High activity hydrotreating catalysts and processes 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 TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 135,167, filed January 8, 2021, the contents of which are incorporated by reference in their entirety herein. [Background technology]

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

[0003] Porous inorganic supports in particulate form 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 of 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 affect the complex nature of catalytic activity and catalyst life.

[0004] Supported catalysts for use in hydrotreating hydrocarbon feedstocks For catalytic applications, the morphological properties of the support, such as surface area, pore volume, pore size, and pore size distribution of the pores that make up the total pore volume, are important. Such properties can affect the nature and concentration of active catalytic sites, the diffusion of reactants to the active catalytic sites, the diffusion of products from the active sites, 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 the most widely used aluminum catalysts in commercial use. Such hydroprocessing applications span a wide range of feed types and operating conditions, but have one or more common objectives, namely, the removal of heteroatom impurities, such as 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 increasing the hydrogen to carbon (H / C) ratio in the product, and reducing aromatics, density and / or carbon residues, as well as reducing the boiling range and average molecular weight by cracking carbon bonds, desirably reducing product viscosity.

[0006] As refiners increase the proportion of heavier, lower quality crude oils in the feedstocks being processed, there is an increasing need for processes and catalysts to process fractions containing high levels of metals, asphaltenes, aromatics, nitrogen, and sulfur. When catalysts, such as resid desulfurization catalysts or vacuum gas oil (VGO) hydrocracking pretreatment catalysts, are exposed to hydrocarbon fractions containing undesirable metals and aromatics, they can be rapidly deactivated and therefore susceptible to premature replacement.

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

[0008] In general, it is desirable to design hydroprocessing catalysts that exhibit high surface areas to maximize the concentration and activity of catalytic sites. are inversely proportional within practical limits. As a result, catalyst supports, such as those comprising alumina or silica-alumina particles and containing primarily small pores, exhibit the highest surface areas. In contrast, sufficiently large pores are required for the diffusion of feed components, especially as the catalyst ages and becomes fouled, but larger pores have lower surface areas. More specifically, catalyst formulators or designers and process engineers are faced with competing considerations that often dictate the balance of morphological properties of the support and the supported catalyst derived therefrom.

[0009] Pores having diameters in the range of less than about 200 angstroms (Å) (20 nm) have the effect of increasing the number of active sites of an alumina or silica-alumina hydrogenation catalyst, but such sites may be susceptible to blockage by coke, thereby causing a decrease in catalytic activity. Conversely, if a supported catalyst has more than about 10% of its total pore volume occupied by pores having a pore diameter greater than 1000 Å (100 nm), the mechanical crush strength and activity of the supported catalyst may be adversely affected. Furthermore, for some alumina or silica-alumina catalysts, maximizing the concentration of pores having a pore diameter between 200 Å (20 nm) and less than 1000 Å (100 nm) may provide a balance between activity and catalyst life, within what is referred to for purposes of this invention as the mesopore region.

[0010] Thus, while increasing the surface area of ​​a catalyst can increase the number of active sites, such an increase in surface area results in an increase in the proportion of smaller pores that may be susceptible to clogging by coke and other components present in the hydrocarbon feed. In other words, increasing the surface area and maximizing the concentration of supported catalysts exhibiting pore sizes in the mesopore range are conflicting properties. Furthermore, not only is a large surface area desirable, but it should also remain stable when exposed to petroleum feedstock conversion conditions such as high temperature and humidity. Thus, the development of supported catalysts that contain catalytically active metals, particularly for producing hydroprocessing catalysts, is becoming more and more popular. There is a continuing search for stable support particles that exhibit a combination of pore size distribution and total surface area that, when used to support a catalyst, can provide a combination of performance properties suitable for use as a catalyst support.

[0011] Furthermore, the physical and chemical properties of porous supports may depend on the procedure followed during their preparation, and many processes have been developed in an attempt to optimize support properties for their use as catalyst supports. Examples of suitable porous support materials and preparation methods are described below. In general, 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, although catalyst supports comprising alumina supports are known, further improvements are needed to provide supports with even more improved properties. Summary of the Invention

[0012] A supported catalyst comprising at least one metal from Group 6 (alternatively referred to as Group VIB) of the Periodic Table of the Elements and at least one metal from Group 8, 9 or 10 (alternatively referred to as Group VIIIB) of the Periodic Table of the Elements, optionally including phosphorus, wherein the Group 6 metal comprises from about 30 to about 45 weight percent and the sum of the Group 6 and Group 8, 9 or 10 metal components or mixtures thereof comprises from about 35 to about 55 weight percent, calculated as the oxides and based on the total weight of the catalyst composition, and wherein the metals, and phosphorus, if present, are supported on and / or within a porous inorganic oxide support or substrate, and the metals ... In some cases, the support prior to incorporation of phosphorus has a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, and (a) a pore size of 100 Angstroms (Å) or less. (b) a TPV of about 25% or more and about 45% in pores having a diameter of up to 200 angstroms (Å) (20 nm); (b) a TPV of about 15% or more and less than about 30% in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); (c) a TPV 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); (d) a TPV of 100 Å (10 nm) to 200 Å (2 (e) from about 35% to about 60% TPV in pores having a diameter of from 200 Å (20 nm) to less than 1000 Å (100 nm); and (f) from 10% to less than 30% TPV in pores having a diameter of from 1000 Å (100 nm) to 30,000 Å (3,000 nm), wherein the pore properties 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% or more to about 45% TPV in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm); (b) about 15% or more to less than about 30% TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); and (c) 10% or more to less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[0014] Further embodiments include processes for treating a hydrocarbon feedstock containing at least one of paraffinic, aromatic, and naphthenic components to produce a process product, the processes including: (I) hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, the process comprising contacting the feedstock in at least one reactor with hydrogen under hydroprocessing or hydrocracking conditions using the supported catalyst described above. and recovering the products; and (II) hydrotreating a hydrocarbon feed containing components boiling 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, comprising subjecting the feed to hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, the process comprising: Hydrogen and the above-described supported catalyst are added under isothermal or substantially isothermal hydrotreating conditions. and recovering a treated product; and (III) hydroconverting a hydrocarbon feed having components boiling above 600° F. (315.6° C.) to form a product having an increased proportion of components boiling below about 600° F. (315.6° C.), wherein the feed is subjected to isothermal or substantially isothermal hydrotreating conditions. and (IV) hydroconverting a feed comprising contacting a feed comprising a hydrocarbon oil with hydrogen and the supported catalyst under conditions of elevated temperature greater than about 600° F. (315.6° C.) and pressure greater than about 500 psig (3.44 MPa) and recovering a product.

[0015] Yet further embodiments include a method for preparing a catalyst for use in at least one petroleum hydrocarbon treatment process, comprising impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Group 6 of the Periodic Table of the Elements (alternatively referred to as Group VIB), at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Groups 8, 9 or 10 of the Periodic Table of the Elements (alternatively referred to as Group VIII), and optionally a phosphorus-containing compound and at least one organic chelate compound, wherein the Groups VIB and VIIIB and the phosphorus compounds are pyrolyzable or thermally decomposable to their corresponding oxides in the presence of an oxygen-containing atmosphere. (A) mixing an 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. drying and calcining, wherein the support 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 distributions and pore contents corresponding to values ​​measured using mercury porosimetry: (i) 25% to 45% TPV in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm), (ii) 15% to less than 30% TPV in pores having 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 having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm). [Brief description of the drawings]

[0016] [Figure 1A] 1 shows typical pore size distributions, as measured using nitrogen desorption techniques, for comparative catalyst support or support particles and catalyst support or support particles prepared in accordance with the present invention. [Figure 1B] 1 shows typical pore size distributions, as measured using mercury porosimetry, for comparative catalyst support or support particles and catalyst support or support particles prepared in accordance with the present invention. [Figure 1C] 1 shows typical pore size distributions, on a logarithmic scale, measured using mercury porosimetry for comparative catalyst support or support particles and catalyst support or support particles prepared according to the invention. [Figure 2A] 1 shows typical pore size distributions, measured using nitrogen desorption techniques, of supported catalysts prepared in accordance with the present invention, with and without fines loading. [Figure 2B] 1 shows typical pore size distributions, measured using mercury porosimetry, of supported catalysts prepared according to the present invention, with and without fines loading. [Figure 2C] 1 shows typical pore size distributions, on a logarithmic scale, measured using mercury porosimetry for supported catalysts prepared according to the present invention, with and without fines loading. [Diagram 3] FIG. 2 is a simplified flow diagram of a bench scale unit (BSU) used to test the petroleum hydrotreating performance of the supported catalysts prepared in the examples. [Figure 4A] 1 is a plot of hydrodenitrogenation reaction rate (kHDN) as a function of catalyst or bench-scale unit operating temperature for comparative and exemplary catalysts. [Figure 4B] 1 is a plot of hydrodesulfurization reaction rate (kHDS) as a function of catalyst or bench-scale unit operating temperature for comparative and exemplary catalysts. [Figure 4C] 1 is a plot of hydrodesulfurization apparent conversion as a function of catalyst temperature in a bench-scale unit for comparative and exemplary catalysts. [Figure 5A]1 is a plot of volume percent aromatics in the stripper bottom (STB) of a bench-scale unit for performance evaluation of comparative catalysts and exemplary catalyst A as a function of apparent conversion. [Figure 5B] 1 is a plot of volume percent naphthenes in the stripper bottoms (STB) of a bench-scale unit for performance evaluation of comparative catalysts and exemplary catalyst A as a function of apparent conversion. [Figure 5C] 1 is a plot of volume percent paraffins in the stripper bottoms (STB) of a bench-scale unit for performance evaluation of comparative catalysts and exemplary catalyst A as a function of apparent conversion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] definition As used herein, the following terms or phrases have the meanings indicated.

