Preferred shapes include powder, spherical, cylindrical, ring, and symmetrical or asymmetrical multi-lobed forms, such as tri-lobed and quadruple-lobed forms. Particles resulting from extrusion, beading, or pelletizing typically have a diameter in the range of about 0.2 to about 10 mm and a length in the range of about 0.5 to about 20 mm, although deviations from these general ranges are possible. Catalysts in the form of extruded materials are generally preferred.

[0087] The present invention also relates to a catalyst composition according to the present invention, wherein the metal components are partially or completely converted to their sulfides. In this case, it is preferable that the catalyst is essentially free of group VIIIB metal disulfides.

[0088] The firing is carried out according to the temperatures and times described above. As stated, the firing conditions, particularly the temperature, for metal-containing (especially post-impregnated) supports or carriers are typically lower than the temperature used for the support or carrier itself. The firing may be carried out in an inert gas such as nitrogen, or in an oxygen-containing gas such as air or pure oxygen, optionally in the presence of water vapor. Preferably, the firing is carried out in an oxygen-containing atmosphere.

[0089] Catalysts prepared by the methods described herein also typically exhibit a loss on ignition (LOI) of about 6% to about 38% by weight, measured at 550°C (1022°F), or a loss on ignition of about 7% or about 8% or about 9% or about 10% or about 11% or about 12% or about 13% or about 14% or about 16% or about 18% or about 20% by weight, up to about 37% or about 36% or about 35% or about 34% or about 33% or about 32% or about 30% or about 28% or about 26% or about 24% by weight.

[0090] Furthermore, the catalyst according to the present invention is particularly useful in hydrocarbon conversion processes that involve contacting a hydrocarbon feedstock with a supporting catalyst in the form of particulate matter under high temperature and high pressure conditions with hydrogen, and the catalyst is prepared according to the present invention. As described herein, such a catalyst comprises at least one catalytically active metal from Group 6 of the periodic table, at least one catalytically active metal from Group 8, Group 9 or Group 10 of the periodic table, and optionally phosphorus, wherein the metals and optionally phosphorus are supported on the above-described alumina-containing carrier, and the pore size distribution characteristics and other particulate properties are also as described.

[0091] Use of catalysts in the hydroprocessing process The catalyst prepared according to the present invention can be reacted under a wide range of reaction conditions, generally, for example, temperatures in the range of about 200°C to about 500°C, hydrogen pressures in the range of about 5 to 300 bar (0.5 MPa to 30 MPa), and about 0.05 to 10 hours. -1 Under liquid hourly space velocity (LHSV) ranges, virtually all hydrogenation processes are available for processing multiple feeds. It can be used in the refining process. The term "hydroprocessing" encompasses a variety of petroleum refining processes that involve reacting hydrocarbon feedstocks with hydrogen at high temperature and pressure (hydroprocessing reaction conditions), including hydrogenation, hydrodesulfurization, hydrodenitrification, hydrometallation, hydrodesaromatherapy, hydrocracking, and hydrocracking under mild pressure conditions, also known as mild hydrocracking.

[0092] More specifically, "hydroprocessing" is the term used herein. When applicable, this refers to a petroleum refining process in which petroleum feedstock (a complex mixture of hydrocarbons present in petroleum) is reacted with hydrogen under pressure in the presence of a catalyst to reduce (a) the concentration of at least one of sulfur, contaminating metals, nitrogen, and Conradson carbon present in the feedstock, and (b) at least one of the viscosity, pour point, and density of the feedstock. Hydroprocessing includes hydrocracking, isomerization / dewaxing, and hydrogenation finishing. Examples include hydrotreating processes that differ in the amount of hydrogen reacted and the properties of the petroleum feedstocks being treated.

[0093] Hydrocracking is typically understood to involve the hydroprocessing of a primarily hydrocarbon compound ("supply material") containing at least five (5) carbon atoms per molecule. The process is carried out (a) at a partial hydrogen pressure of ultra-atmospheric pressure, b) at a temperature typically below 593.3°C (1100°F), (c) with an overall net chemical consumption of hydrogen, and (d) in the presence of a solid-supported catalyst containing at least one hydrogenation component.

[0094] Hydrotreating typically involves at least five carbon atoms per molecule. It is understood that the process includes (a) a hydroprocessing of a primarily hydrocarbon compound containing ("supply material") for the desulfurization and / or denitrification of the supply material, and the process is This is carried out at a partial hydrogen pressure of ultra-atmospheric pressure, (b) at a temperature typically below 593.3°C (1100°F), (c) using the overall net chemical consumption of hydrogen, and (d) in the presence of a solid-supported catalyst containing at least one hydrogenation component.

[0095] Hydrotreating operations for heavy hydrocarbon streams such as petroleum hydrocarbon residues. The conditions are known in the art and include a pressure in the range of approximately 1,000 psia (68 atm) to approximately 3,000 psia (204 atm), an average catalyst bed temperature in the range of approximately 700°F (371°C) to approximately 850°F (454°C), a liquid space velocity (LHSV) in the range of approximately 0.1 hydrocarbon volumes per hour per catalyst to approximately 5 hydrocarbon volumes per hour per catalyst, and a standard cubic feet per barrel (SCFB) of approximately 2,000 (356 m³). 3 / m 3 ) ~ approximately 15,000 SCFB (2,671m 3 / m 3 This includes a hydrogen recirculation rate or hydrogenation rate within the range of ). Preferably, the operating conditions include a total pressure in the range of about 1,200 psia to about 2,000 psia (81 to 136 atm), an average catalyst bed temperature in the range of about 730°F (387°C) to about 820°F (437°C), an LHSV in the range of about 0.1 to about 4.0, and about 3,000 SCFB (534 m 3 / m 3 ) ~ approximately 10,000 SCFB (1,781m 3 / m 3 This includes a hydrogen recirculation rate or hydrogenation rate within the range of ). Generally, the process temperature and space velocity are selected such that at least 30 vol% of the feed fraction boiling above 1,000°F is converted to a product boiling below 1,000°F, more preferably at least 50 vol% is converted to a product boiling below 1,000°F, and even more preferably at least 70 vol% of the target fraction is converted to a product boiling below 1,000°F.

