High-Activity Hydrogenation Catalyst and Process Using the Same

Abstract

A supported catalyst for hydroprocessing, hydrotreating, or hydrocracking a hydrocarbon feedstock, comprising 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 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. The metal, and phosphorus, if present, are supported on and / or within a porous inorganic oxide support or substrate, the support prior to incorporation of the metal and phosphorus having a total pore volume (TPV) of from about 0.8 cc / g to about 1.5 cc / g and comprising a specified pore size distribution, the supported catalyst comprising the specified pore size distribution.

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 on January 8, 2021, the contents of which are hereby incorporated by reference in their entirety into this specification.

Background Art

[0002] In the petroleum industry, there continues to be a need for improved catalyst supports and supported catalysts that exhibit a desirable balance of enhanced activity, improved catalyst life, and morphological properties for use in hydrotreating hydrocarbon feedstocks.

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

[0004] For supported catalysts used in hydrotreating hydrocarbon feedstocks, morphological properties of the support such as surface area, pore volume, pore size, and the 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 catalyst sites, the diffusion of reactants to the active catalyst sites, the diffusion of products from the active sites, and catalyst life. In addition, the support and its dimensions also affect mechanical strength, density, and reactor filling characteristics, all of which are important in commercial applications.

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

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

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

[0008] In general, it is desirable to design a hydroprocessing catalyst that exhibits a large surface area in order to maximize the concentration and activity of the catalytic sites. However, the surface area and pore diameter are inversely proportional within practical limits. As a result, catalyst supports, such as alumina or silica-alumina particles, which mainly contain small pores, exhibit the largest surface areas. In contrast, for the diffusion of feedstock components, particularly as the catalyst ages and becomes contaminated, sufficiently large pores are required, but larger pores have a lower surface area. More specifically, catalyst formulators or designers and process engineers often face competing considerations that often define the balance of the 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 hydroprocessing catalyst, but such sites are likely to be blocked by coke, thereby causing a decrease in catalyst activity. Conversely, if the supported catalyst has more than about 10% of the total pore volume occupied by pores having a pore diameter greater than 1000 Å (100 nm), the mechanical crushing 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 pore diameters in the range of 200 Å (20 nm) to less than 1000 Å (100 nm) can provide a balance between activity and catalyst life within a region referred to as the mesopore region for the purposes of the present invention.

[0010] Therefore, increasing the surface area of the catalyst can increase the number of active sites, but such an increase in surface area results in an increase in the proportion of smaller pores that are more likely to be clogged by coke and other components present in the hydrocarbon feed. That is, increasing the surface area and maximizing the concentration of the support catalyst exhibiting pore diameters in the mesopore range are opposing characteristics. 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. Accordingly, a stable support particle exhibiting a combination of pore size distribution and total surface area that can provide a combination of performance characteristics suitable for use as a catalyst support, particularly when used to support catalytically active metals for manufacturing hydroprocessing catalysts, continues to be sought.

[0011] Furthermore, the physical and chemical properties of the porous support can depend on the procedure followed during its preparation, and many processes have been developed in attempts to optimize the support properties for their use as catalyst supports. Examples of suitable porous support materials and preparation methods are described below. Generally, an alumina support 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. Accordingly, catalyst supports containing alumina supports are known, but further improvements are needed to provide supports having even more improved properties. SUMMARY OF THE INVENTION

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

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

[0014] Further embodiments include a process for treating a hydrocarbon feedstock comprising at least one of paraffin, aromatic, and naphthene components to produce a treated product, the process comprising: (I) hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, wherein the process comprises contacting the feedstock in at least one reactor with hydrogen using the supported catalyst described above under hydroprocessing or hydrocracking conditions and recovering the product, hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking; (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, the hydrotreating comprising contacting the feed with hydrogen and the supported catalyst described above under isothermal or substantially isothermal hydrotreating conditions and recovering the treated product; (III) hydroconverting a hydrocarbon feed having components with boiling points above 600°F (315.6°C) to form a product having an increased proportion of components with boiling points below about 600°F (315.6°C), the forming comprising contacting the feed with hydrogen and the supported catalyst described above under isothermal or substantially isothermal hydrotreating conditions and recovering the product; and (IV) hydroconverting the feed, the hydroconverting comprising contacting a feed containing hydrocarbon oil with hydrogen and the supported catalyst described above under conditions of a temperature above about 600°F (315.6°C) and a pressure above about 500 p.s.i.g. (3.44 MPa) and recovering the product, selected from the group consisting of.

[0015] A further embodiment includes a method for preparing a catalyst for use in at least one petroleum hydrocarbon processing process, the method comprising impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalyst agent or catalyst agent precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the Periodic Table of the Elements, at least one catalyst agent or catalyst agent precursor selected from the group consisting of compounds of Group 8, Group 9 or Group 10 (or Group VIII) of the Periodic Table of the Elements, optionally a phosphorus-containing compound and at least one organic chelating compound, wherein the Group VIB and Group VIIIB and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere; and then drying and calcining the resulting impregnated support, wherein the support is prepared by (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, and 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, namely, (i) 25% or more to 45% of the TPV in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm), (ii) more than 15% to less than 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (iii) 10% or more to less than 30% of the pore volume in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), and comprises a porous inorganic oxide.

Brief Description of the Drawings

[0016]

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BEST MODE FOR CARRYING OUT THE INVENTION

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

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

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

[0020] The term "about", when used as a modifier of a variable, feature, or condition, or used 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 temperature, speed, time, concentration, amount, content, pore size, pore volume, and size including surface area that are outside the recited ranges or different from a single recited value will achieve the desired result or results described in this application, namely, 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" = subtract from 100 the percentage of hydrocarbons boiling above 700°F (371.1°C) based on a SimDist (simulated distillation) test conducted according to ASTM D2887, "Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography", after hydroprocessing, for example, including HDA, HCR, HDN, and / or HDS.