[0018] Use of the term "alumina" is a convenient shorthand intended to encompass any and all of the inorganic oxides further disclosed below as useful herein, both individually and in combination. Included are powder forms of the inorganic oxides, as well as their subsequent processing to form supports for use in preparing supported catalysts.

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

[0020] The term "about," when used as a modifier of or in conjunction with a variable, feature, or condition, is intended to convey that the numbers, ranges, features, and conditions disclosed herein are flexible, and that the practice of the invention by one of ordinary skill in the art using properties such as temperatures, rates, times, concentrations, amounts, contents, pore sizes, pore volumes, sizes including surface areas, etc. that are outside the recited ranges or differ from the single recited value will achieve the desired result or results described in this application, i.e., the preparation of porous catalyst support particles having defined characteristics, and their use in the preparation of active catalysts, and processes using such catalysts.

[0021] "Apparent conversion" = 100 to, for example, the ASTM D2887 "Gas Chromatograph" conversion after hydroprocessing, including HDA, HCR, HDN and / or HDS. Subtract the percentage of hydrocarbons boiling above 700°F (371.1°C) based on a SimDist (simulated distillation) test in accordance with the Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography.

[0022] For example, "component" as applied to a metal of the catalyst impregnation solution or to the catalyst itself refers to any compound or complex, including a salt, oxide, sulfide, or any intermediate form between the oxide and sulfide of the metal in question.

[0023] "Comprise" or "comprising": Throughout this specification, including the claims, the terms "comprising" and "comprises," as well as "including" and "comprising" are used interchangeably. "have," "having," "includes," "include "Comprise," "including," and variations thereof The words "and variations of these words mean that the specified step, element, component, or material to which it refers is essential, but that other steps, elements, components, or materials may be added and still form a composition within the scope of the claim or disclosure. When set forth in the description and claims of the invention, it means that the invention and what is claimed is considered to be the following, and potentially more. These terms, particularly when applied to the claims, are inclusive or open-ended and do not exclude additional, unrecited elements, components, or method steps.

[0024] The "feedstocks" or petroleum feedstocks typically processed using processes involving the catalysts of the present invention are often described in terms of being "heavy" or "light". The terms "light" and "heavy" with respect to petroleum fractions are used herein in their ordinary sense within the refining industry to refer to relatively low and high boiling ranges, respectively. Heavy fuel oil (HFO) includes both the end products (residual fuels) and the primary refinery streams into which they are blended. Members of the heavy fuel oil category are available in a wide range of molecular weights, carbon numbers (typically around C 7 ~About C 50 ) and boiling point (approx. 250°F to approx. 1112°F) F (about 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. Final heavy fuels (residual fuels) are products that primarily comprise the residue of the refining process after substantially all of the high-quality hydrocarbons have been distilled, cracked, or catalytically removed from the crude oil feedstock. Substantially all (at least 90% by volume) of the hydrocarbon feed stream or feedstock typically falls within the boiling range of about 300°F to 1050°F (about 148.9°C to 565.6°C), preferably about 600°F to 1000°F (about 315.6°C to 537.8°C). The feedstock may include a mixture of petroleum fractions, such as atmospheric and vacuum gas oils (AGO and VGO). Suitable feedstocks include heavy hydrocarbon mineral or synthetic oils, or a mixture of one or more fractions thereof. Thus, known feedstocks such as straight run gas oil, vacuum gas oil, demetallized oil, deasphalted vacuum residual, coker distillate, catalytic cracking distillate, shale oil, tar sands oil, coal liquids, and the like are contemplated. Preferred feedstocks have a boiling range beginning at a temperature greater than about 260° C. (greater than about 500° F.). Hydrocracked feedstocks may contain nitrogen, typically present in amounts of 1 ppm to 1.0 wt. % as organic nitrogen compounds. The feedstocks also typically contain sufficient sulfur-containing compounds to provide a sulfur content greater than 0.15 wt. %. The boiling ranges of the various product fractions recovered in 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) has recommended to the Environmental Protection Agency (EPA) a list of common names for refinery streams that are consistent with industry operations and that encompass all known processes used by refiners. A list including the common names, Chemical Abstracts Service (CAS) numbers, and definitions of each stream is available at The definitions for these streams are published by the U.S. EPA in "Dedum I, Generic Terms Covering Petroleum Refinery Process Streams." "High Production The results of this test can also be found in the EPA's "Heavy Fuel Oils Category, Test Plan for Heavy Fuel Oils, Volume (HPV) Chemical Challenge Program." Petroleum streams suitable 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 Groups of the Periodic Table of the Elements preferably refers to a Group or Groups as reflected in the Periodic Table of the Elements using the IUPAC system for numbering Groups of the elements as Groups 1 to 18. However, to the extent that a group is identified by Roman numerals according to the Periodic Table of the Elements as published in, for example, "Hawley's Condensed Chemical Dictionary" (2001) (the "CAS" system), one or more elements of the group are further identified to avoid confusion and to provide cross-references to the numerical IUPAC identifiers.

[0026] "Median pore diameter" (MPD) can be calculated, for example, based on volume, surface area, or based on pore size distribution data. Median pore diameter calculated by volume means the pore diameter where half of the total pore volume is present, and median pore diameter calculated by surface area means the pore diameter where half of the total pore surface area is present. In addition, median pore diameter calculated based on pore size distribution means the pore diameter where half of the pores have a larger diameter according to the pore size distribution determined, for example, using mercury intrusion porosimetry, as described elsewhere herein.

[0027] "Micropores" is understood to refer to pores typically present in a supported catalyst or catalyst support and having a diameter of less than 20 Å (2 nm).

[0028] "Mesopores" are understood to refer to pores present in a supported catalyst or catalyst support that typically have diameters of less than 20 A (2 nm) to 1000 A (100 nm). However, within this broader range, there are also "subranges" of mesopores that are important to the inventions disclosed herein, including the ranges of 100 A (10 nm) to 200 A (20 nm) and 200 A (20 nm) to 1000 A (100 nm).

[0029] "Macropores" is understood to refer to pores present in a supported catalyst or catalyst support that typically have a diameter of 1000 Å (100 nm) or more, for example, from 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[0030] Each of the above definitions of micropores, mesopores, mesopore subranges and macropores are unique and distinct such that no pore is counted twice when summing up the percentages or values ​​in the distribution of pore sizes for any given sample.

[0031] "d50" means for the purposes of the present invention the median pore diameter measured by mercury porosimetry. d50 therefore corresponds to the median pore diameter calculated based on the pore size distribution, above which half of the pores have a larger diameter.

[0032] As used herein, "total pore volume" penetration is determined by either nitrogen desorption or mercury penetration, also known as mercury porosimetry. By "surface area" is meant the cumulative volume in cc / g of all possible pores. For catalyst support or carrier particles, such as alumina powders and alumina or silica-alumina powders or carrier particles, the pore size distribution and pore volume can be calculated by reference to the nitrogen desorption isotherm (assuming cylindrical pores) by 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), see also ASTM D3037, which identifies the procedure for determining surface area using the nitrogen BET method. It is generally accepted that the nitrogen desorption method is particularly useful for smaller sized pores, while the mercury porosimetry is well suited for larger sized pores. Unless otherwise stated, the mercury porosimetry method is used for convenience to measure and express values ​​and ranges over the entire range of pore sizes present in the powders, carriers, catalyst supports or carriers, and supported catalysts disclosed herein.

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

[0034] The pore size distribution using mercury porosimetry can be calculated according to the following formula:

[0035]

number

[0036] Total N of sample 2The pore volume is the sum of the nitrogen pore volumes determined by the nitrogen desorption method described above. Similarly, the total mercury pore volume of a sample is the sum of the mercury pore volumes determined by the mercury penetration method described above, using, for example, a contact angle of 130°, a surface tension of 485 dynes / cm, and a Hg density of 13.5335 gm / cc.

[0037] As used herein, "surface area" refers to the specific surface area, whether in powder or aggregate form, as determined by nitrogen adsorption using the BET technique described above.

[0038] Pore ​​volume, PV (cc / g), or surface area, SA (m 2 All weight-related morphological properties, such as mass per unit mass (g), can be normalized to a "metal-free basis" according to procedures known in the art. However, the morphological properties reported herein are on an "as measured" basis, uncorrected for metal content.

[0039] "Periodic Table": All references in this specification to the Periodic Table of the Elements are based on the International Union of Pure and Applied Chemistry (IUPAC) Refers to the published Periodic Table of the Elements, with the 19 February 2010 version posted online at http: / / old.iupac.org / reports / periodic_table / .

[0040] When used herein in connection with numerical ranges, the terms "approximately," "about," "substantially," and similar terms are understood by those of ordinary skill in the art. The terms "approximately," "about," "substantially," and similar terms, when applied to structural features, will vary to some extent depending on the context in which they are used. If there are uses of a term that are not clear to one of ordinary skill in the art, given the context in which it is used, the term will be plus or minus 10% of the disclosed value. For example, to describe its shape, size, orientation, direction, etc., these terms are meant to encompass minor variations in structure that may result, for example, from the manufacturing or assembly process, and are intended to have a broad meaning consistent with common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains. These terms should therefore be interpreted as indicating that insubstantial or insignificant modifications or variations of the subject matter described and claimed are considered to be within the scope of the present disclosure as set forth in the appended claims. Unless otherwise defined with respect to a specific property, characteristic, or variable, the term "substantially" as applied to any criterion, such as a property, characteristic, or variable, means that the described criterion is met to such a degree that one of ordinary skill in the art would understand that the benefit to be achieved, or a desired condition or property value is met. See, for example, below for the use of the term "substantially" in connection with the description of substantially isothermal.