[0096] In the treatment of hydrocarbon distillates, the operating conditions are typically: an average catalyst bed temperature in the range of approximately 200 psia (13 atm) to approximately 3,000 (204 atm), an LHSV of approximately 1,000 SCFB (178 m³) in the range of approximately 0.4 to 6 volumes of hydrocarbons per hour per volume of catalyst. 3 / m 3 ) ~ approx. 10,000S CFB (1,381m 3 / m 3 This would include hydrocarbon recirculation rates or hydrogenation rates within the range of ). Preferred operating conditions for the hydrotreating of hydrocarbon distillates are , hydrogen partial pressure within the range of approximately 200 psia (13 atm) to approximately 1,200 psia (81 atm), average catalyst bed temperature within the range of approximately 600°F (315°C) to approximately 750°F (398°C), LHSV within the range of approximately 0.5 hydrocarbon volumes per hour per catalyst to approximately 4 hydrocarbon volumes per hour per catalyst volume, and approximately 1,000 SCFB (178 m 3 / m 3 ) ~ approximately 6,000 SCFB (1,068 m 3 / m 3 This includes hydrogen recirculation rates or hydrogen addition rates within the range of ).

[0097] However, the most desirable conditions for the conversion of a particular feedstock to a given product can best be obtained by converting the feedstock at several different temperatures, pressures, space velocities, and hydrogenation rates, correlating the effect of each of these variables, and selecting the best compromise between the overall conversion rate and selectivity. The catalyst composition of the present invention is particularly suitable for hydrotreating heavy hydrocarbon feedstock, also referred to as feedstock or feedstock blend. be.

[0098] Therefore, the generally described invention will be more readily understood by referring to the following examples, which are provided as illustrations and are not intended to limit the invention. [Examples]

[0099] Preparation of the supporting catalyst. Generally, the catalyst metal impregnation solution is prepared as follows: Nickel and molybdenum-containing solutions are prepared by mixing water, a molybdenum source, a nickel source, and water ammonia in appropriate proportions. Various molybdenum and nickel sources, as disclosed above, can be used. These solutions are used to impregnate a support to prepare the final catalyst. The component weights and addition order are selected to ensure solution stability and the chosen target concentration of metal on the final catalyst for the intended catalytic application. The solution treatment temperature and time are selected to ensure solution stability. The required component weights, addition order, treatment temperature, and treatment time are typical and generally known to those skilled in the art.

[0100] Comparative Example 1. (I) Preparation of Comparative Substrate To prepare a comparative substrate, also referred to herein as a carrier or support, for use in preparing a comparative catalyst, the following steps were taken: (1) In a two-stage precipitation process in which temperature and pH are varied and controlled at each stage, see, for example, U.S. Patent Application Publication No. 2014 / 0367311, U.S. Patent No. 6,589,908 or U.S. Patent No. 6,984,310 (incorporated herein by reference). For example, in the first stage, half of the total amount of aluminum sulfate and sodium aluminate is mixed to form a precipitate of alumina at approximately pH 8 and 55°C (131°F). In the second stage, before adding the second half of aluminum sulfate and sodium aluminate, the temperature is raised to approximately 65°C (150°F), the pH is raised to approximately 9, the reactants are mixed, and the second stage of precipitation is completed. (2) The obtained alumina is washed and mixed with a silica-alumina composition containing about 75% by weight silica and 25% by weight alumina. (3) The mixture from (2) is introduced into a heated auger to dry It was dried. (4) The mixture from (3) was placed in an Eirich mixer along with water, nitric acid, recycled substrate, and catalyst fine powder from the later stages of the process, and mixed until the resulting mixture was granulated. (5)(4) The material was extruded to form a substrate or support precursor. (6) The extruded substrate precursor was introduced into a rotary calcination furnace and heated until the volatile matter level, as determined by the loss on ignition (LOI) test, decreased to <2%. The LOI was found to be present in the sample. LOI is a measure of the total volatile matter or components that can volatilize at high temperatures. The LOI test is performed by exposing the sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for 1 hour, thereby decomposing, oxidizing, or igniting any present organic matter and eliminating residual moisture to the target endpoint.

[0101] (II) Comparative supporting catalysts were prepared as follows: (1) The substrate or support prepared in I above was placed in a dip-soak impregnation basket. (2) The substrate was continuously lowered and immersed in a tank containing a desired impregnation solution consisting of molybdenum, nickel, phosphorus, and a chelating agent at a desired concentration. (3) The impregnated catalyst was then passed through a rotary calcination furnace until it reached a target LOI level of 5% by weight.

[0102] Embodiment A of the present invention The substrate or support A was prepared as follows: (1) 1200 g of silica-alumina powder (based on the standard of not containing volatile substances) containing 5% by weight of silica dispersed in alumina was placed in an Eirich mixer at room temperature. (2) 17.15 g of concentrated nitric acid (70% by weight HNO3) and 2000 g of deionized water were added to a blender at a rate of approximately 150 cc / min. The composition was mixed for a total of 5 minutes (including the time for adding water). (3) Stop mixing and scrape off the sides of the mixer, and at that point add a small amount of water (20g each) as needed to form an extrudeable paste. (4) The LOI of the paste was measured at 69%, which was suitable for extrusion. (5) The paste mixture obtained in (4) was extruded using a 1 / 16” AQ plastic insert die and a water-cooled extruder barrel. (6) The extruded material was placed on a screen tray to a depth of approximately 1 / 2 inch and placed in a preheated Gruenberg drying oven at 250°F (121.1°C) for 2 hours, followed by another 2 hours at 400°F (204.4°C). (7) A 200g dry extruded from (6) was fired in a 1400°F (760°C) oven for 40 minutes using 2 SCFH (standard cubic feet per hour) of dry air. (8) Next, the fired extruded material was cooled to room temperature.