[0022] For example, "component" as applied to a metal in a catalyst impregnation solution or to the catalyst itself refers to any compound or complex, including salts, oxides, sulfides, 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 "have", "having", "includes", "include", and "including", and variations thereof, such as the word "comprise" and its variations, mean that the specified step, element, component, or material to which it refers is essential, but other steps, elements, components, or materials may be added and still form a composition within the scope of the claim or disclosure. When described in the description and claims of the present invention, it means that the present invention and what is claimed are considered to be the following and potentially more. These terms are inclusive or open-ended, especially when applied to the claims, and do not exclude elements, components, or method steps not additionally described.

[0024] The "feedstock" or petroleum feedstock typically processed using the process of the present invention is often described in terms of being "heavy" or "light" in terms of the perspective. The terms "light" and "heavy" with respect to petroleum fractions are used herein in their ordinary meaning within the refining industry to refer to relatively low and high boiling point ranges, respectively. Heavy Fuel Oil (HFO) includes both the final product (residual fuel) and the primary refinery stream into which they are blended. Members of the heavy fuel oil category have a wide range of molecular weights, carbon numbers (typically from about C7 to about C 50)and a diverse group of substances including hydrocarbons having a boiling point of about 250°F to about 1112°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 compounds or metal compounds. The final heavy fuel (residual fuel) is a product mainly containing the residue of the refining process after substantially all 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 a 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 can include a mixture of petroleum fractions such as atmospheric and vacuum gas oils (AGO and VGO). Suitable feedstocks include heavy hydrocarbon minerals or synthetic oils, or mixtures of one or more fractions thereof. Thus, known feedstocks such as straight-run gas oil, vacuum gas oil, demetallized oil, deasphalted vacuum residue, coker distillate, catalytic cracking distillate, shale oil, tar sand oil, coal liquefaction oil, etc. are contemplated. Preferred feedstocks have a boiling range starting at a temperature above about 260°C (above about 500°F). The hydrocracking feedstock may typically contain nitrogen present in an amount of 1 ppm to 1.0 wt% as an organic nitrogen compound. The feedstock also typically includes sulfur-containing compounds sufficient to provide a sulfur content above 0.15 wt%. The boiling range of the various product fractions recovered at any particular refinery varies depending on factors such as the characteristics of the crude oil source, the regional market of the refinery, and the product price. The American Petroleum Institute (API) recommended to the Environmental Protection Agency (EPA) a list of generic names for refinery streams that is consistent with industry practice and encompasses all known processes used by refiners.A list containing the common name, Chemical Abstracts Service (CAS) number, and the definition of each stream was published by the EPA as "Addendum I, Generic Terms Covering Petroleum Refinery Process Streams". The definitions for these streams can also be found in the "High Production Volume (HPV) Chemical Challenge Program, Test Plan, Heavy Fuel Oils Category" submitted by the U.S. EPA, The Petroleum HPV Testing Group (June 17, 2004), Appendix A, pages 38 - 42. The petroleum streams suitable for treatment using the catalyst of the present invention are specified in the EPA document, the content of which is incorporated herein by reference to the extent permitted.

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

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

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

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

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

[0030] Each of the above definitions of micropores, mesopores, mesopore sub-ranges, and macropores is distinct and without overlap, such that pores are not double-counted when summing percentages or values in the pore diameter distribution for any given sample.

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

[0032] As used herein, "total pore volume" penetration means the cumulative volume in cc / g of all pores distinguishable by either the nitrogen desorption method or mercury penetration, also known as mercury intrusion porosimetry. For catalyst supports or carrier particles, for example, alumina powder and alumina or silica-alumina powder or support particles, the pore size distribution and pore volume can be calculated with reference to the nitrogen desorption isotherm (assuming cylindrical pores) by the B.E.T. (or BET) technique described by S. Brunauer, P. Emmett, and E. Teller in the Journal of American Chemical Society, 60, pp209-31.9 (1939), and reference is also made to ASTM D3037, which identifies the procedure for determining the surface area using the nitrogen BET method. The nitrogen desorption method is particularly useful for smaller-sized pores, while the mercury intrusion method is generally recognized as being better suited for larger-sized pores. Unless otherwise specified, the mercury intrusion method is conveniently used to measure and represent values and ranges over the entire range of pore diameters present in the powders, carriers, catalyst supports or carriers, and supported catalysts disclosed herein.

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

[0034] The pore size distribution using the mercury intrusion method can be calculated according to the following equation:

[0035]

Equation

[0036] The total N2 pore volume of the sample is the sum of the nitrogen pore volumes determined by the nitrogen desorption method described above. Similarly, the total mercury pore volume of the sample is the sum of the mercury pore volumes determined by the mercury intrusion 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 determined by nitrogen adsorption using the BET technique described above, whether in powder form or in aggregate form.

[0038] All morphological properties related to weight, such as pore volume, PV (cc / g), or surface area, (surface area, SA) (m 2 / g), can be normalized to a "metal-free basis" according to procedures known in the art. However, the morphological properties reported herein are on a "measured as is" basis without correction for metal content.

[0039] "Periodic Table": All references to the periodic table of elements herein refer to the periodic table of elements published by the International Union of Pure and Applied Chemistry (IUPAC), and the version dated February 19, 2010, of http: / / old.iupac.org / reports / periodic_table / is publicly available online.

[0040] When used in this specification with respect to a numerical range, the terms "approximately", "about", "substantially", and similar terms are understood by those skilled in the art and will vary to some extent depending on the context in which they are used. Where the use of a term is not clear to those skilled in the art, considering the context in which it is used, the term will be plus or minus 10% of the disclosed value. When the terms "approximately", "about", "substantially", and similar terms are applied to structural features (e.g., to describe its shape, size, orientation, direction, etc.), these terms are meant to include, for example, minor variations in the structure that may result from the manufacturing or assembly process, and are intended to have a broad meaning that is consistent with the common and accepted usage by those skilled in the art to which the subject matter of this disclosure pertains. Accordingly, these terms should be construed as indicating that non-substantive or insignificant modifications or variations of the described and claimed subject matter are within the scope of this disclosure as recited in the appended claims. Unless otherwise defined with respect to a specific property, feature, or variable, the term "substantially" as applied to any criterion such as a property, feature, or variable means that those skilled in the art would understand that the benefit to be achieved, or the desired condition or property value is met, to the extent that the recited criterion is satisfied. For example, for the use of the term "substantially" in relation to the description of substantially isothermal, see the following.