[0041] The phrase "substantially isothermal" when used in reference to various processes for processing hydrocarbon feedstocks is typically understood to mean that the process is operated such that the temperature may typically vary throughout the catalyst bed by less than about 50° F., preferably less than about 40° F., more preferably less than about 30° F., such as less than about 20° F., for example, near 0° F., up to about 20° F. or 30° F. or 40° F., or as much as 50° F. Alternatively, the operation of such a process may be referred to as operating isothermally while still exhibiting temperature variations as described above.

[0042] "A" and "an" and "the" and similar referents in the context of describing elements (particularly in the context of the claims below) should be construed to cover both the singular and the plural, unless otherwise indicated herein or the content clearly contradicts. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or the content clearly contradicts otherwise. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended only to better illustrate the embodiments and does not impose limitations on the scope of the claims, unless otherwise indicated. No language in this specification should be construed as indicating any non-claimed 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 methods for preparing supported catalysts for hydroprocessing, hydrocracking (HCR), hydrodearomatization, and the like. The present invention includes the use of the supported catalyst for deaeration (HDA), hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and hydrodesorption microcarbon 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, the embodiments also relate to a porous catalyst carrier or support and a method for preparing a supported catalyst using such a carrier, the supported catalyst having preferred defined pore characteristics including pore size and pore size distribution, and containing at least one metal and / or metal compound of Group 6 (also referred to as Group VIB) and Groups 8, 9 and 10 (also referred to as Group VIIIB) of the Periodic Table of Elements, and optionally phosphorus.

[0044] Exemplary carriers or supports are generally identified as inorganic oxide porous carriers, and it will be understood that such carriers generally have a number of holes, perforations, and / or porosity. Examples of suitable porous carrier materials include silica, silica gel, silica-alumina, alumina, alumina with silica-alumina dispersed in the alumina, alumina coated silica, silica coated alumina, titania, titania-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate ... oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide, magnesium oxide Examples of suitable porous support materials include silica, silica-alumina, alumina, titania, titania-alumina, zirconia, bentonite, boria, and mixtures thereof, with silica, silica-alumina, alumina, and mixtures thereof being particularly preferred, as well as alumina containing up to about 20% by weight silica, preferably up to about 12% by weight silica, for example up to about 10% by weight 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 support can be prepared by converting an alumina precursor, for example in the pseudoboehmite form, typically using calcination, to a preferred form for use as a support material, including, for example, gamma-alumina.

[0048] Preparation of alumina-containing powders As disclosed above, the following disclosure specifically referring to alumina-containing compositions also applies, with appropriate adjustments known to those skilled in the art, to other inorganic oxides identified herein as useful, specifically silica-alumina, and combinations thereof.

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

[0050] In a preferred embodiment for preparing alumina or silica-alumina, the filter cake produced during synthesis is dried to produce a powder that can be conveniently stored without decomposition for extended periods of time before use in further processing. Drying of the filter cake can be accomplished by several methods, such as tray drying, belt drying, spray drying, or combinations thereof. Drying conditions are typically adjusted to effect partial removal of water, for example, to a level of about 20% to about 35% volatiles by weight, preferably about 22% to about 30% volatiles by weight, for example, about 23, 24, 25, 26, 27, 28, or 29% volatiles by weight.

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

[0052] The mixture resulting from the previous step is referred to as the wet mix. This mix is ​​formed into a carrier, e.g., in the form of a pill or other shape, as described elsewhere herein. This step is conveniently carried out by extruding the wet mix, typically followed by drying and calcining the pills.

[0053] Calcination can be carried out batchwise or continuously by contacting the shaped alumina support product with hot gas, which can be either indirectly heated gas or the product of conventional fuel and air combustion. Regardless of the particular method used, the product is typically preheated for a limited time at a temperature below the target calcination temperature and then calcined at a temperature of from about 1000°F (537.8°C) to about 2000°F (1093.3°C), alternatively from about 1200°F (648.9°C) to about 1900°F (1037.8°C), e.g., from about 1400°F (760°C) to about 1800°F (982.2°C), for a period of from about 30 minutes to about 3 hours, preferably from about 30 minutes to about 2 hours. Alternatively, the pills can be heated and calcined to achieve the desired target level of loss on ignition, as described elsewhere herein.

[0054] Characteristics of silica-alumina supports As mentioned above, the powder is then mixed with water and, optionally, recycled fines (catalyst powder and / or catalyst support powder) and an acid such as nitric acid, extruded to produce support particles, such as in the form of pills, and then dried and preferably calcined. The recycled fines typically comprise the inorganic oxide itself or the ground catalyst or its corresponding support or carrier, typically exhibiting a particle size in the range of 10 to 100 micrometers. In the following description, the products produced at this stage of the process are referred to as "alumina support particles", catalyst support particles or "catalyst support particles", or simply "support" or "support" particles.

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

[0056] Several properties of the alumina support particles produced according to the above synthesis methods are typically measured and generally characterize the particles. The various properties and test methods are defined above and are also referred to in the examples below. Typical values ​​for some of the properties are summarized below.

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

[0058] The support or carrier particles of the present invention have a total pore volume (TPV), prior to incorporation of catalytic metals and other catalytic components, which is sometimes also referred to as total intrusion volume (TIV) or total mercury pore volume, referring to measurements made using mercury intrusion porosimetry, and is typically 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.

[0059] On the other hand, the "as measured" total pore volume of the supported catalyst according to the present invention, including the catalytic metal and other catalytic components, such as chelating agents or chelating agent residues after drying and / or calcination, is typically Typically significantly lower, e.g., about half of the values ​​recited above for the support itself. The TPV values ​​measured for the supported catalysts of the examples herein, due in part to the high catalytic metal content, were about 0.45 cc / g.

[0060] Silica-alumina support or carrier particles produced in accordance with the present invention have m as determined by nitrogen adsorption using the BET technique. 2 / g, i.e., at least about 185, or at least about 195, or at least about 205 m 2 / g, with respect to each of the recited values ​​being about 425 m 2 / g, or about 400m 2 / g, or about 375m 2 / g, or about 350m 2 / g, or about 325m 2 / g, or about 300m 2 / g, or about 275m 2 / g of total nitrogen surface area.

[0061] The content of pore sizes of 1000 Å or more and 30,000 Å or less (3,000 nm) or more as measured using mercury penetration is typically 10% or more and 30% or less of the total pore volume, for example, 12%, or 14%, or 16%, or 18%, or 20%, or 22%, or 24%, or 26% or more 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 arising from the recited lower and upper values, the amounts "greater than" and "less than" include values ​​expressed in tenths of a percent as well as 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 penetration, 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% or more 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 arising from the recited lower and upper values, the amounts "greater than" and "less than" include the values ​​expressed in tenths of a percent.

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

[0064] Support particles suitable for use in the present invention may also contain pores within a pore size range exhibiting a pore size of about 100 Å (10 nm) to about 200 Å (20 nm), also measured and reported using the mercury penetration method described above. The content of pores within the range of about 100 Å (10 nm) to about 200 Å (20 nm) is typically about 25% to about 45% or more, or greater than 26%, or 27%, or 28%, or 29%, or 30%, or 31%, or 32%, or 33%, or 34%, or 35%, or 36%, or 37%, or 38%, or 39%, or 40%, and is about 44%, or 43%, or 42%, or 41%, or 40%, or 39%, or 38% or less. Moreover, for each of the ranges arising from the recited lower and upper limits, the amounts "greater than" and "less than" (or their values) include values ​​expressed in tenths of a percent as well as unit percentage values.

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

[0066] The carrier or support particles are typically further characterized by a d50 (also measured using mercury infiltration) of 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), e.g., greater than about 125 Å (12.5 nm) and less than about 135 Å (13.5 nm), whereas the supported catalysts of the present invention are typically further characterized by a d50 (also measured using mercury infiltration) of 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), e.g., greater than about 135 Å (13.5 nm) and less than about 200 Å (20.5 nm). 1A-1C, it will be observed that when measured using nitrogen, an initial peak appears at about 80 Å (8 nm), and when measured using mercury penetration, an initial peak appears at about 90 Å-100 Å (9-10 nm).

[0067] Typical pore size distributions for supported catalysts prepared according to the present invention, with and without added fines, are shown in Figures 2A-2C. An initial peak located at the smaller pore diameters is observed to be between 50 Å (5 nm) and 100 Å (10 nm), and is estimated from Figures 2A and 2C to be about 65 Å (6.5 nm) and 75 Å (7.5 nm) based on nitrogen measurements, and about 110 Å (11.0 nm) based on mercury porosimetry.

[0068] Supported catalysts prepared according to the invention disclosed herein exhibit a pore size distribution, as measured using the mercury porosimetry method also disclosed herein, that includes the following characteristics: (A) for pores having a diameter less than 200 angstroms (Å) (20 nm), about 50% or more and up to about 75% TPV, 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 about 73%, or about 71%, or about 69%, or about 67%, or about 65%, or 63% TPV; (B) exhibiting a pore size of about 100 Å (10 nm) to about 200 Å (20 nm), similarly measured and reported using mercury penetration techniques, and typically having a pore content of about 35% to about 60%, or greater than 36%, or 37%, or 38%, or 39%, or 40%, or 41%, or 42%, or 43%, or 44%, or 45%, or 46%, or 47%, or 48%, or 49%, or 50%, or 51%, or 52%, and less than or equal to about 59%, or 58%, or 57%, or 56%, or 55%, or 54%, or 53%, or 52%, or 51%, or 50%. Further, for each of the ranges arising from the recited lower and upper limits, the amounts "greater than" and "less than" include values ​​expressed in tenths of a percent as well as unit percentage values. (C) pores within the size range of pores generally identified as exhibiting pore diameters of greater than 0 Å (0 nm) or greater than 20 Å (2 nm) to about 100 Å (10 nm), and also measured and reported using mercury penetration techniques, typically have a pore content of greater than about 4% to about 14%, or greater than 5%, or 6%, or 7%, or 8%, or 9%, or 10%, and A pore content of about 13%, or 12%, or 11%, or 10% or less. Further, for each of the ranges arising from the recited lower and upper limits, the "greater than" and "less than" amounts include values ​​expressed in tenths of a percent as well as unit percentage values. (D) for pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), a TPV of greater than about 15% and less than about 30%, or a TPV of greater than about 17%, or greater than about 20%, or greater than about 22% and less than about 28%, or less than about 25%, or less than about 23%; (E) For pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), a TPV of 10% or more and less than 30%, or a TPV of 12% or more, or 15% or more, or 17% or more, or 20% or more and less than a maximum of 28%, or less than a maximum of 25%, or less than a maximum of 23%.