[0103] Catalyst sample A was prepared as follows: (1) Weigh 50g of base material A (standard that does not contain volatile substances) prepared above. (2) The substrate from (1) was impregnated with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations using the induce wetness method. (3) The impregnated samples from (2) were heated at 400°F (204.4°C) for 40 minutes. (4) The obtained catalyst sample A was cooled to room temperature.

[0104] Catalyst sample A was prepared as follows: (1) Weigh 50g of base material A (standard that does not contain volatile matter) prepared above. (2) The substrate from (1) was impregnated with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations using the induce wetness method. (3) The impregnated samples from (2) were heated at 400°F (204.4°C) for 40 minutes. (4) The obtained catalyst sample A was cooled to room temperature.

[0105] Example B of the present invention A substrate or support for catalyst sample B (including recycled fine powder) was prepared as follows: (1) 1200 g of silica-alumina powder containing 5% by weight of silica dispersed in alumina (on a substrate free of volatile matter) was placed in an Eirich mixer at room temperature. (2) 60g of pulverized catalyst B fine powder (recycled fine powder) and 60g of pulverized base material B fine powder (recycled fine powder) were placed in a mixer. (3) 17.1 g of concentrated nitric acid (70 wt% HNO3) and 2000 g of deionized water were placed in a mixer and mixing was started. (4) The mixer was stopped and the sides were scraped off, and water was added as needed to obtain the desired paste viscosity. (5) After 10 minutes, the formed mixture formed granules with a 66.2% LOI. (6) The mixture from (5) was extruded using a 1 / 16” AQ plastic insert die and a water-cooled extruder barrel. (7) The extruded material was placed in a drying oven at 250°F (121.1°C) for 2 hours. (8) The dried extruded material from (7) was introduced into a rotary firing furnace according to the following protocol: filled at 250°F (121.1°C), held for 10 minutes, increased to 1400°F (760°C) for 40 minutes, and held at 1400°F (760°C) for 40 minutes. (9) The fired substrate was then cooled to room temperature.

[0106] Catalyst sample B was prepared as follows. (1) 175 g of the base material (excluding volatile substances) from (9) above was weighed. (2) The substrate from (1) was impregnated using the dip-soak impregnation method with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations. (3) The impregnated substrates from (2) were introduced into a rotary firing furnace according to the following protocol: 320°F (160°C) for 10 minutes, then increased to 670°F (354.4°C) for 40 minutes, and held at 670°F (354.4°C) for 10 minutes. (4) Next, the obtained support catalyst B was cooled to room temperature.

[0107] The pore size distribution (PSD) of the comparative and present invention substrates (supports) and catalysts prepared as described above was measured using the standard Hg porosimetry method confirmed above. The distributions are shown in Figures 1A to 1C and Figures 2A to 2C.

[0108] Figures 1A to 1C show a comparison of PSDs between the three catalyst substrates. A comparison of the bulk properties and chemical composition of the three catalyst substrates is summarized in Table 1 below. The PV (pore volume, in other words, total pore volume) of exemplary substrate A is approximately 20% higher than that of comparative example substrates, while the PV of exemplary substrate B (including fine powder) is 15% higher.

[0109] Figures 2A to 2C show a comparison of the PSDs of the three catalysts prepared in the above examples. A comparison of the bulk properties and chemical compositions of the three catalysts is summarized in Table 2 below. It will be observed that the total metal load of exemplary catalysts A and B is higher than that of the comparative catalyst.

[0110] [Table 2]

[0111] [Table 3]

[0112] Exemplary catalysts A and B, as well as the comparative catalyst, were tested under the following bench-scale unit (BSU) test protocol: Total pressure=2300psi H2 / oil=5500SCFB LHSV = -2.0 h-1 CAT (Catalyst Temperature): 710°F (376.7°C) for 7 days, followed by 720°F (382.2°C) for 5 days, followed by 735°F (390.6°C) for 5 days. Feed: Vacuum-reduced gas oil (VGO) feed blend with the following characteristics: API (American Petroleum Institute) specific gravity = 19.7, N = 1810 ppm, S = 27150 ppm

[0113] A simplified flowchart of the bench scale test unit (BSU) used to perform performance tests using the catalysts prepared in the examples is shown in Figure 3. Recirculation was not used in BSU operation. The whole liquid product (WLP) was sent to an online stripper controlled to target a cut point. Stripper overhead (STO), stripper bottom (STB), and Samples were collected from the gas valve and tested daily for their properties. The target cut point for both the STO product and the STB product was 470°F (243.3°C) to ensure that the STB product had a boiling point higher than 470°F (243.3°C).

[0114] Test results Table 3 shows a comparison of catalysts for VGO hydrogenation denitrification (HDN), hydrogenation desulfurization (HDS), and hydrogenation or hydrogenation dearomaticization (HDA) of aromatic compounds, and Table 4 shows the effect on product viscosity (note that HDA is represented here using apparent conversion rate).