[0041] When used with respect to various processes for treating a hydrocarbon feedstock, the phrase "substantially isothermal" is typically understood to mean that the operation of the process is such that the temperature can vary by typically less than about 50°F, preferably less than about 40°F, more preferably less than about 30°F, for example less than about 20°F, for example near 0°F, up to a maximum of about 20°F or 30°F or 40°F or 50°F across the catalyst bed. Alternatively, the operation of such a process may be referred to as operating isothermally while exhibiting temperature variations as described above.

[0042] In the context of describing elements (especially in the context of the following claims), the words "a", "an", and "the", and similar designations shall, unless otherwise indicated herein or unless the context clearly dictates otherwise, be construed to cover both the singular and the plural forms. The recitation of a range of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, 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 unless the context clearly dictates otherwise. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is merely intended to better illustrate the embodiments and is not intended to limit the scope of the claims unless otherwise specified. No language in this specification should be construed as indicating any non-claimed element as essential.

[0043] Embodiments of the present invention include a catalyst support and a method for preparing a supported catalyst using such a support, as well as the use of the supported catalyst for hydroprocessing, hydrocracking (HCR), hydrodearomatization (HDA), hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), and hydrodemicrocarbon residue (HDMCR) or microcarbon reduction activity. The supports or carriers disclosed herein are also useful for preparing other catalysts useful in various processes. More specifically, embodiments also relate to a porous catalyst support or carrier 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 from Group 6 (also referred to as Group VIB) and at least one of Groups 8, 9, and 10 (also referred to as Group VIIIB) of the Periodic Table of the Elements, and optionally containing phosphorus.

[0044] Exemplary carriers or supports are generally identified as inorganic oxide porous carriers, and such carriers will generally be understood to have many pores, perforations, and / or porosity. Examples of suitable porous carrier materials include silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed 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 or anionic clay, such as saponite, bentonite, kaolin, sepiolite or hydrotalcite, and mixtures thereof. Preferred porous carrier materials are silica, silica-alumina, alumina, titania, titania-alumina, zirconia, bentonite, boria, and mixtures thereof, with silica, silica-alumina, alumina and mixtures thereof being particularly preferred, and alumina containing up to about 20 wt% silica, preferably up to about 12 wt% silica, for example up to about 10 wt% silica being the same.

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

[0046] [Table 1]

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

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

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

[0050] In a preferred embodiment for preparing alumina or silica-alumina, the filter cake produced during the synthesis process is dried to produce a powder that can be conveniently stored without significant degradation over a long period of time prior to further processing. Drying of the filter cake can be carried out by several methods such as tray drying, belt drying, spray drying, combinations thereof, etc. The drying conditions are typically adjusted to effect partial removal of water, for example, to a level of volatile matter of about 20 wt% to about 35 wt%, preferably about 22 wt% to about 30 wt%, for example, about 23, 24, 25, 26, 27, 28, or 29 wt% of volatile matter.

[0051] Mix dry alumina and / or silica-alumina powder with water to provide a moist or wetted mixture or mass, which is referred to as a wet mixture or dough. Optionally, an acidic or basic aqueous medium, such as an aqueous solution of an acid or acidic salt, can also be added to the mixture. When an acid is included, preferably an aqueous solution of a monobasic mineral acid is mixed with water and alumina to provide the mixture. Hydrochloric acid, and other strong monobasic acids including nitric acid may be used. Nitric acid is preferred. Other useful acids include organic acids such as acetic acid, formic acid, propionic acid, etc. Alternatively, an aqueous base such as ammonium hydroxide can be used. Additionally, as disclosed in the art, recycled calcined product fines in an amount up to about 25 wt% of the total alumina can be advantageously added during this step.

[0052] The mixture obtained from the previous step is referred to as a wet mixture. This mixture is formed into a carrier, for example, in the form of pills or other shapes, as described elsewhere in this specification. This step is conveniently carried out by extruding the wet mixture, typically followed by drying and firing of the pills.

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

[0054] Properties of the Silica-Alumina Support As described 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 in the form of pills, etc., and then dried and preferably calcined. The recycled fines typically contain the inorganic oxide itself or a milled catalyst or its corresponding support or carrier and typically exhibit a particle size in the range of 10 to 100 micrometers. In the following description, the product produced at this stage of the process is referred to as "alumina support particles", catalyst support particles or "catalyst carrier particles" or simply "support" or "carrier" particles.

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

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

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

[0058] The support particles or carrier particles of the present invention have a total pore volume (TPV) before incorporating the catalytic metal and other catalyst components, which is sometimes also referred to as the total intrusion volume TIV or total mercury pore volume, referring to measurements performed using, for example, the mercury intrusion method, 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 in 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 catalyst components, such as chelating agents or chelating agent residues after drying and / or calcination, is typically significantly lower, for example, about half of the values listed above for the support itself. The TPV values measured for the supported catalysts of the examples herein were due in part to the high content of the catalytic metal and were about 0.45 cc / g.

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

[0061] The content of pore sizes of 1000 Å or more and 30,000 Å (3,000 nm) or less measured using the mercury intrusion method 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. Further, for each of the ranges resulting from the listed lower and upper limits, the "greater" and "lesser" amounts include values expressed in tenths of a percent as well as unit percentage values.

[0062] The content of pores in the carrier particles useful in the present invention, that is, the content of pores having a diameter of 200 Å (20 nm) or more and less than 1000 Å (100 nm) measured using the mercury intrusion method is typically in the range of about 15% or more to 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. Further, for each of the ranges resulting from the listed lower and upper limits, the "greater" and "lesser" amounts include values expressed in tenths of a percent.