[0069] Catalyst preparation In general, hydrotreating catalysts can be prepared using alternative methods. In the impregnation method (note that pre-impregnation and post-impregnation methods are further described 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, and a Group 6 (e.g., Mo) metal compound or precursor and a Group 8, 9, or 10 (e.g., Ni) metal compound or precursor are impregnated onto the support. The impregnated wet pellets are then dried and calcined to obtain a supported catalyst. In another preparation method, an alumina-containing powder, such as silica-alumina, catalytic metal precursors, water, and additives, such as extrusion aids, peptizing chemicals, etc., are combined, mixed, and extruded into pellets. The metal-containing wet pellets are 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. Pat. Nos. 7,390,766, 7,560,407 and 7,642,212 (assigned to DPKlein, Advanced Refining Technologies), the disclosures of which are incorporated herein to the full extent permitted. Suitable methods and compositions include adding to a suitable amount of water (A) at least one substantially water insoluble Group 8, 9 or 10 metal component, and (B) at least one substantially water soluble phosphorus-containing acidic component, typically in an amount insufficient to cause dissolution of the at least one Group 8, 9 or 10 metal component, to produce a slurry at ambient temperature; combining the slurry with (C) at least one Group 6 metal component; (D) mixing the combination of (A), (B) and (C) and heating the mixture for a time and at a temperature sufficient for (A), (B) and (C) to form a solution; and (E) adding additional amounts of water as necessary to obtain a solution concentration of at least one Group 8, 9 or 10 metal, at least one Group 6 metal, and phosphorus useful for impregnating the support, where Group 6, and Groups 8, 9 and 10 refer to the Groups of the Periodic Table of the Elements. In various preferred embodiments, the molar ratio of the at least one Group 8, 9 or 10 metal to the Group 6 metal is from about 0.05 to about 0.45, the concentration of the Group 6 metal expressed as the oxide is at least about 3 to about 50 weight percent based on the weight of the composition, and the amount of the phosphorus-containing acidic component is sufficient to provide a molar ratio of phosphorus to Group 6 metal of from about 0.05 to less than about 0.25, provided that the amount of the at least one Group 8, 9 or 10 metal is sufficient to promote the catalytic effect of the Group 6 metal. In still further embodiments, the process includes separating a volatile portion of the solution from the impregnated green support to obtain a dried catalyst having the desired moisture content.

[0071] "Pre-impregnated" catalyst refers to a catalyst in which the metal-containing solution(s) are added before the porous catalyst support is calcined. The metal-containing solution(s) can be added before or after shaping of the catalyst particles, but in important aspects, the metal-containing solution(s) are added before the support material is calcined. However, there are significant advantages to be gained by shaping the green support after impregnation (contact) with an aqueous solution containing one or more catalytic metals. These advantages are observed in the form of a more desirable distribution of metals throughout the support in the final catalyst. Thus, a "pre-impregnated" catalyst can be made as follows: The uncalcined alumina-containing silica-alumina powder is thoroughly mixed with water or, optionally, with a dilute 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, 9 or 10 metal compound or precursor, and optionally but preferably phosphorus, e.g., molybdenum, nickel and phosphorus compounds, and also optionally additional amounts of one or more metals of groups 8, 9 and 10, if necessary, to provide the desired amount of metal on the final catalyst. The one or more metals of groups 8, 9 or 10 used to achieve the optional additional amount of one or more metals of groups 8, 9 or 10 are typically selected to be water-soluble under the temperature conditions encountered. Furthermore, as described elsewhere herein, a chelating agent or compound may be optionally but preferably included in the impregnation solution.

[0072] The metal-containing mixture, which typically contains about 50 to about 65 weight percent moisture, is formed, preferably by extrusion, into catalyst particles having a desired size. The formed catalyst particles are dried using alternative or combined heating methods, including high temperature drying and combinations of high and moderate calcination temperatures. For example, the 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), e.g., 400°F (204.4°C), for about 30 to 60 minutes, e.g., 40 minutes, or the entire time, to achieve the desired target LOI level as disclosed elsewhere herein. Alternatively, the wet impregnated catalyst particles can be subjected to an initial hot drying temperature of about 300°F (148.9°C) to about 340°F (171.1°C), e.g., 320°F (160°C), for a limited time, e.g., about 8 to 12 minutes, e.g., 10 minutes, and then the temperature is increased to a mild calcination temperature of about 650°F (343.3°C) to about 690°F (365.6°C), e.g., 670°F (354.4°C), for about 30 to about 60 minutes, e.g., 40 minutes, and then the catalyst particles can be held at the final ramp temperature for about 8 to 12 minutes, e.g., about 10 minutes, or the entire time, to achieve the desired target LOI level as disclosed elsewhere herein. Regardless of which drying method is used, careful consideration should be given to the presence or absence of a chelating agent in the impregnation solution, and if more than one drying method is used, the overall drying conditions are 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 agent, complex, or thermal by-products in the dried supported catalyst.

[0073] "Post-impregnated" catalyst refers to a catalyst in which the metal-containing solution(s) are added after the porous catalyst support is calcined. Suitable calcination conditions for the support itself are described above. The porous catalyst support can be calcined before or after shaping of the catalyst support particles, but the key aspect of post-impregnation is that the metal-containing solution(s) are added after the support material is calcined. Thus, a "post-impregnated" catalyst can be made as follows: The uncalcined alumina-containing or silica-alumina powder is thoroughly mixed with water or, optionally, with a dilute aqueous solution of nitric acid, and the alumina mixture, containing about 50-75% water by weight, is then formed, preferably by extrusion, into catalyst particles having the desired size and shape. The formed particles are dried at a temperature of about 110 to about 150° C. and then heated to about 400° C. The dried and calcined particles are then calcined at a temperature of about 750° C. for about 1 to 2 hours. The dried and calcined particles are contacted with a suitable amount of a stable metal solution. For example, such a solution may contain, in addition to molybdenum, nickel and phosphorus, an optional additional amount of a solution of one or more metals of Groups 8, 9 or 10 (also identified as Group VIIIB according to the CAS designation), as needed, to provide the desired amount of metal on the final catalyst while substantially and uniformly filling the pores. After the suitable contact time, the formed catalyst particles are dried according to one of the alternative conditions described immediately above.

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

[0075] Suitable catalytically active metals from groups 8, 9 and 10 present in the components of the present invention include suitable compounds of Fe, Co, Ni, Pd, Pt, and mixtures thereof. Of these, most preferred are Co and Ni. Suitable group VIB elements or metals include Cr, Mo, W, and mixtures thereof, with Mo and W being most preferred. Preferred combinations of metal components include, for example, nickel and molybdenum, cobalt and molybdenum, tungsten and nickel or cobalt, molybdenum, cobalt and nickel, tungsten, nickel and cobalt, molybdenum, chromium and nickel, and the like, with 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 the appropriate ratios. A variety of 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. Component weights can be varied to ensure solution stability and the appropriate concentrations and ratios of the metals. The required component weights, order of addition, temperatures, and reaction times 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 provide chelation when combined with one or more of the catalytically active metal components. Suitable compounds or chelating agents include organic additives such as (i) an organic compound selected from the group consisting of compounds containing at least two oxygen atoms and 2-10 carbon atoms, and compounds composed or derived from these compounds, or (ii) an organic compound containing at least one covalently bonded nitrogen atom and at least one carbonyl moiety, or both (i) and (ii). The organic compound according to (i) above is preferably selected from the group of compounds containing at least two oxygen-containing moieties, such as carboxyl, carbonyl, or hydroxyl moieties, and 2-10 carbon atoms, and compounds composed or derived from these compounds. The compound composed or derived from the organic compound may be, for example, an ether, ester, acetal, acid chloride, acid amide, oligomer, or polymer of an organic compound. 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, pyruvic aldehyde, glycolaldehyde, and acetaldol. The organic compound is selected from the group consisting of compounds containing at least two hydroxyl groups and 2 to 10 carbon atoms per molecule, and compounds consisting of these compounds. More preferred are. Suitable compounds include, for example, tartaric acid or aliphatic alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane. Compounds composed of these organic compounds include oligomers and polymers, for example, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, and tetrapentylene glycol. This range can be extrapolated to include polyethers, for example, polyethylene glycol. With regard to polyethylene glycol, polyethylene glycols having a molecular weight of 200 to 8,000 are preferred. Other compounds composed of these organic compounds are ethers, for example, 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, inter alia, 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 is formed by monosaccharides, for example, glucose and fructose. Compounds comprised of these organic compounds include oligomers and polymers, for example disaccharides such as lactose, maltose, and saccharose, as well as polysaccharides. A particularly preferred organic compound or chelating agent is citric acid.