[0115] [Table 4]

[0116] Referring to Table 3, Exemplary catalyst A is more active than the comparative catalyst for HDN, HDS, and HDA (or HCR), but Exemplary catalyst B (including the fine powder) is also more active. The table also includes the ratio of kHDS and kHDN (reaction rates for the indicated reactions) for the exemplary catalysts to the comparative catalysts, which further demonstrates the advantages of the exemplary catalysts in each case.

[0117] The improved performance or catalytic activity of the catalyst of the present invention can also be observed in Figures 4A-4C and 5A-5C. Figure 4A is a plot of the reaction rate of hydrodenitrification (kHDN) as a function of the operating temperature of the catalyst or bench-scale unit for comparative and exemplary catalysts. It is observed that the exemplary catalyst is more effective at a given temperature, or that equivalent HDN performance of the exemplary catalyst can be achieved at a lower temperature. Similar advantageous results for the catalyst of the present invention are observed in Figure 4B for HDS and in Figure 4C for apparent conversion rate or hydrocracking at 700°F for producing higher concentration paraffins. Therefore, when the supporting catalyst of the present invention is used in a hydroprocessing process for the removal of sulfur, nitrogen, or hydrogenation of aromatic compounds, the treated carbonized water The levels of these components in the elementary product improve measurably as a function of the process operating temperature. Operating at higher temperatures results in lower sulfur or nitrogen content in the processed product, but doing so incurs higher operating costs.

[0118] Similarly, the improved performance of the catalysts of the present invention can be seen in Figures 5A, 5B, and 5C, which show the respective volume percentages of aromatic, naphthenic, and paraffinic elements in the stripper bottom (STB) of bench-scale units used to evaluate the performance of exemplary catalyst A versus comparative catalyst, as a function of apparent conversion rate. In each case, a significant improvement can be observed, and this improvement is more pronounced at lower operating temperatures, which is a favorable advantage in itself.

[0119] When exemplary catalyst A, prepared in the examples herein, was compared with a comparative catalyst, the improved performance achieved by using the supported catalyst of the present invention was also achieved by improvements in product viscosity and viscosity index (VI) at 100°C. The results are summarized in Table 4. The following improvements were achieved with the catalyst of the present invention: the STB and WLP viscosities of exemplary catalyst A at 100°C were lower than those of the comparative catalyst, but STB VI was higher.

[0120] [Table 5]

[0121] The data above indicates that a combination of higher catalyst metal packing, higher substrate pore volume, and higher concentration of larger pores is the key feature that leads exemplary catalyst A to exhibit higher VGO HDN, HDS, and HDA activity. In other words, even with the addition of recycled fine powder to the substrate, exemplary catalyst B (shown in the table and figure above) maintains its advantage in activity for HDN, HDS, and HDA.

[0122] The comparative catalyst and catalyst A, prepared according to the above examples, were further evaluated in BSU under the following conditions using the same feed blend as above.

[0123] [Table 6]

[0124] Table 5 below summarizes the types of hydrocarbons in STB from BSU tests measured by GC-MS.

[0125] [Table 7]

[0126] As can be seen, compared to the comparative catalyst, the use of catalyst A according to the present invention resulted in an increase in paraffin content, a significant increase in naphthene content, and a significant decrease in aromatic content in the treated feedstock.

[0127] Further data was obtained from BSU testing by measuring the product properties of the comparative support catalyst and exemplary catalyst A, prepared according to the above examples, using the same feed as described above. The test results are summarized in Tables 6A (Comparative Catalyst) and 6B (Exemplary Catalyst A) below. In each case, the same feed as in the previous table was used. Simdist = ASTM D2887 simulated distillation.

[0128] [Table 8]

[0129] [Table 9]

[0130] The petroleum feedstock used in the catalyst's BSU test was selected because it exhibited lower VI, higher viscosity, and higher content of aromatic and sulfur compounds, although improvements in all of these aspects were desirable. Considering the BSU test results, the following conclusions and observations were made. 1. Under each of the experimental conditions using exemplary catalyst A, the STB product VI was higher, and the viscosity and total aromatic content were lower, both of which are desirable results. 2. As the catalyst concentration increases, the VI of the STB product increases, while the viscosity and total aromatic content decrease. This is also desirable. 3. Under each of the execution conditions, the hydrogenolysis conversion rate up to 700°F using example catalyst A is higher than that of the comparative catalyst, clearly demonstrating its advantage. 4. Exemplary catalyst A yields a higher apparent conversion rate, and therefore a lower STB product aromatic content, as well as a higher paraffin and naphthene content, compared to the comparative catalyst. 5. Under each execution condition, exemplary catalysts A and B exhibit higher HDN / HDS activity than the comparative catalysts.