[0063] The pore content of the carrier particles measured using the mercury intrusion method, that is, the pore content of the carrier particles showing pores having a diameter of less than 200 Å (20 nm) is typically more than about 55% to about 75%, or exceeds 57%, or 59%, or 61%, or 63%, or 65%, or 67%, or 69%, and is about 74%, or 73%, or 72%, or 71%, or 70%, or 69%, or 68%, or 67%, or 65% or less. Further, for each of the ranges resulting from the listed lower and upper limits, the "greater" and "lesser" (or the amounts of its value) include values expressed in tenths of a percent as well as unit percentage values.

[0064] Carrier particles suitable for use in the present invention can also contain pores within a pore size range exhibiting a pore size of about 100 Å (10 nm) to about 200 Å (20 nm), which is also measured and reported using the mercury intrusion 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 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% or more, and about 44%, or 43%, or 42%, or 41%, or 40%, or 39%, or 38% or less. Further, for each of the ranges resulting from the listed lower and upper limits, "greater" and "less" (or amounts of its value) include values expressed in tenths of a percent as well as unit percentage values.

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

[0066] The carrier particles or support particles typically have a d50 (also measured using the mercury intrusion method) greater than about 110 Å (11 nm) and less than about 170 Å (17 nm), or greater than about 120 Å (12 nm) and less than about 160 Å (16 nm), for example, greater than about 125 Å (12.5 nm) and less than about 135 Å (13.5 nm). On the other hand, the supported catalyst of the present invention typically has a d50 (also measured using the mercury intrusion method) greater than about 125 Å (12.5 nm) and less than about 210 Å (21 nm), or greater than about 130 Å (13 nm) and less than about 200 Å (20 nm), for example, greater than about 135 Å (13.5 nm) and less than about 200 Å (20.5 nm). Referring to FIGS. 1A - 1C, when measured using nitrogen, an initial peak appears at about 80 Å (8 nm), and when measured using the mercury intrusion method, an initial peak appears at about 90 Å - 100 Å (9 - 10 nm).

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

[0068] The supported catalyst prepared according to the present invention disclosed herein shows a pore size distribution measured using the mercury porosimetry method disclosed herein as well, including the following characteristics: (A) For pores having a diameter of less than 200 angstroms (Å) (20 nm), the TPV is about 50% or more and up to about 75%, or 51% or more, or 52% or more, or 53% or more, or 54% or more, or 55% or more, or 56% or more, or 57% or more, or 58% or more, or 59% or more, or 60% or more, or 62% or more, or 64% or more, and up to about 73%, or about 71%, or about 69%, or about 67%, or about 65%, or 63% of the TPV. (B) It shows pore sizes of about 100 Å (10 nm) to about 200 Å (20 nm) that are similarly measured and reported using the mercury intrusion method, and typically has a pore content of about 35% to about 60%, or more 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 up to about 59%, or 58%, or 57%, or 56%, or 55%, or 54%, or 53%, or 52%, or 51%, or 50% of the pore content. Further, for each of the ranges resulting from the listed lower and upper limits, "greater" and "lesser" amounts include values expressed in tenths of a percent as well as unit percentage values. (C) Pores within the pore size range generally specified as having a pore diameter 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 the mercury intrusion method typically have a pore content of more than about 4% to about 14%, or more than 5%, or 6%, or 7%, or 8%, or 9%, or 10%, and up to about 13%, or 12%, or 11%, or 10% of the pore content. Further, for each of the ranges resulting from the listed lower and upper limits, "greater" and "lesser" amounts include values expressed in tenths of a percent as well as unit percentage values. (D) For pores with diameters of 200 Å (20 nm) to less than 1000 Å (100 nm), the TPV is more than about 15% and less than about 30% at most, or more than about 17%, or more than about 20%, or more than about 22%, and less than about 28% at most, or less than about 25%, or less than about 23%. (E) For pores with diameters of 1000 Å (100 nm) to 30,000 Å (3,000 nm), the TPV is 10% or more and less than 30%, or 12% or more, or 15% or more, or 17% or more, or 20% or more, and less than 28% at most, or less than 25% at most, or less than 23% at most.

[0069] Catalyst Preparation Generally, the hydrotreating catalyst can be produced using alternative methods. In the impregnation method (note that the pre-impregnation method and the post-impregnation method will be 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, calcined, and impregnated with a Group 6 (e.g., Mo) metal compound or precursor and a Group 8, 9, or 10 (e.g., Ni) metal compound or precursor on the support. Then, the impregnated wet pellets are dried and calcined to obtain a supported catalyst. In another preparation method, an alumina-containing powder, e.g., silica-alumina, a catalyst metal precursor, water, and additives such as an extrusion aid, peptizing chemical, etc. are combined, mixed, and extruded into pellets. Then, the metal-containing wet pellets are 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. Patent Nos. 7,390,766, 7,560,407, and 7,642,212 (assigned to D.P. Klein, Advanced Refining Technologies), the disclosures of which are incorporated herein by reference to the extent permitted. Suitable methods and compositions involve adding to a suitable amount of water (A) at least one substantially water-insoluble Group 8, Group 9, or Group 10 metal component and (B) at least one substantially water-soluble phosphorus-containing acidic component in an amount insufficient to cause dissolution of at least one Group 8, Group 9, or Group 10 metal component to form a slurry typically at ambient temperature, combining the slurry with (C) at least one Group 6 metal component, mixing the combination of (A), (B), and (C), heating the mixture to a time and temperature sufficient for (A), (B), and (C) to form a solution, and (E) adding additional water as necessary to obtain a solution concentration of at least one Group 8, Group 9, or Group 10 metal, at least one Group 6 metal, and phosphorus useful for impregnating 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 at least one Group 8, Group 9, or Group 10 metal to the Group 6 metal is about 0.05 to about 0.45, provided that the amount of at least one Group 8, Group 9, or Group 10 metal is sufficient to promote the catalytic effect of the Group 6 metal, the concentration of the Group 6 metal expressed as an oxide is at least about 3 to about 50 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 the Group 6 metal of less than about 0.05 to about 0.25. In still further embodiments, the process includes separating the volatile portion of the solution from the impregnated and unfired support to obtain a dried catalyst having the desired water content.