[0078] The organic compounds according to (ii) preferably contain at least two carbonyl moieties. It is preferred that at least one carbonyl moiety is present in a carboxyl group. Even more preferred is 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 R′ is independently selected from alkyl, alkenyl, and aryl having up to 10 carbon atoms, optionally substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amido. 3 is -O- or -NR 4 R is an alkylene group having up to 10 carbon atoms which may be interrupted by -. 4 is R 1 are selected from the same groups as those listed above for R 3 The alkylene group may be substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. As stated 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 '(Formula (I)) and R 1 , R 2 , and R 1 '(Formula (II)) at least two of which are of the formula -R 5 -C(O)OX, where R 5is an alkylene group having 1 to 4 carbon atoms, and X is hydrogen or another cation, such as an ammonium, sodium, potassium, and / or lithium cation. When X is a polyvalent cation, one X may be two or more -R 5 It can be bonded to the -C(O)O- group. Typical examples of compounds of formula (I) are ethylene diamine(tetra)acetic acid (EDTA), hydroxyethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. Typical examples of compounds of formula (II) are nitrilotriacetic acid (NTA).

[0079] The catalyst composition typically comprises a total of about 30 to about 45 weight percent of at least one metal component from Group 6 of the Periodic Table of the Elements (alternatively referred to as Group VIB) and at least one metal component from Groups 8, 9, or 10 of the Periodic Table of the Elements (alternatively referred to as Group VIIIB), or mixtures thereof, the Group VIB and Group VIIIB metal components being calculated as oxides and based on the total weight of the catalyst composition. Further, the total weight of the Group 6 metal component and the Group 8, 9, or 10 metal components, calculated as oxides, constitutes about 35 to 55 weight percent, based on the total weight of the catalyst composition. Alternatively, the Group 6 metal oxide may be present in a range of about 30 to about 45 weight percent of the total weight of the catalyst composition. The total weight of the metal oxide content and the Group 8, 9 or 10 metal oxide content is from about 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or 45% by weight to about 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, calculated as the oxide, comprises from about 30 to about 45 weight percent, or from about 31, 32, 33, 34, 35, 36, 37, or 38 weight percent to about 45, 44, 43, 42, 41, 40, 39, 38, 37, or 36 weight percent.

[0081] The Group VIIIB metal is typically present in an amount of 3 to about 15 weight percent, or from about 3.5, 4, 5, 6, 7, 8, 9, or 10 weight percent to about 15, 14, 13, 12, 11, 10, 9, 8, or 7 weight percent, calculated as the oxide. 2 O 5 Typically, the metals are present in an amount of about 1 to about 10 weight percent, or from about 1.5, 2.5, 3, 4, or 5 weight percent to about 6, 7, 8, 9, or 10 weight percent, calculated as 1. The amount of Group VIB and Group VIIIB metals present in the catalyst composition can be measured using atomic absorption spectrometry (AAS), inductively coupled plasmaspectrometer (ICP) analysis, and / or x-ray fluorescence (XRF).

[0082] The supported catalyst composition after impregnation, drying and calcination, i.e., the metal-containing components and phosphorus (if included) are present as their oxides, and preferably prior to the sulfiding step, if any, exhibits the above properties.

[0083] The term "agglomerate" refers to a product combining particles held together by various physicochemical bonds, and the term "molded" and its grammatical variations refer to the act of forming an agglomerate. More specifically, each agglomerate is composed of a plurality of adjacent constituent primary porous carrier particles, preferably joined and connected at their contact points. Thus, the agglomerate particles typically exhibit a higher macropore content than the constituent primary particles that make up the agglomerate particles, due to the 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, such as the specific pore size or range and pore size distribution characteristics.

[0084] The agglomeration of the porous carrier, e.g., alumina, composite, is carried out according to methods known in the art, in particular by pelleting, extrusion, forming into beads in a rotating coating drum, etc. Modular techniques can be used in which composite particles having a diameter of about 0.1 mm or less are agglomerated into particles having a diameter of at least about 0.8 mm using a granulation liquid. As known to those skilled in the art, the agglomeration can be carried out optionally in the presence of additional amorphous or crystalline binders, and pore formers can be added to the agglomerated mixture. Conventional binders include other forms of alumina, silica, silica-alumina, clay, zirconia, silica-zirconia, magnesia, and silica-boria. Conventional pore formers can be used, and examples of suitable agents include wood flour, charcoal, cellulose, starch, naphthalene, and generally organic compounds that promote pore formation and can be removed by calcination. However, the addition of pore formers is not necessary or desirable.

[0085] The catalyst compositions may have different shapes, selected for their suitability for the process and / or equipment in which they are used. For example, when the catalyst composition is used in a slurry type reactor, a fluidized bed, a moving bed, or an expanding bed, spray drying or beading is generally applied. For fixed bed or ebullated bed applications, the catalyst composition is generally extruded, pelletized, and / or beaded. In the latter case, at any stage before or during the shaping process, Any additives normally used to facilitate shaping can 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 shaping step, for example, for the purpose of increasing the mechanical strength of the aggregates. In the present invention, the shaping step is carried out in the presence of water. For extrusion and beading, the amount of water in the shaping mixture, expressed as LOI, is preferably in the range of 20-80%. Additional water can be added if required by the shaping operation, or if the amount of water is too high, the water can be reduced, for example, by solid-liquid separation by filtration, decantation, or evaporation. It is within the scope of one skilled in the art to appropriately control the amount of water.

[0086] Suitable shapes include powders, spheres, cylinders, rings, and symmetrical or asymmetrical multilobal forms, e.g., trilobes and tetralobes. Particles resulting from extrusion, beading, or pelletizing typically have diameters ranging from about 0.2 to about 10 mm, and lengths ranging from about 0.5 to about 20 mm, although deviations from these general ranges are possible. Catalysts in the form of extrudates are generally preferred.

[0087] The present invention also relates to a catalyst composition according to the invention in which the metal components have been partially or completely converted to their sulfides, in which case the catalyst is preferably essentially free of Group VIIIB metal disulfides.

[0088] Calcination is carried out according to the temperature and time described above. As described, the calcination conditions, especially the temperature, of the metal-containing (especially post-impregnated) support or carrier are typically lower than those used for the support or carrier itself. Calcination can 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, calcination is carried out in an oxygen-containing atmosphere.

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

[0090] Furthermore, the catalyst according to the invention is particularly useful in a hydrocarbon conversion process which involves contacting a hydrocarbon feedstock with a supported catalyst in particulate form under conditions of high temperature and high hydrogen pressure, the catalyst being made according to the invention. As described herein, such catalysts comprise at least one catalytically active metal from Group 6 of the Periodic Table, at least one catalytically active metal from Groups 8, 9 or 10 of the Periodic Table, and optionally phosphorus, the metals and optionally phosphorus being supported on an alumina-containing support as described above, with pore size distribution characteristics and other particle characteristics also as described.

[0091] Use of catalysts in hydroprocessing processes The catalysts prepared according to the present invention can be used under a wide range of reaction conditions, generally, for example, at temperatures ranging from about 200° C. to about 500° C., at hydrogen pressures ranging from about 5 to 300 bar (0.5 MPa to 30 MPa), and at temperatures ranging from about 0.05 to 10 h. -1 Virtually all hydroprocessing systems are capable of processing multiple feeds at liquid hourly space velocities (LHSVs) in the range of The term "hydroprocessing" encompasses a variety of petroleum refining processes in which a hydrocarbon feed is reacted with hydrogen at high temperatures and pressures (hydroprocessing reaction conditions), including hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydrocracking, and hydrocracking under mild pressure conditions, also referred to as mild hydrocracking.

[0092] More specifically, "hydroprocessing" refers to the process as that term is used herein. When used herein, hydroprocessing refers to a petroleum refining process in which a petroleum feedstock (a complex mixture of hydrocarbons present in petroleum) is reacted with hydrogen in the presence of a catalyst under pressure to reduce (a) the concentration of at least one of sulfur, contaminant metals, nitrogen, and Conradson carbon present in the feedstock, and (b) at least one of the viscosity, pour point, and density of the feedstock. and hydrotreating processes which differ in the amount of hydrogen reacted and the nature of the petroleum feedstock being treated.

[0093] Hydrocracking is understood to involve the hydroprocessing of primarily hydrocarbonaceous compounds ("feedstocks") that typically contain at least five (5) carbon atoms per molecule. and the process is carried out (a) at superatmospheric hydrogen partial pressures, b) at temperatures typically less than 1100°F (593.3°C), (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 the synthesis of olefins having at least 5 carbon atoms per molecule. is understood to include the hydroprocessing of a primarily hydrocarbonaceous compound ("feedstock") containing (c) with superatmospheric hydrogen partial pressures, (b) at temperatures typically less than 1100°F (593.3°C), (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.

[0095] Procedures for hydrotreating heavy hydrocarbon streams, such as petroleum hydrocarbon residues The conditions are known in the art and include pressures in the range of about 1,000 psia (68 atm) to about 3,000 psia (204 atm), average catalyst bed temperatures in the range of about 700° F. (371° C.) to about 850° F. (454° C.), liquid hourly space velocities (LHSV) in the range of about 0.1 volumes of hydrocarbon per volume of catalyst per hour to about 5 volumes of hydrocarbon per volume of catalyst per hour, and standard cubic feet per barrel (SCFB) of about 2,000 (356 m). 3 / m 3 ) ~ Approx. 15,000 SCFB (2,671 m 3 / m 3 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 a hydrogen recycle or hydrogen addition rate in the range of about 3,000 SCFB (534 m 3 / m 3 ) ~ Approx. 10,000 SCFB (1,781 m 3 / m 3 ) in the range of 1,000° F. Typically, the process temperature and space velocity are selected to convert at least 30% by volume of the feed fraction boiling above 1,000° F. to products boiling below 1,000° F., more preferably at least 50% by volume to products boiling below 1,000° F., and even more preferably at least 70% by volume of the target fraction to products boiling below 1,000° F.