[0131] Alternative Embodiments The following sections illustrate various and alternative embodiments of the present invention. 1. A supporting catalyst comprising at least one metal from Group 6 (or Group VIB) of the periodic table and at least one metal from Group 8, Group 9, or Group 10 (or Group VIIIB) of the periodic table, optionally comprising phosphorus. Calculated as oxides and based on the total weight of the catalyst composition, Group 6 metals constitute approximately 30 to 45% by weight, and the sum of the metal components of Group 6, Group 8, Group 9, or Group 10, or mixtures thereof, constitutes approximately 35 to 55% by weight. The metal, and phosphorus if present, is supported on and / or within a porous inorganic oxide carrier or support, and the support before the incorporation of the metal and phosphorus has a total pore volume (TPV) of approximately 0.8 cc / g to approximately 1.5 cc / g, (a) In pores with a diameter of 100 angstroms (Å) (10 nm) to 200 angstroms (Å) (20 nm), the TPV is approximately 25% or more to approximately 7545%. (b) In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), TPV of more than 15% to less than 30%. (c) In pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm), containing 10% or more to less than 30% TPV. The supporting catalyst, (d) In pores with a diameter of 100 Å (10 nm) to 200 Å (20 nm), TPV of approximately 35% or more to approximately 60%. (e) In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), TPV of more than 15% to less than 30%. (f) In pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm), containing 10% or more to less than 30% TPV. A supported catalyst whose pore properties and content are measured using mercury porosimetry. 2. The support catalyst according to item 1, further characterized in that the support exhibits a d50 of 110 Å (11 nm) or more and approximately 170 Å (17 nm) or less, or the support catalyst exhibits a d50 of approximately 125 Å (12.5 nm) or more and approximately 210 Å (21 nm) or less. 3. The supporting catalyst according to item 1, further characterized in that more than 17% to less than 28% of the TPV of the supporting catalyst is located within pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm). 4. The supporting catalyst according to item 1, further characterized in that approximately 12% or more to less than approximately 28% of the TPV of the supporting catalyst is located within pores having a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm). 5. The supporting catalyst according to item 4, further characterized in that approximately 15% or more to less than approximately 25% of the TPV of the supporting catalyst is located within pores having a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm). 6. The supporting catalyst according to item 1, further characterized in that approximately 40% to 55% of the TPV is contained within pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm). 7. The support catalyst according to item 1, wherein the support is selected from silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, alumina-coated silica, silica-coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, cationic clay, or anionic clay, and mixtures thereof. 8. The supporting catalyst according to claim 1, further characterized in that the Group 6 metal is molybdenum, and the Group 8, Group 9, or Group 10 metal is selected from the group consisting of cobalt, nickel, and mixtures thereof. 9. The supporting catalyst according to item 8, further comprising phosphorus. 10. Below: (I) Hydroprocessing of petroleum supplies, (II) Hydrocracking (HCR) of petroleum supply raw materials, (III) Hydrogenated dearomatic (HDA) of petroleum supply raw materials, (IV) Hydrodesulfurization (HDS) of petroleum supply raw materials, (V) Hydrogen denitrification (HDN) of petroleum supply raw materials, (VI) Hydrogenated demetallation (HDM) of petroleum supply raw materials, and (VII) Hydrotreating of filled hydrocarbon feedstock or petroleum feedstock, comprising a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof. A supporting catalyst according to item 1, which is useful in at least one process. 11. The support catalyst according to item 10, wherein the catalyst is pre-impregnated, molded, dried, and calcined. 12. The supporting catalyst according to item 10, further relating to a d50 of approximately 120 Å (12 nm) or more and approximately 200 Å (20 nm) or less. 13. A process for processing a hydrocarbon feedstock containing at least one of paraffin, aromatic, and naphthenic components to produce a processed product, wherein the process is as follows: (I) Hydrometallation, hydronitrification, hydrosulfurization, and hydrocracking, the process comprising contacting a feedstock in at least one reactor with hydrogen under hydrocracking conditions using a support catalyst as described in item 1, and recovering the product, (II) Hydrotreating a hydrocarbon feedstock containing a component that boils above 1000°F (537.8°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof, wherein the feedstock is heated isothermally or substantially isothermally. The process involves contacting the catalyst with hydrogen and the supporting catalyst described in item 1 under hydrotreating conditions. Hydrogenation treatment, including the recovery of the product, (III) Hydrogenating a hydrocarbon feedstock having a boiling point higher than 600°F (315.6°C) to form a product in which the proportion of components with a boiling point lower than approximately 600°F (315.6°C) is increased, wherein the feedstock is brought into contact with hydrogen and the supporting catalyst described in item 1 under isothermal or substantially isothermal hydrotreating conditions, and the product is recovered. Including the act of forming, (IV) A process selected from the group comprising hydrogenation of a feed, comprising contacting a feed containing hydrocarbon oil with hydrogen and a supporting catalyst as described in item 1 under conditions of a high temperature exceeding about 600°F (315.6°C) and a pressure exceeding about 500 p.sig (3.44 MPa), and recovering the product. 14. The process according to item 13, wherein the recovered product after treatment exhibits at least one of the following compared to the untreated hydrocarbon feedstock: a decrease in aromatic content, an increase in paraffin content, a decrease in viscosity, and an increase in viscosity index. 15. A method for preparing a catalyst, wherein the catalyst is as follows: (I) Hydroprocessing of petroleum supply raw materials, (II) Hydrocracking (HCR) of petroleum supply raw materials, (III) Hydrogenated dearomatic (HDA) of petroleum supply raw materials, (IV) Hydrodesulfurization (HDS) of petroleum supply raw materials, (V) Hydrogen denitrification (HDN) of petroleum supply raw materials, (VI) Hydrogen demetallation (HDM) of petroleum supply raw materials, and (VI) A filling hydrocarbon containing a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof. At least one procedure selected from the group consisting of hydrogenation of the feedstock It is intended for use in the process. The method involves impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the periodic table, at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9, or Group 10 (or Group VIII) of the periodic table, and optionally a phosphorus-containing compound and at least one organic chelate compound, wherein the impregnation is such that the Group VIB, Group VIIIB and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere, and then drying and calcining the resulting impregnated support, wherein the support is (A) Mixing alumina-containing powder with water and optionally nitric acid to form a wet mixture, (B) A suitable support for the wet mixture for use in a hydroprocessing reactor. The preparation is made by shaping to form body particles, and includes drying and firing, The carrier has a total pore volume (TPV) of approximately 0.6 cc / g to approximately 1.1 cc / g, and the following pore size distribution and pore content correspond to values ​​measured by mercury porosimetry: The support has the following pore size distribution and pore content, corresponding to a total pore volume (TPV) of approximately 0.8 cc / g to approximately 1.5 cc / g and values ​​measured using mercury porosimetry: (i) 25% to 45% TPV in pores with a diameter of 100 Å (10 nm) to 200 Å (20 nm), (ii) TPV of more than 15% to less than 30% in pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (iii) A method comprising a porous inorganic oxide having a pore volume of 10% or more and less than 30% in pores having a diameter of 1000 Å (100 nm) or more and 30,000 Å (3,000 nm). 16. The method according to item 15, wherein after step (B) for preparing the carrier, (C) the carrier particles are dried and calcined to form calcined pills. 17. The method according to item 15, wherein the aqueous solution contains an organic chelate compound selected from acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and mixtures thereof. 18. The method according to item 17, wherein the organic chelate compound comprises citric acid.