[0071] The term "pre-impregnated" catalyst refers to a catalyst in which a metal-containing solution (one or more) is added before the porous catalyst support is calcined. The metal-containing solution (one or more) can be added before or after the formation of the catalyst particles, but in an important aspect, the metal-containing solution (one or more) is added before the support material is calcined. However, there are significant advantages in that the unfired support can be obtained by forming it after impregnation (contact) with an aqueous solution containing one or more catalyst metals. These advantages are observed in the form of a more desirable distribution of the metal throughout the support in the final catalyst. Thus, a "pre-impregnated" catalyst can be prepared as follows: The uncalcined alumina-containing silica-alumina powder is thoroughly mixed with water and, optionally, 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, for example, molybdenum, nickel, and phosphorus compounds, and further an optional additional amount of one or more metal solutions of Group 8, 9, and 10 to provide the desired amount of metal on the final catalyst, if necessary. The one or more metals of Group 8, 9, or 10 used to achieve the optional additional amount of one or more metals of Group 8, 9, or 10 are typically selected to be water-soluble under the temperature conditions encountered. Further, as described elsewhere herein, a chelating agent or compound may optionally but preferably be included in the impregnation solution.

[0072] A metal-containing mixture typically containing from about 50 to about 65 weight percent moisture is preferably formed into catalyst particles of a desired size by extrusion. The formed catalyst particles are dried using alternative or combined heating methods including high-temperature drying and a combination of high and moderate calcination temperatures. For example, wet-impregnated catalyst particles can be subjected to high-temperature drying conditions of from about 375°F (190.6°C) to about 425°F (218.3°C), such as 400°F (204.4°C), for about 30 to 60 minutes, such as 40 minutes, or for the total time, to achieve the desired target LOI level disclosed elsewhere herein. Alternatively, wet-impregnated catalyst particles can be subjected to an initial high-temperature drying temperature of from about 300°F (148.9°C) to about 340°F (171.1°C), such as 320°F (160°C), for a limited time, such as about 8 to 12 minutes, such as 10 minutes, and then the temperature is raised to a moderate calcination temperature of from about 650°F (343.3°C) to about 690°F (365.6°C), such as 670°F (354.4°C), for about 30 to about 60 minutes, such as 40 minutes, and then the catalyst particles are held at the final ramp temperature for about 8 to 12 minutes, such as about 10 minutes, or for the total time, to achieve the desired target LOI level disclosed elsewhere herein. Regardless of the drying method used, careful consideration must be given to whether a chelating agent is included in the impregnation solution, and when one or more drying methods are 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 can be utilized to measure the residual levels of chelating agents, complexes, or thermal by-products in the dried supported catalyst.

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

[0074] A significant difference between the pre-impregnated catalyst and the post-impregnated catalyst is that the post-impregnated catalyst undergoes two calcination steps. Typically, the first step consists essentially of calcining a porous support, and in a subsequent second step, the calcined support is impregnated with a catalytically active metal component and optionally a phosphorus component. In contrast, the pre-calcined catalyst undergoes one calcination step as described.

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

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

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

[0078] (ii) The organic compound according to preferably contains at least two carbonyl moieties. It is preferred that at least one carbonyl moiety is present in a carboxyl group. It is even more preferred that at least one nitrogen atom is covalently bonded to at least two carbon atoms. The preferred organic compound satisfies formula (I) or (II), (R 1 R)N-R 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 ’ are 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 amide. R 3 is an alkylene group having up to 10 carbon atoms which may be interrupted by -O- or -NR 4 -. R 4 is R 1is selected from the same groups as those shown above. R 3 The alkylene group may be substituted with one or more groups selected from carbonyl, carboxyl, ester, ether, amino, or amide. As described above, it is essential that the organic compound of formula (I) or (II) contains at least one carbonyl moiety. Preferably, R 1 , R 2 , R 1 ’, and R 2 ’ (in formula (I)), and at least two of R 1 , R 2 , and R 1 ’ (in formula (II)) have the formula -R 5 -C(O)OX, where R 5 is 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 can be bonded to two or more -R 5 -C(O)O- groups. Typical examples of the compounds of formula (I) are ethylenediamine(tetra)acetic acid (EDTA), hydroxyethylenediamine triacetic acid, and diethylenetriamine pentaacetic acid. A typical example of the compound of formula (II) is nitrilotriacetic acid (NTA).

[0079] The catalyst composition typically contains, in total, about 30 to about 45% by weight of at least one metal component of Group 6 of the Periodic Table (or Group VIB) and at least one metal component of Group 8, 9, or 10 of the Periodic Table (or Group VIIIB), or a mixture thereof, and the Group VIB and Group VIIIB metal components are calculated as oxides and are 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 component constitutes about 35 to 55% by weight, calculated as oxides and based on the total weight of the catalyst composition. Alternatively, the total weight of the Group 6 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 constitutes about 30 to about 45% by weight, calculated as an oxide, or from about 31, 32, 33, 34, 35, 36, 37, or 38% by weight to about 45, 44, 43, 42, 41, 40, 39, 38, 37, or 36% by weight.

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

[0082] After impregnation, drying, and firing, the supported catalyst composition, i.e., the metal-containing component and phosphorus (if included), exist as their oxides and preferably exhibit the above characteristics before the sulfurization step, if any.

[0083] The term "aggregate" refers to a product combining particles held together by various physicochemical bonds, and the term "forming" and its grammatical variations refer to the action of forming aggregates. More specifically, each aggregate is composed of a plurality of adjacent primary porous support particles as constituent components, preferably joined and connected at their contact points. Thus, aggregate particles typically exhibit a higher macropore content than the primary particles that are the constituent components for producing the aggregate particles due to the interparticle voids between the composite particles that are the constituent components. These larger voids are not included as part of the characteristic properties of the primary porous support particles, such as a specific pore size or range and pore size distribution characteristics.