[0096] For processing of hydrocarbon distillates, operating conditions are typically from about 200 psia (13 atm) to about 3,000 (204 atm), an average catalyst bed temperature within the range of about 600°F (315°C) to about 800°F (426°C), an LHSV of about 1,000 SCFB (178 m3) within the range of about 0.4 to about 6 volumes of hydrocarbon per hour per volume of catalyst. 3 / m 3 ) ~ approx. 10,000S CFB(1,381m 3 / m 3 The preferred operating conditions for hydrotreating the hydrocarbon distillate are , a hydrogen partial pressure in the range of about 200 psia (13 atm) to about 1,200 psia (81 atm), an average catalyst bed temperature in the range of about 600°F (315°C) to about 750°F (398°C), an LHSV in the range of about 0.5 volumes of hydrocarbon per hour per volume of catalyst to about 4 volumes of hydrocarbon per hour per volume of catalyst, and a SCFB (Frequency of Flow) of about 1,000 m 3 / m 3 ) ~ Approx. 6,000 SCFB (1,068 m 3 / m 3 ) including hydrogen recycle or hydrogen addition rates in the range of

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

[0098] The invention having thus been generally described will be more readily understood with reference to the following examples, which are provided by way of illustration and are not intended to limit the invention. EXAMPLES

[0099] Preparation of Supported Catalysts. Generally, a 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 aqueous ammonia in the appropriate ratios. Various molybdenum and nickel sources as disclosed above may be used. These solutions are used to impregnate supports to prepare the final catalyst. Component weights and addition order are selected to ensure solution stability and the selected target concentration of metals on the final catalyst for the intended catalytic application. Solution processing temperatures and times are selected to ensure solution stability. The component weights, addition order, processing temperatures, and processing times required 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 in this disclosure as a carrier or support, for use in preparing the comparative catalyst, the following steps were followed: (1) In a two-stage precipitation process in which the temperature and pH are changed and controlled at each stage, the temperature and pH are changed and controlled at each stage. For example, see US Patent Application Publication No. 2014 / 0367311, US Patent No. 6,589,908, or US 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 precipitation seed alumina at about pH 8 and 55°C (131°F). In the second stage, the temperature is increased to about 65°C (150°F), the pH is increased to about 9, the reactants are mixed, and the second stage precipitation is completed before the second half of the aluminum sulfate and sodium aluminate is added. (2) The resulting 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 dried by introducing it into a heated auger. Allowed to dry. (4) The mixture from (3) was placed in an Eirich mixer along with water, nitric acid, recycled base material, and catalyst fines from the latter part of the process, and mixed until the resulting mixture was granulated. (5) The material from (4) was extruded to form a substrate or support precursor. (6) The extruded substrate precursor was introduced into a rotary calciner and heated until the volatiles level was reduced to <2%, as determined by loss on ignition (LOI). LOI is the amount of volatiles present in the sample. LOI is a measure of the total volatile matter or components capable of volatilizing at the elevated temperatures present. The LOI test is performed by exposing a sample to an oxygen-containing atmosphere at 1020°F (548.9°C) for one hour, thereby decomposing, oxidizing, or igniting any organic material that may be present and eliminating any residual moisture to a target endpoint.

[0101] (II) A comparative supported catalyst was 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 the desired impregnation solution of molybdenum, nickel, phosphorus, and a chelating agent in the desired concentrations. (3) The impregnated catalyst was then conveyed through a rotary calciner to a target LOI level of 5 wt.%.

[0102] Example A of the Invention Substrate or support A was prepared as follows: (1) 1200 g of silica-alumina powder (volatile free basis) containing 5 wt. % silica dispersed in alumina was charged to an Eirich mixer at room temperature. (2) 17.15 g of concentrated nitric acid (70% by weight HNO 3 ) and 2000 g of deionized water were added to the mixer at a rate of approximately 150 cc / min. The composition was mixed for a total of 5 minutes (including the time to add the water). (3) Mixing was stopped and the sides of the mixer were scraped, at which point small amounts of water (20 g each) were added as needed to form an extrudable paste. (4) The LOI of the paste was measured to be 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 extrudate was placed on a screen tray approximately 1 / 2 inch deep and placed in a preheated Gruenberg drying oven at 250°F (121.1°C) for 2 hours followed by an additional 2 hours at 400°F (204.4°C). (7) 200 g of the dried extrudates from (6) were calcined in a furnace at 1400° F. (760° C.) for 40 minutes using 2 SCFH (standard cubic feet per hour) of dry air. (8) The calcined extrudates were then cooled to room temperature.

[0103] Catalyst sample A was prepared as follows: (1) Weigh out 50 g of the substrate A (based on not containing volatile substances) prepared above. (2) The substrate of (1) was impregnated with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations by the incipient wetness method. (3) The impregnated sample from (2) was 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 out 50 g of the substrate A (based on the basis of no volatile matter) prepared above. (2) The substrate of (1) was impregnated with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations by the incipient wetness method. (3) The impregnated sample from (2) was 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 Invention The substrate or support for catalyst sample B (containing recycled fines) was prepared as follows: (1) 1200 g of silica-alumina powder (on a volatile free substrate) containing 5 wt. % silica dispersed in alumina was charged into an Eirich mixer at room temperature. (2) 60 g of ground Catalyst B fine powder (recycled fine powder) and 60 g of ground Substrate B fine powder (recycled fine powder) were placed in a mixer. (3) 17.1 g of concentrated nitric acid (70% by weight HNO 3 ) and 2000 g of deionized water were added to the mixer and mixing was started. (4) The mixer was stopped, the sides scraped down, and water added as needed to obtain the desired paste consistency. (5) After 10 minutes, the mixture formed granules with an LOI of 66.2%. (6) The mixture from (5) was extruded using a 1 / 16" AQ plastic insert die and a water cooled extruder barrel. (7) The extrudate was placed in a drying oven at 250°F (121.1°C) for 2 hours. (8) The dried extrudate from (7) was introduced into a rotary calciner according to the following protocol: charge at 250°F (121.1°C), hold for 10 minutes, ramp to 1400°F (760°C) for 40 minutes, hold 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) Weigh out 175 g of the substrate (volatile free basis) from (9) above. (2) The substrate from (1) was impregnated with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at the desired concentrations using a dip soak impregnation method. (3) The impregnated substrate from (2) was introduced into a rotary calciner according to the following protocol: 320°F (160°C) for 10 minutes, then ramp to 670°F (354.4°C) for 40 minutes, and hold at 670°F (354.4°C) for 10 minutes. (4) The resulting supported catalyst B was then cooled to room temperature.

[0107] The pore size distributions (PSD) of the comparative and inventive substrates and catalysts prepared as described above were measured using the standard Hg porosimetry method identified above, and are shown in Figures 1A-1C and 2A-2C.

[0108] 1A-1C show the PSD comparison between the three catalytic substrates. The bulk properties and chemical composition comparison between the three catalytic substrates is summarized in Table 1 below. The PV (pore volume, i.e., total pore volume) of Exemplary Substrate A is about 20% higher than the PV of the Comparative Substrate, while the PV of Exemplary Substrate B (including fines) is 15% higher.

[0109] 2A-2C show the PSD comparison between the three catalysts prepared in the above examples. The bulk properties and chemical composition comparison between the three catalysts are summarized below in Table 2. It can be observed that the total metal loading of the 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 and the Comparative Catalyst were tested under the following Bench Scale Unit (BSU) testing protocol: Total pressure=2300psi H 2 / 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: A vacuum gas oil (VGO) feed blend having the following properties: API (American Petroleum Institute Gravity) = 19.7, N = 1810 ppm, S = 27150 ppm

[0113] A simplified flow diagram of the bench scale test unit (BSU) used to carry out performance testing using the catalysts prepared in the examples is shown in Figure 3. No recycle was used in the BSU operation. The whole liquid product (WLP) was sent to an online stripper with a controlled cut point target. Stripper overhead (STO), stripper bottoms (STB), and Samples were collected from the gas valve and tested daily for properties. The cut point target for the STO and STB products was 470°F (243.3°C) so that a STB product with a boiling point higher than 470°F (243.3°C) was produced.

[0114] Test results A comparison of catalysts in VGO hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and aromatics hydrogenation or hydrodearomatization (HDA) is shown in Table 3, and the effect on product viscosity is shown in Table 4 (note that apparent conversion is used here to represent HDA).

[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 (containing fines) is also more active. The table also includes the ratios of kHDS and kHDN (reaction rates for the indicated reactions) for the exemplary catalysts versus the comparative catalysts, which further illustrates 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 hydrodenitrogenation (kHDN) as a function of catalyst or bench-scale unit operating temperature for comparative and exemplary catalysts. It is observed that the exemplary catalyst is more effective at a given temperature, or comparable 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 Figure 4C for apparent conversion or hydrocracking at 700°F to produce higher paraffins. Thus, when the supported catalyst of the present invention is used in hydroprocessing processes for sulfur, nitrogen removal, or aromatics hydrogenation, the treated hydrocarbons are decomposed at a high temperature. The levels of these components in the raw product improve measurably as a function of the operating temperature of the process: operating at higher temperatures will result in lower sulfur or nitrogen contents in the treated product, but doing so comes at the expense of higher costs to operate at the higher temperatures.

[0118] Similarly, the improved performance of the catalysts of the present invention can be seen in Figures 5A, 5B, and 5C, which show the volume percent of aromatics, naphthenes, and paraffins, respectively, in the stripper bottoms (STB) of a bench-scale unit used to evaluate the performance of exemplary Catalyst A versus the comparative catalyst, as a function of apparent conversion. In each case, significant improvements can be observed, which are more pronounced at lower operating temperatures, a beneficial advantage in itself.