[0132] 19. The method according to item 15, wherein the alumina-containing powder in step (A) is silica-alumina. 20. A porous inorganic oxide support or substrate having a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, (a) In pores with a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), TPV of approximately 25% or more to approximately 45%. (b) In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), TPV of more than 15% to less than 30%. (c) A porous inorganic oxide support or substrate containing 10% to less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm). . 21. A porous inorganic oxide carrier or support according to item 20, wherein the support is selected from silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, alumina-coated silica, silica-coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, cationic clay, or anionic clay, and mixtures thereof. 22. A porous inorganic oxide support or support according to item 20, wherein the support exhibits a d50 of 110 Å (11 nm) or more and approximately 170 Å (17 nm) or less. 23.About 185m 2 / g ~ approx. 425m 2 A porous inorganic oxide carrier or support according to item 20, having a total surface area determined by nitrogen adsorption using the BET technique, at a density of / g. 24. A porous inorganic oxide carrier or support according to item 20, having approximately 55% to approximately 75% of pores having a diameter of less than 200 Å (20 nm) as measured by mercury osmosis. 25. A porous inorganic oxide carrier or support according to item 20, comprising Al2O3 and SiO2, having approximately 85% to approximately 98% by weight of Al2O3 and approximately 15% to approximately 2% by weight of SiO2.

[0133] All documents described herein, including any patent applications and / or test procedures, are incorporated herein by reference. The principles, preferred embodiments, and operating modes of the present invention are described in the preceding specification.

[0134] Furthermore, any number of ranges described in the specification or claims, such as those representing characteristics, units of measurement, conditions, physical states, or specific sets of percentages, is intended to be explicitly and literally incorporated herein by reference or otherwise, including any subset of any number within such ranges. For example, the lower limit RL and upper limit R U Whenever a numerical range containing is disclosed, any number R that falls within that range is specifically disclosed. In particular, the following numbers R within the range are specifically disclosed: R=R L +k(R U -R L ), In the formula, k is a variable ranging from 1% to 100% in 1% increments, for example, k can be 1%, 2%, 3%, 4%, 5%, .... 50%, 51%, 52%, .... 95%, 96%, 97%, 98%, 99%, or 100%. Furthermore, any numerical range represented by any two values ​​of R calculated above is also specifically disclosed.

[0135] While the present invention has been described herein with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the invention. Therefore, it should be understood that numerous modifications can be made to the exemplary embodiments and other configurations can be devised without departing from the spirit and scope of the invention as defined by the appended claims. This disclosure is not limited to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the invention. In addition to those enumerated herein, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure is limited only by the conditions of the appended claims, along with the entire scope of equivalents to which such claims are entitled. It should be understood that this disclosure is not limited to specific methods, reagents, compounds, compositions, or biological systems, and these may naturally vary. It should also be understood that the terminology used herein is for describing specific embodiments only and is not intended to limit them.

[0136] The embodiments described herein as exemplary may be preferably practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” should be interpreted broadly and without limitation. It should be taken. In addition, the terms and expressions used herein are not limiting but are used as descriptive terms, and in the use of such terms and expressions, it is not intended to exclude any equivalent of any of the features or parts thereof shown or described, but it is recognized that various modifications are possible within the scope of the claimed art. In addition, the phrase "consisting essentially of" is specifically enumerated. It will be understood that these elements, as well as these additional elements, do not materially affect the basic and novel features of the claimed technology. The phrase "excludes all elements that are not specified."

[0137] [Table 10]

[0138] Other embodiments are described in the following claims. The present invention includes the following embodiments. [1] A supporting catalyst comprising at least one metal from Group 6 (or Group VIB) of the periodic table and at least one metal from Group 8, Group 9, or Group 10 (or Group VIIIB) of the periodic table, optionally comprising phosphorus, Calculated as oxides and based on the total weight of the catalyst composition, the Group 6 metal constitutes approximately 30 to approximately 45% by weight, and the sum of the metal components of Group 6, Group 8, Group 9, or Group 10, or mixtures thereof, constitutes approximately 35 to approximately 55% by weight. The aforementioned metal, and phosphorus if present, is supported on and / or within a porous inorganic oxide carrier or support, and the support before the incorporation of the aforementioned metal and phosphorus, if present, has a total pore volume (TPV) of approximately 0.8 cc / g to approximately 1.5 cc / g, (a) In pores with a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), TPV of approximately 25% or more to approximately 45%. (b) In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), TPV of more than 15% to less than 30%. (c) In pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), containing 10% or more to less than 30% TPV. The aforementioned supporting catalyst (d) In pores with a diameter of 100 Å (10 nm) to 200 Å (20 nm), TPV of approximately 35% or more to approximately 60%. (e) In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), TPV of more than 15% to less than 30%. (f) In pores with a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), containing 10% or more to less than 30% TPV, A supported catalyst whose pore properties and content are measured using mercury porosimetry. [2] The support has a diameter of 110 Å (11 nm) or more and approximately 170 Å (17 nm) or less. 50 The supporting catalyst according to claim 1, wherein the supporting catalyst exhibits a d50 of approximately 125 Å (12.5 nm) or more and approximately 210 Å (21 nm) or less. [3] The supporting catalyst according to claim 1 or 2, wherein more than 17% to less than 28% of the TPV of the supporting catalyst is located in pores having a diameter of 200 Å to less than 1000 Å. [4] The supporting catalyst according to any one of claims 1 to 3, wherein approximately 12% or more to less than approximately 28% of the TPV of the supporting catalyst is located in pores having a diameter of 1,000 Å (100 nm) to 30,000 Å (3,000 nm). [5] The supporting catalyst according to claim 4, wherein approximately 15% or more to less than approximately 25% of the TPV is contained within pores having a diameter of 1,000 Å (100 nm) to 30,000 Å (3,000 nm). [6] The supporting catalyst according to any one of claims 1 to 5, wherein approximately 40% to approximately 55% of the TPV is located in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm). [7] The support catalyst according to any one of claims 1 to 6, wherein the support is silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, alumina-coated silica, silica-coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, cationic clay, anionic clay, or any two or more mixtures thereof. [8] The supporting catalyst according to any one of claims 1 to 7, wherein the metal of Group 6 is Mo, and the metal of Group 8, Group 9, or Group 10 is selected from the group consisting of Co, Ni, and mixtures thereof. [9] The supporting catalyst according to 8, further comprising phosphorus.