[0084] Agglomeration of the porous support, e.g., alumina, composites, is carried out according to methods known in the art, in particular, methods such as pelletization, extrusion, and forming into beads in a rotating coating drum. A modularization technique can be used to agglomerate composite particles having a diameter of about 0.1 mm or less into particles having a diameter of at least about 0.8 mm using a granulating liquid. As known to those skilled in the art, agglomeration can optionally be carried out in the presence of an additional amorphous or crystalline binder, and a pore former can be added to the mixture to be agglomerated. Conventional binders include other forms of alumina, silica, silica-alumina, clay, zirconia, silica-zirconia, magnesia, and silica-boria. Conventional pore-forming agents can be used, and examples of suitable reagents include wood flour, charcoal, cellulose, starch, naphthalene, and generally organic compounds that promote pore formation and can be removed by firing. However, the addition of a pore former may not be necessary or desirable.

[0085] Catalyst compositions can have different shapes selected for their suitability for the processes and / or apparatuses in which they are used. For example, when catalyst compositions are used in slurry reactors, fluidized beds, moving beds, or expanded beds, spray drying or beading is generally applied. For fixed bed or fluidized bed applications, generally, the catalyst compositions are extruded, pelletized, and / or beaded. In the latter case, at any stage before or during the shaping process, any additives commonly used to facilitate shaping can be added. These additives can include aluminum stearate, surfactants, graphite, starch, methylcellulose, bentonite, polyethylene glycol, polyethylene oxide, or mixtures thereof. Further, as considered elsewhere, when alumina is used as a support, nitric acid may be added prior to the shaping process, for example, for the purpose of increasing the mechanical strength of the aggregates. In the present invention, the shaping process 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. Controlling the amount of water appropriately is within the scope of those skilled in the art.

[0086] Suitable shapes include powders, spheres, cylinders, rings, and symmetric or asymmetric multi-lobed forms, such as trilobal and quadrilobal. Particles resulting from extrusion, beading, or pelletizing typically have a diameter in the range of about 0.2 to about 10 mm and a length in the range of about 0.5 to about 20 mm, although deviations from these general ranges are possible. Catalysts in the form of extrudates are generally preferred.

[0087] The present invention also relates to a catalyst composition according to the present invention, in which the metal components are partially or completely converted to their sulfides. In that case, the catalyst preferably essentially does not contain Group VIIIB metal disulfides.

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

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

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

[0091] Use of the catalyst in a hydroprocessing process The catalyst prepared according to the present invention can be used in substantially all hydroprocessing processes for treating a plurality of feeds under a wide range of reaction conditions, generally, for example, temperatures in the range of about 200 °C to about 500 °C, hydrogen pressures in the range of about 5 to 300 bar (0.5 MPa to 30 MPa), and liquid hourly space velocities (LHSV) in the range of about 0.05 to 10 h -1 under. The term "hydroprocessing" includes various petroleum refining processes in which a hydrocarbon feed is reacted with hydrogen at high temperature and high pressure (hydroprocessing reaction conditions), including hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydrocracking, and hydrocracking under mild pressure conditions, also known as mild hydrocracking.

[0092] More specifically, "hydroprocessing", as used herein, means reacting a petroleum feedstock (a complex mixture of hydrocarbons present in petroleum) with hydrogen in the presence of a catalyst under pressure to (a) reduce the concentration of at least one of sulfur, contaminating metals, nitrogen, and Conradson carbon present in the feedstock, and (b) reduce at least one of the viscosity, pour point, and density of the feedstock. Hydroprocessing includes hydrocracking, isomerization / dewaxing, hydrofinishing, and hydrotreating processes that differ in the amount of hydrogen reacted and the nature of the petroleum feedstock being processed.

[0093] Hydrocracking is typically understood to include the hydroprocessing of predominantly hydrocarbonaceous compounds (the "feedstock") containing at least five (5) carbon atoms per molecule, and the process is carried out (a) at a hydrogen partial pressure above atmospheric pressure, (b) at a temperature typically below 593.3 °C (1100 °F), (c) using the overall net chemical consumption of hydrogen, and (d) in the presence of a solid-supported catalyst containing at least one hydrogenation component.

[0094] Hydrotreating is typically understood to include hydroprocessing of a predominantly hydrocarbonaceous compound (the "feedstock") containing at least five carbon atoms per molecule for the desulfurization and / or denitrification of the feedstock, and the process is carried out (a) at a hydrogen partial pressure above atmospheric pressure, (b) at a temperature typically below 593.3 °C (1100 °F), (c) using the overall net chemical consumption of hydrogen, and (d) in the presence of a solid-supported catalyst containing at least one hydrogenation component.

[0095] Operating conditions for the hydrotreating of heavy hydrocarbon streams such as petroleum hydrocarbon residues 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), an average catalyst bed temperature in the range of about 700 °F (371 °C) to about 850 °F (454 °C), a liquid hourly space velocity (LHSV) in the range of about 0.1 to about 5 volumes of hydrocarbon per volume of catalyst per hour, and a hydrogen recycle rate or hydrogen addition rate in the range of about 2,000 standard cubic feet per barrel (SCFB) (356 m 3 / m 3 ) to about 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 - 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 rate or hydrogen addition rate in the range of about 3,000 SCFB (534 m 3 / m 3 ) to about 10,000 SCFB (1,781 m 3 / m 3) includes a hydrogen recycle rate or a hydrogen addition rate within the range. Generally, the process temperature and the space velocity are such that at least 30% by volume of the feed fraction boiling above 1,000°F is converted to a product boiling below 1,000°F, more preferably at least 50% by volume is converted to a product boiling below 1,000°F, and even more preferably at least 70% by volume of the target fraction is converted to a product boiling below 1,000°F.

[0096] In the treatment of hydrocarbon distillates, the operating conditions typically include an average catalyst bed temperature in the range of about 200 psia (13 atm) to about 3,000 (204 atm), about 600°F (315°C) to about 800°F (426°C), a LHSV in the range of about 0.4 to about 6 volumes of hydrocarbon per hour per volume of catalyst, and a hydrocarbon recycle rate or a hydrogen addition rate in the range of about 1,000 SCFB (178 m 3 / m 3 ) to about 10,000 SCFB (1,381 m 3 / m 3 ) would include. Preferred operating conditions for the hydrotreating of hydrocarbon distillates include 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), a LHSV in the range of about 0.5 to about 4 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or a hydrogen addition rate in the range of about 1,000 SCFB (178 m 3 / m 3 ) to about 6,000 SCFB (1,068 m 3 / m 3 ) would include.