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

[0120] [Table 5]

[0121] The above data indicates that the combination of higher catalytic metal loading, higher substrate pore volume, and higher concentration of larger pores are the key features that lead to Exemplary Catalyst A exhibiting higher VGO HDN, HDS, and HDA activity. In other words, even with the addition of recycled fines to the substrate, Exemplary Catalyst B (in the above tables and figures) maintains its activity advantages for HDN, HDS, and HDA.

[0122] The Comparative Catalyst and Catalyst A prepared according to the above examples were further evaluated in a BSU under the following conditions using the same feed blends as above.

[0123] [Table 6]

[0124] The types of hydrocarbons in the STB from the BSU tests as determined by GC-MS are summarized in Table 5 below.

[0125] [Table 7]

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

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

[0128] [Table 8]

[0129] [Table 9]

[0130] The petroleum feedstock used in the BSU testing of the catalyst was selected because it exhibited a lower VI, higher viscosity, and higher aromatic and S-compound content, all of which would be desirable to improve. In consideration of the BSU test results, the following conclusions and observations were made: 1. At each of the experimental conditions using exemplary catalyst A, the STB product VI was higher and the viscosity and total aromatics content was lower, both desirable results. 2. As catalyst concentration increases, the VI of the STB product increases and the viscosity and total aromatics content decrease, which is also desirable. 3. At each of the run conditions, the hydrocracking conversion up to 700° F. using exemplary catalyst A is higher than that of the comparative catalyst, which is clearly advantageous. 4. Exemplary Catalyst A provides higher apparent conversion and therefore lower STB product aromatics content and higher paraffin and naphthene content versus the comparative catalyst. 5. At each run condition, exemplary catalysts A and B exhibit higher HDN / HDS activity than the comparative catalyst.

[0131] Alternative Embodiments The following enumerated paragraphs illustrate various and alternative embodiments of the present invention. 1. A supported catalyst comprising at least one metal from group 6 (alternatively referred to as group VIB) of the periodic table of the elements and at least one metal from group 8, 9 or 10 (alternatively referred to as group VIIIB) of the periodic table of the elements, and optionally phosphorus; the Group 6 metal comprises from about 30 to about 45 weight percent, and the sum of the Group 6, Group 8, Group 9, or Group 10 metal components, or mixtures thereof, comprises from about 35 to about 55 weight percent, calculated as oxides and based on the total weight of the catalyst composition; the metal, and, if present, phosphorus, are supported on and / or within a porous inorganic oxide support or substrate, the support having a total pore volume (TPV) of from about 0.8 cc / g to about 1.5 cc / g prior to incorporation of the metal and, if present, phosphorus; (a) a TPV of about 25% or more to about 75% or more in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 angstroms (Å) (20 nm); (b) a TPV of greater than about 15% to less than about 30% in pores having a diameter of from 200 Å (20 nm) to less than 1000 Å (100 nm); (c) containing 10% to less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm); The supported catalyst is (d) a TPV of greater than about 35% to about 60% in pores having a diameter of 100 ((Å)) (10 nm) to 200 Å (20 nm); (e) a TPV of greater than about 15% to less than about 30% in pores having a diameter of from 200 Å (20 nm) to less than 1000 Å (100 nm); (f) containing 10% to less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm); A supported catalyst, the pore characteristics and content of which are measured using mercury porosimetry. 2. The supported catalyst of claim 1, further characterized in that the support exhibits a d50 of at least 110 Å (11 nm) and not more than about 170 Å (17 nm), or the supported catalyst exhibits a d50 of at least about 125 Å (12.5 nm) and not more than about 210 Å (21 nm). 3. The supported catalyst of claim 1, further characterized in that greater than about 17% to less than about 28% of the TPV of the supported catalyst is in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm). 4. The supported catalyst of claim 1, further characterized in that about 12% to less than about 28% of the TPV of the supported catalyst is in pores having a diameter of about 1000 Å (100 nm) to about 30,000 Å (3,000 nm). 5. The supported catalyst of claim 4, further characterized in that about 15% to less than about 25% of the TPV of the supported catalyst is in pores having a diameter of about 1000 Å (100 nm) to about 30,000 Å (3,000 nm). 6. The supported catalyst of claim 1, further characterized in that about 40% to about 55% of the TPV is in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm). 7. The supported catalyst of claim 1, wherein the support is selected from silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, silica coated with alumina, alumina coated with silica, 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 supported catalyst of claim 1, further characterized in that the Group 6 metal is molybdenum and the Group 8, 9, or 10 metal is selected from the group consisting of cobalt, nickel, and mixtures thereof. 9. The supported catalyst of claim 8, further comprising phosphorus. 10. The following: (I) hydroprocessing of petroleum feeds; (II) Hydrocracking (HCR) of petroleum feedstocks; (III) hydrodearomatization (HDA) of petroleum feedstocks; (IV) hydrodesulfurization (HDS) of petroleum feedstocks; (V) hydrodenitrogenation (HDN) of petroleum feedstocks; (VI) Hydrodemetallization (HDM) of petroleum feedstocks; and (VII) hydrotreating a loaded hydrocarbon feed or petroleum feedstock containing components boiling 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. Item 1. The supported catalyst according to item 1, useful in at least one process for 11. The supported catalyst of claim 10, wherein the catalyst is pre-impregnated, shaped, dried, and calcined. 12. The supported catalyst of claim 10, further exhibiting a d50 of about 120 Å (12 nm) or more and about 200 Å (20 nm) or less. 13. A process for treating a hydrocarbon feedstock containing at least one of paraffinic, aromatic, and naphthenic components to produce a treated product, the process comprising: (I) hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, and hydrocracking, the process comprising contacting a feedstock in at least one reactor with hydrogen under hydrocracking conditions using a supported catalyst as described in paragraph 1, and recovering products; (II) hydrotreating a hydrocarbon feed containing components boiling 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, by subjecting the feed to isothermal or substantially isothermal hydrotreating. The process is carried out by contacting the supported catalyst described in item 1 with hydrogen under hydrotreating conditions. hydrotreating, including recovering the product; (III) hydroconverting a hydrocarbon feedstock having components boiling above 600°F (315.6°C) to form a product having an increased proportion of components boiling below about 600°F (315.6°C), by contacting the feed with hydrogen and a supported catalyst described in paragraph 1 under isothermal or substantially isothermal hydrotreating conditions, and recovering the product. forming a (IV) hydroconverting a feed, comprising contacting a feed comprising a hydrocarbon oil with hydrogen and the supported catalyst described in paragraph 1 under conditions of an elevated temperature of greater than about 600°F (315.6°C) and a pressure of greater than about 500 psig (3.44 MPa), and recovering a product. 14. The process of claim 13, wherein the treated recovered product exhibits at least one of a reduced aromatic content, an increased paraffin content, a reduced viscosity, and an increased viscosity index, as compared to the untreated hydrocarbon feedstock. 15. A method for preparing a catalyst, comprising the steps of: (I) hydroprocessing of petroleum feedstocks; (II) Hydrocracking (HCR) of petroleum feedstocks; (III) hydrodearomatization (HDA) of petroleum feedstocks; (IV) hydrodesulfurization (HDS) of petroleum feedstocks; (V) hydrodenitrogenation (HDN) of petroleum feedstocks; (VI) Hydrodemetallization (HDM) of petroleum feedstocks; and (VI) A charged hydrocarbon containing a component boiling 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 process selected from the group consisting of hydrotreating the feed. for use in a process that The method comprises impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Group 6 (alternatively referred to as Group VIB) of the Periodic Table of the Elements, at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Groups 8, 9 or 10 (alternatively referred to as Group VIII) of the Periodic Table of the Elements, and optionally a phosphorus-containing compound and at least one organic chelate compound, wherein Groups VIB and VIIIB and the phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere, and thereafter drying and calcining the resulting impregnated support, such that the support is (A) mixing an alumina-containing powder with water and optionally nitric acid to form a wet mixture; and (B) Providing the wet mixture on a support suitable for use in a hydroprocessing reactor. drying and calcining the mixture, the mixture being prepared by shaping the mixture to form a solid particle; The support has a total pore volume (TPV) of about 0.6 cc / g to about 1.1 cc / g, the following pore size distribution and pore content corresponding to values ​​measured by mercury porosimetry: The support has 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: (i) a TPV of 25% or more to 45% in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm); (ii) a TPV of greater than 15% and less than 30% in pores having a diameter of from 200 Å (20 nm) to less than 1000 Å (100 nm); and (iii) 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 support particles are dried and calcined to form calcined pills. 17. The method of claim 15, wherein the aqueous solution contains an organic chelating compound selected from acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvic aldehyde, glycolaldehyde, acetaldole, 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 of claim 17, wherein the organic chelating 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 carrier or support having a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g; (a) a TPV of greater than about 25% to about 45% in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm); (b) a TPV of greater than about 15% to less than about 30% in pores having a diameter of from 200 Å (20 nm) to less than 1000 Å (100 nm); (c) a porous inorganic oxide carrier or support 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 paragraph 20, wherein the support is selected from silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, silica coated with alumina, alumina coated with silica, 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. The porous inorganic oxide carrier or support according to item 20, wherein the support exhibits a d50 of 110 Å (11 nm) or more and about 170 Å (17 nm) or less. 23.About 185m 2 / g ~ approx. 425m 2 Item 21. The porous inorganic oxide carrier or support according to item 20, having a total surface area, as determined by nitrogen adsorption using the BET technique, of 1000 nm to 1000 nm / g. 24. The porous inorganic oxide carrier or support according to item 20, having greater than about 55% to about 75% of pores having a diameter of less than 200 Å (20 nm) as measured using mercury penetration spectroscopy. 25. About 85% to about 98% by weight of Al 2 O 3 and about 15% by weight to about 2% by weight of SiO 2 and Al 2 O 3 and SiO 2 Item 21. The porous inorganic oxide carrier or support according to item 20.