[10] below: Hydroprocessing of petroleum supply raw materials, Hydrocracking (HCR) of petroleum supply raw materials, Hydrogenated aromatic (HDA) of petroleum supply raw materials, Hydrodesulfurization (HDS) of petroleum supply raw materials, Hydrogenated denitrification (HDN) of petroleum supply raw materials, Hydrometallation (HDM) of petroleum supply raw materials, or A support catalyst according to claim 1, useful in at least one process which is the hydrotreating of a filled hydrocarbon feed or petroleum feedstock, comprising a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof.

[11] The support catalyst according to 10, wherein the catalyst is pre-impregnated, molded, dried, and calcined.

[12] The catalyst has a d of approximately 125 Å (12.5 nm) or more and approximately 210 Å (21 nm) or less. 50 A supporting catalyst as described in 10 or 11, which shows the following.

[13] A process for processing a hydrocarbon feedstock containing at least one of paraffin, aromatic, and naphthenic components to produce a processed product, wherein the process is as follows: (I) Hydrometallation, hydrodenitrification, hydrodesulfurization, hydrodesaromatherapy, and hydrocracking, wherein the process comprises contacting a feedstock in at least one reactor with hydrogen under hydroprocessing or hydrocracking conditions using the support catalyst described in 1, and recovering the product, (II) Hydrotreating a hydrocarbon feed comprising a component that boils above 1000°F and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof, comprising contacting the feed with hydrogen and the supporting catalyst described in 1 under isothermal or substantially isothermal hydrotreating conditions, and recovering the treatment product. (III) Hydrogenating the hydrocarbon feed having components with a boiling point higher than 600°F (315.6°C) to form a product in which the proportion of components with a boiling point lower than approximately 600°F (315.6°C) is increased, comprising contacting the feed with hydrogen and the supporting catalyst described in 1 under isothermal or substantially isothermal hydrotreating conditions, and recovering the product. (IV) A process selected from the group comprising: hydrogenating the feed, wherein the feed containing hydrocarbon oil is brought into contact with hydrogen and the supporting catalyst described in (1) under conditions of a high temperature exceeding about 600°F (315.6°C) and a pressure exceeding about 500 p.sig (3.44 MPa), and the product is recovered.

[14] The process according to 13, wherein the recovered product after processing exhibits at least one of the following compared to the unprocessed hydrocarbon feedstock: a decrease in aromatic component content, an increase in paraffin component content, a decrease in viscosity, and an increase in viscosity index.

[15] A method for preparing a catalyst, wherein the catalyst is as follows: (I) Hydroprocessing of petroleum supplies, (II) Hydrocracking (HCR) of petroleum supply raw materials, (III) Hydrogen desulfurization of hydrocarbons, (IV) Hydrogenation and denitrification of hydrocarbons, (V) Hydrogenated dearomatic (HDA) of petroleum supply raw materials, (VI) Hydrogen demetallation of hydrocarbons, (VII) For use in at least one process selected from the group consisting of hydrotreating a filled hydrocarbon feedstock, comprising a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof. The method involves impregnating a porous inorganic oxide support with an aqueous solution comprising: at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the periodic table; at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9, or Group 10 (or Group VIII) of the periodic table; and optionally, a phosphorus-containing compound and at least one organic chelate compound, wherein the impregnation is such that the Group VIB, Group VIIIB and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere; and then drying and calcining the resulting impregnated support, wherein the support is Mixing alumina-containing powder with water and optionally nitric acid to form a wet mixture, and The aforementioned moist mixture is prepared by shaping it to form support particles suitable for use in a hydroprocessing reactor, and includes drying and calcining. The support has a total pore volume (TPV) of approximately 0.8 cc / g to approximately 1.5 cc / g, and the following pore size distribution and pore content correspond to values ​​measured using mercury porosimetry before the incorporation of metal and, if present, phosphorus: TPV of 25% to 45% in pores with a diameter of 100 Å (10 nm) to 200 Å (20 nm), TPV of more than 15% to less than 30% in pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and A method comprising a porous inorganic oxide having a pore volume of 10% or more and less than 30% in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[16] The method according to 15, further comprising drying and firing the support particles after molding to form a fired pill.

[17] The method according to 15 or 16, wherein the aqueous solution contains an organic chelate compound which is acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, or any two or more mixtures thereof.