[0097] However, the most desirable conditions for the conversion of a particular feedstock to a desired product can best be obtained by converting the feedstock at several different temperatures, pressures, space velocities, and hydrogenation rates, correlating the effects 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.

[0098] Accordingly, the invention as generally described will be more readily understood by 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 catalyst. Generally, the catalyst metal impregnation solution is prepared as follows: The nickel- and molybdenum-containing solution is prepared by mixing water, a molybdenum source, a nickel source, and aqueous ammonia in appropriate ratios. Various molybdenum and nickel sources as disclosed above can be used. These solutions are used to impregnate the support to prepare the final catalyst. The component weights and addition order are selected to ensure the selected target concentration of the metal on the final catalyst for solution stability and the intended catalyst use. The solution treatment temperature and time are selected to ensure solution stability. The required component weights, addition order, treatment temperature, and treatment time are typical and generally known to those skilled in the art.

[0100] Comparative Example 1. (I) Preparation of comparative substrate To prepare a comparative substrate, also referred to herein as a carrier or support, for use in preparing a comparative catalyst, the following procedure was followed: (1) In a two-stage precipitation process that varies and controls temperature and pH at each stage, the temperature and pH are varied and controlled at each stage. For example, see U.S. Patent Application Publication No. 2014 / 0367311, U.S. Patent No. 6,589,908, or U.S. Patent No. 6,984,310 (incorporated herein by reference). For example, in the first stage, half of the total amount of aluminum sulfate and sodium aluminate is mixed to form precipitated seed alumina at about pH 8 and 55 °C (131 °F). In the second stage, before adding the second half of the aluminum sulfate and sodium aluminate, the temperature is raised to about 65 °C (150 °F), the pH is raised to about 9, the reactants are mixed, and the precipitation in the second stage is completed. (2) The obtained alumina is washed and mixed with a silica-alumina composition containing about 75 wt% silica and 25 wt% alumina. (3) The mixture from (2) was dried by introducing it into a heated auger. (4) The mixture from (3) was placed in an Eirich mixer together with water, nitric acid, recycled substrate, and catalyst fines from the latter half 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 firing furnace and heated until the volatile matter level determined by the loss on ignition (LOI) test decreased to <2%. LOI is a measure of the total volatile substances or components that can volatilize at high temperatures present in the sample. The LOI test is performed by exposing the sample to an oxygen-containing atmosphere at 1020 °F (548.9 °C) for 1 hour, thereby decomposing, oxidizing, or igniting any organic substances that may be present and removing residual moisture to the target endpoint.

[0101] (II) A comparative support catalyst was prepared as follows: (1) The substrate or support prepared in I above was placed in a dip-sock impregnation basket. (2) The substrate was continuously lowered and immersed in a tank containing a desired impregnation solution composed of molybdenum, nickel, phosphorus, and a chelating agent at a desired concentration. (3) Subsequently, the impregnated catalyst was conveyed through a rotary calcination furnace up to a target LOI level of 5 wt%.

[0102] Example A of the present invention The substrate or support A was prepared as follows: (1) 1200 g of silica-alumina powder (on a volatile-free basis) containing 5 wt% of silica dispersed in alumina was charged into an Eirich mixer at room temperature. (2) 17.15 g of concentrated nitric acid (70 wt% HNO3) and 2000 g of deionized water were added to the mixer at a rate of about 150 cc / min. The composition was mixed for a total of 5 minutes (including the water addition time). (3) Mixing was stopped and the sides of the mixer were scraped, and at that 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 with a depth of about 1 / 2 inch and preheated in a Gruenberg drying oven at 250°F (121.1°C) for 2 hours, followed by 400°F (204.4°C) for an additional 2 hours. (7) 200 g of the dried extrudate from (6) was calcined in a furnace at 1400°F (760°C) for 40 minutes using 2 SCFH (standard cubic feet per hour) of dry air. (8) Subsequently, the calcined extrudate was cooled to room temperature.

[0103] The catalyst sample A was prepared as follows: (1) Weigh 50 g of the substrate A prepared above (on a volatile-free basis). (2) An aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at a desired concentration was used to impregnate the substrate of (1) 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 50 g of the substrate A prepared above (based on the non-volatile content). (2) An aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at a desired concentration was used to impregnate the substrate of (1) 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 present invention A substrate or support for catalyst sample B (including recycled fine powder) was prepared as follows: (1) 1200 g of silica-alumina powder (on a non-volatile substrate) containing 5 wt% silica dispersed in alumina was charged into an Eirich mixer at room temperature. (2) 60 g of crushed catalyst B fine powder (recycled fine powder) and 60 g of crushed substrate B fine powder (recycled fine powder) were put into the mixer. (3) 17.1 g of concentrated nitric acid (70 wt% HNO3) and 2000 g of deionized water were put into the mixer and mixing was started. (4) The mixer was stopped and the sides were shaved off, and water was added as necessary to obtain the desired paste viscosity. (5) After 10 minutes, the formed mixture formed granules having 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 firing furnace according to the following protocol: charged at 250°F (121.1°C), held for 10 minutes, raised to 1400°F (760°C) over 40 minutes, and held at 1400°F (760°C) for 40 minutes. (9) Thereafter, the fired substrate was cooled to room temperature.

[0106] Catalyst sample B was prepared as follows. (1) 175 g of the substrate from (9) above (on a volatile-free basis) was weighed. (2) The substrate from (1) was impregnated using the dip soak impregnation method with an aqueous solution containing molybdenum, nickel, phosphorus, and a chelating agent at desired concentrations. (3) The impregnated substrate from (2) was introduced into a rotary firing furnace according to the following protocol: at 320°F (160°C) for 10 minutes, then raised to 670°F (354.4°C) over 40 minutes, and held 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 (supports) and catalysts prepared as described above were measured using the standard Hg porosimetry method confirmed above. The distributions are shown in FIGS. 1A - 1C and FIGS. 2A - 2C.