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

[0134] Additionally, any range of numbers set forth in the specification or claims, such as those expressing a particular set of properties, units of measurement, conditions, physical states, or percentages, is intended to expressly and literally incorporate herein by reference or otherwise any numbers that fall within such range, including any subset of numbers within any range so set forth. L and upper limit R U Whenever a numerical range having a range is disclosed, any number R falling within that range is specifically disclosed. Specifically disclosed are the following numbers R falling within the range: R=R L +k(R U -R L ), where k is a variable ranging from 1% to 100% in 1% increments, for example, k is 1%, 2%, 3%, 4%, 5%....50%, 51%, 52%....95%, 96%, 97%, 98%, 99%, or 100%. Additionally, any numerical range represented by any two values ​​of R calculated above is specifically disclosed.

[0135] Although the invention has been described herein with reference to particular embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the invention. It should thus 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. The present disclosure is not limited with respect to the particular 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. Functionally equivalent methods and compositions within the scope of the present disclosure, in addition to those enumerated herein, 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. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It should be understood that the disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which may, of course, vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0136] The embodiments illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc. shall be read expansively and without limitation. In addition, the terms and expressions used herein are used as terms of description rather than of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the shown and described features or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" is used to refer to the specific recited features. It will be understood that the term "consisting of" includes those elements described above, as well as those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. " excludes any elements not specified.

[0137] [Table 10]

[0138] Other embodiments are within the scope of the following claims.

Claims

1. A supported catalyst comprising at least one metal from Group 6 (alternatively referred to as Group VIB) of the Periodic Table of the Elements and at least one metal from Groups 8, 9 or 10 (alternatively referred to as Group VIIIB) of the Periodic Table of the Elements, and optionally phosphorus; the Group 6 metal comprises from about 30 to about 45 weight percent, and the sum of the Group 6 and Group 8, 9, or 10 metal components, or mixtures thereof, comprises from about 35 to about 55 weight percent, calculated as oxides and based on the total weight of the catalyst composition; the metal, and, if present, phosphorus, are supported on and / or within a porous inorganic oxide support or substrate, the support having a total pore volume (TPV) of from about 0.8 cc / g to about 1.5 cc / g prior to incorporation of the metal and, if present, phosphorus; (a) a TPV of greater than about 25% to about 45% in pores having a diameter between 100 angstroms (Å) (10 nm) and 200 Å (20 nm); (b) a TPV of greater than about 15% to less than about 30% in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); (c) containing greater than or equal to 10% and less than 30% TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm); The supported catalyst is (d) a TPV of greater than about 35% to about 60% in pores having a diameter of 100 (Å) (10 nm) to 200 Å (20 nm); (e) a TPV of greater than about 15% to less than about 30% in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); (f) comprising greater than or equal to 10% and less than 30% TPV in pores having a diameter between 1000 Å (100 nm) and 30,000 Å (3,000 nm); A supported catalyst, the pore characteristics and content of which are measured using mercury porosimetry.

2. The support has a d ５０ or wherein the supported catalyst exhibits a d50 of about 125 Å (12.5 nm) or greater and about 210 Å (21 nm) or less.

3. 3. The supported catalyst of claim 1 or 2, wherein greater than about 17% and less than about 28% of the TPV of the supported catalyst is in pores having a diameter of 200 Å to less than 1000 Å.

4. 4. The supported catalyst of any one of claims 1 to 3, wherein greater than or equal to about 12% and less than about 28% of the TPV of the supported catalyst is in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

5. 5. The supported catalyst of claim 4, wherein greater than or equal to about 15% and less than about 25% of the TPV is in pores having a diameter between 1000 Å (100 nm) and 30,000 Å (3,000 nm).

6. 6. The supported catalyst of any one of claims 1 to 5, wherein about 40% to about 55% of the TPV is in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm).

7. 7. The supported catalyst of any one of claims 1 to 6, wherein the support is silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, silica coated with alumina, alumina coated with silica, 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 a mixture of any two or more thereof.

8. 8. The supported catalyst of claim 1, wherein the Group 6 metal is Mo and the Group 8, 9, or 10 metal is selected from the group consisting of Co, Ni, and mixtures thereof.

9. 9. The supported catalyst of claim 8 further comprising phosphorus.

10. below: hydroprocessing of petroleum feedstocks; Hydrocracking (HCR) of petroleum feedstocks; Hydrodearomatization (HDA) of petroleum feedstocks; Hydrodesulfurization (HDS) of petroleum feedstocks; Hydrodenitrogenation (HDN) of petroleum feedstocks; Hydrodemetallization (HDM) of petroleum feedstocks; or At least one process is the hydrotreating of a loaded hydrocarbon feed or petroleum feedstock containing components boiling 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.

2. The supported catalyst of claim 1 useful in the process of

11. 11. The supported catalyst of claim 10, wherein the catalyst is pre-impregnated, shaped, dried, and calcined.

12. The catalyst has a d ５０ 12. The supported catalyst of claim 10 or 11, wherein

13. 1. A process for processing a hydrocarbon feedstock comprising at least one of paraffinic, aromatic, and naphthenic components to produce a processed product, the process comprising: (I) Hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, the processes comprising contacting a feedstock in at least one reactor with hydrogen under hydroprocessing or hydrocracking conditions using the supported catalyst of claim 1. and recovering the products; (II) hydrotreating the hydrocarbon feed containing components boiling 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 subjecting the feed to isothermal or substantially isothermal hydrotreating.

2. The method of claim 1, further comprising contacting the supported catalyst of claim 1 with hydrogen under hydrotreating conditions. hydrotreating, including recovering the product; (III) hydroconverting said hydrocarbon feed having components boiling above 600° F. (315.6° C.) to form a product having an increased proportion of components boiling below about 600° F. (315.6° C.), comprising contacting said feed with hydrogen and the supported catalyst of claim 1 at isothermal or substantially isothermal hydrotreating conditions, and forming the product, including recovering the product; (IV) hydroconverting the feed, comprising contacting the feed containing a hydrocarbon oil with hydrogen and the supported catalyst of claim 1 under conditions of elevated temperature greater than about 600°F (315.6°C) and pressure greater than about 500 p.s.i.g. (3.44 MPa), and recovering the product.

14. 14. The process of claim 13, wherein the recovered product after treatment exhibits at least one of a reduced content of aromatic components, an increased content of paraffinic components, a reduced viscosity, and an increased viscosity index compared to the untreated hydrocarbon feedstock.

15. 1. A method for preparing a catalyst, comprising the steps of: (I) hydroprocessing of petroleum feeds; (II) Hydrocracking (HCR) of petroleum feedstocks; (III) Hydrodesulfurization of hydrocarbons; (IV) Hydrodenitrogenation of hydrocarbons; (V) hydrodearomatization (HDA) of petroleum feedstocks; (VI) Hydrodemetallization of hydrocarbons, and (VII) hydrotreating a loaded hydrocarbon feed containing components boiling 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. For use in a process, The method comprises impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Group 6 (alternatively referred to as Group VIB) of the Periodic Table of the Elements, at least one catalytic agent or catalytic agent precursor selected from the group consisting of compounds of Groups 8, 9 or 10 (alternatively referred to as Group VIII) of the Periodic Table of the Elements, and optionally a phosphorus-containing compound and at least one organic chelate compound, wherein the Groups VIB and VIIIB and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere, and thereafter drying and calcining the resulting impregnated support, wherein the support is mixing an alumina-containing powder with water and optionally nitric acid to form a wet mixture; and The wet mixture is then mixed with a support suitable for use in a hydroprocessing reactor. drying and calcining the powder, which has been prepared by shaping to form particles; The support has 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, prior to incorporation of metals and, if present, phosphorus, corresponding to values ​​measured using mercury porosimetry: ≧25% to 45% TPV in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm); a TPV of greater than 15% to less than 30% in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); and The method includes a porous inorganic oxide having 10% or more and less than 30% of its pore volume in pores having diameters of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

16. 16. The method of claim 15, further comprising drying and calcining the substrate particles after shaping to form calcined pills.

17. The aqueous solution may contain any of the following: acetic acid, citric acid, tartaric acid, oxalic acid, maleic acid, malonic acid, malic acid, butanediol, pyruvic aldehyde, 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 ...

17. The method of claim 15 or 16, wherein the organic chelate compound is diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, or a mixture of any two or more thereof.

18. The method of any one of claims 15 to 17, wherein the organic chelating compound comprises citric acid.

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

20. 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; a TPV of greater than about 25% to about 45% in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm); a TPV of greater than about 15% to less than about 30% in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm); A porous inorganic oxide carrier or support comprising greater than 10% and less than 30% TPV in pores having diameters between 1000 Å (100 nm) and 30,000 Å (3,000 nm).

21. 21. The porous inorganic oxide carrier or support of claim 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 clays, synthetic clays, cationic clays, anionic clays, or mixtures of any two or more thereof.

22. 22. The porous inorganic oxide carrier or support of claim 20 or 21, wherein the support exhibits a d50 of greater than or equal to 110 Å (11 nm) and less than or equal to about 170 Å (17 nm).

23. Approximately 185m ２ / g ~ approx. 425m ２ 23. The porous inorganic oxide carrier or support of any one of claims 20 to 22, having a total surface area as determined by nitrogen adsorption using the BET technique of 0.1 g / g.

24. 24. The porous inorganic oxide carrier or support of any one of claims 20 to 23, having greater than about 55% to about 75% of pores having a diameter of less than 200 Å (20 nm) as measured using mercury penetration techniques.

25. About 85% to about 98% by weight Al ２ O ３ and about 15% to about 2% by weight of SiO ２ and Al ２ O ３ and SiO ２ The porous inorganic oxide carrier or support according to any one of claims 20 to 24, comprising:

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