[18] The method according to any one of claims 15 to 17, wherein the organic chelate compound comprises citric acid.

[19] The method according to any one of claims 15 to 18, wherein the alumina-containing powder is silica-alumina.

[20] A porous inorganic oxide support or substrate having a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, In pores with a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), the TPV is approximately 25% or more to approximately 45%. In pores with a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), the TPV is approximately 15% to less than 30%. A porous inorganic oxide support or substrate containing 10% to less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[21] The porous inorganic oxide carrier or support according to 20, wherein the support is silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, alumina-coated silica, silica-coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, diatomaceous earth, pumice, natural clay, synthetic clay, cationic clay, anionic clay, or any two or more mixtures thereof.

[22] The porous inorganic oxide support or support according to 20 or 21, wherein the support exhibits a d50 of 110 Å (11 nm) or more and approximately 170 Å (17 nm) or less.

[23] Approximately 185m 2 / g ~ approx. 425m2 A porous inorganic oxide carrier or support according to any one of items 20 to 22, having a total surface area determined by nitrogen adsorption using the BET technique at a density of / g.

[24] A porous inorganic oxide support or support according to any one of items 20 to 23, having approximately 55% to approximately 75% of pores having a diameter of less than 200 Å (20 nm) as measured using mercury osmosis.

[25] Approximately 85% to 98% by weight of Al 2 O 3 and approximately 15% to 2% by weight of SiO 2 Al 2 O 3 and SiO 2 A porous inorganic oxide carrier or support according to any one of items 20 to 24, including the following:

Claims

1. A method for preparing a catalyst, wherein the catalyst is as follows: (I) Hydrogenation treatment of petroleum supply raw materials, (II) Hydrocracking (HCR) of petroleum supply raw materials, (III) Hydrogen desulfurization of hydrocarbons, (IV) Hydrogen denitrification of hydrocarbons, (V) Hydrogenated dearomatic (HDA) of petroleum supply raw materials, (VI) Hydrogenation and demetallation of hydrocarbons, (VII) For use in at least one process selected from the group consisting of hydrogenation treatment of hydrocarbon feedstocks, comprising a component that boils above 600°F (315.6°C) and at least one component selected from the group consisting of sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof, The method involves impregnating a porous inorganic oxide support with an aqueous solution comprising: at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the periodic table; at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9, or Group 10 (or Group VIIIIB) of the periodic table; and optionally, a phosphorus-containing compound and at least one organic chelate compound, wherein the Group VIB, Group VIIIIB, and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere; and subsequently drying and calcining the resulting impregnated support, wherein the support is Mixing alumina-containing powder with water and optionally nitric acid to form a wet mixture, and The aforementioned moist mixture is prepared by shaping it to form support particles suitable for use in a hydrogenation reactor, and includes drying and calcining. The alumina-containing powder is silica-alumina. The support, before the incorporation of metal and, if present, phosphorus, has a total pore volume (TPV) of 0.8 cc / g to 1.5 cc / g, and the following pore size distribution and pore content: TPV of 25% to 45% in pores with a diameter of 100 Å (10 nm) or more to 200 Å (20 nm), TPV of more than 15% to less than 30% in pores with a diameter of 200 Å (20 nm) or more to less than 1000 Å (100 nm), and It contains a porous inorganic oxide having a pore volume of 10% to less than 30% in pores with a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less, In the catalyst, calculated as an oxide and based on the total weight of the catalyst composition, the Group 6 metal constitutes 30 to 45% by weight, and the sum of the metal components of Group 6, Group 8, Group 9, or Group 10, or mixtures thereof, constitutes 35 to 55% by weight. The catalyst, In pores with a diameter of 100 angstroms (Å) (10 nm) or more to 200 Å (20 nm) or less, the TPV is 35% or more to 60% or less. In pores with a diameter of 200 Å (20 nm) or more and less than 1000 Å (100 nm), the TPV is greater than 15% and less than 30%. In pores having a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less, the TPV is 10% or more to less than 30%. A method in which pore properties and content are measured using mercury porosimetry.

2. The method according to claim 1, further comprising drying and firing the support particles after molding to form a fired pill.

3. The method according to claim 1 or 2, wherein the aqueous solution contains an organic chelate compound which is acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, or any two or more mixtures thereof.

4. The method according to any one of claims 1 to 3, wherein the organic chelate compound comprises citric acid.

5. The method according to any one of claims 1 to 4, wherein the support has a d 50 of 110 Å (11 nm) or more and 170 Å (17 nm) or less, or the catalyst has a d 50 of 125 Å (12.5 nm) or more and 210 Å (21 nm) or less, where d 50 is the median pore diameter measured by mercury porosimetry.

6. The method according to any one of claims 1 to 5, wherein more than 17% to less than 28% of the TPV of the catalyst is contained in pores having a diameter of 200 Å or more to less than 1000 Å.

7. The method according to any one of claims 1 to 6, wherein 12% or more to less than 28% of the TPV of the catalyst is contained in pores having a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less.

8. The method according to any one of claims 1 to 7, wherein 15% or more to less than 25% of the TPV of the catalyst is contained in pores having a diameter of 1,000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less.

9. The method according to any one of claims 1 to 8, wherein 40% to 55% of the TPV of the catalyst is contained within pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm).

10. The method according to any one of claims 1 to 9, wherein the metal of group 6 is Mo, and the metal of group 8, group 9, or group 10 is selected from the group consisting of Co, Ni, and mixtures thereof.

11. The method according to any one of claims 1 to 9, wherein the metal of group 6 is Mo, and the metal of group 8, group 9, or group 10 is Ni.

12. The method according to claim 10 or 11, wherein the catalyst further comprises phosphorus.

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