[0108] FIGS. 1A - 1C show the PSD comparison among three catalyst substrates. A comparison of the bulk properties and chemical compositions among the three catalyst substrates is summarized in Table 1 below. The PV (pore volume, in other words, total pore volume) of the exemplary substrate A is about 20% higher than that of the comparative example substrate, while the PV of the exemplary substrate B (containing fine powder) is 15% higher.

[0109] Figures 2A to 2C show the PSD comparison among the three catalysts prepared in the above examples. The comparison of the bulk properties and chemical compositions among the three catalysts is summarized in Table 2 below. It will 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] The exemplary catalysts A and B and the comparative catalyst were tested under the following bench scale unit (BSU) test protocol: Total pressure = 2300 psi H2 / oil = 5500 SCFB LHSV = -2.0 h-1 CAT (catalyst temperature): 710 °F (376.7 °C) for 7 days, followed by 720 °F (382.2 °C) for 5 days, followed by 735 °F (390.6 °C) for 5 days Feed: Vacuum gas oil (VGO) feed blend having the following properties: API (American Petroleum Institute gravity) = 19.7, N = 1810 ppm, S = 27150 ppm

[0113] Figure 3 shows a simplified flow diagram of the bench scale test unit (BSU) used to conduct performance tests using the catalysts prepared in the examples. Gas recirculation was not used in the BSU operation. The whole liquid product (WLP) was sent to an on-line stripper with the cut point controlled to a target. Samples were collected from the stripper overhead (STO), stripper bottom (STB), and gas valve and inspected daily for properties. The cut point targets for the STO and STB products were 470°F (243.3°C) so that STB products with boiling points higher than 470°F (243.3°C) were produced.

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

[0115] [Table 4]

[0116] Referring to Table 3, the exemplary catalyst A is more active than the comparative catalyst for HDN, HDS, and HDA (or HCR), but the exemplary catalyst B (including fines) is also more active. The table also includes the ratios of kHDS and kHDN (reaction rates for the reactions shown) for the exemplary catalysts relative to the comparative catalyst, which further shows the advantages for 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 FIGS. 4A-4C and FIGS. 5A-5C. FIG. 4A is a plot of the hydrodenitrogenation reaction rate (kHDN) as a function of the operating temperature of the catalyst or bench-scale unit for the comparative example and the exemplary catalyst. It is observed that the exemplary catalyst is more effective at a given temperature, or that equivalent HDN performance of the exemplary catalyst can be achieved at a lower temperature. Similar advantageous results for the catalyst of the present invention are observed in FIG. 4B for HDS and in FIG. 4C for the apparent conversion or hydrocracking at 700° F. for producing higher concentrations of paraffins. Thus, when the supported catalyst of the present invention is used in a hydroprocessing process for the removal of sulfur, nitrogen, or the hydrogenation of aromatic compounds, the levels of these components in the processed hydrocarbon product are measurably improved as a function of the operating temperature of the process. Operating at higher temperatures results in lower sulfur or nitrogen contents in the processed product, but doing so incurs higher costs for operating at higher temperatures.

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

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

[0120]

Table 5

[0121] The above data indicate that a combination of a higher catalyst metal loading, a higher substrate pore volume, and a higher concentration of larger pores is a major feature leading to the higher VGO HDN, HDS, and HDA activities of exemplary catalyst A. In other words, even when recycle fines are added to the substrate, exemplary catalyst B (in the above tables and figures) maintains the 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 blend as above.

[0123]

Table 6

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

[0125]

Table 7

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

[0127] Using the same feed as above, the product properties were measured by comparing a comparative support catalyst with the exemplary catalyst A prepared according to the above examples to obtain additional data from the BSU test. The test results are summarized in Tables 6A (comparative catalyst) and 6B (exemplary catalyst A) below. In each case, the same feed as in the previous table was used. Simdist = simulated distillation according to ASTM D2887.

[0128]

Table 8

[0129]

Table 9

[0130] The petroleum feedstock used in the BSU test of the catalyst was selected because it showed a lower VI, a higher viscosity, and a higher content of aromatic and S compounds, all of which it was desirable to improve. Considering the BSU test results, the following conclusions and observations were made. 1. In each of the experimental conditions using the exemplary catalyst A, the STB product VI was higher, and the viscosity and total aromatic content were lower, both of which are desirable results. 2. As the catalyst concentration increases, the VI of the STB product increases, and the viscosity and total aromatic content decrease. This is also desirable. 3. In each of the operating conditions, the hydrocracking conversion rate up to 700°F using the exemplary catalyst A is higher than that of the comparative catalyst, which is clearly advantageous. 4. The exemplary catalyst A results in a higher apparent conversion rate compared to the comparative catalyst, and thus a lower STB product aromatic content, as well as a higher paraffin and naphthene content. 5. In each operating condition, the exemplary catalysts A and B show a higher HDN / HDS activity than the comparative catalyst.

[0131] Alternative Embodiments The items listed below illustrate various and alternative embodiments of the present invention. 1. A supported catalyst comprising at least one metal from Group 6 (or Group VIB) of the Periodic Table and at least one metal from Group 8, 9, or 10 (or Group VIIIB) of the Periodic Table, optionally comprising phosphorus, Calculated as the oxide and based on the total weight of the catalyst composition, the Group 6 metal constitutes about 30% to about 45% by weight, and the total of the metal components of Group 6 and Group 8, 9, or 10 or mixtures thereof constitutes about 35% to about 55% by weight, The metal, and phosphorus if present, are supported on and / or within a porous inorganic oxide support or carrier, and the support prior to incorporating the metal and phosphorus if present has a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, and (a) in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 angstroms (Å) (20 nm), about 25% or more to about 7545% of the TPV, (b) in pores having a diameter of more than 200 Å (20 nm) to less than 1000 Å (100 nm), more than about 15% to less than about 30% of the TPV, (c) in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm), containing 10% or more to less than 30% of the TPV, The supported catalyst is (d) in pores having a diameter of 100 ((Å)) (10 nm) to 200 Å (20 nm), about 35% or more to about 60% of the TPV, (e) in pores having a diameter of more than 200 Å (20 nm) to less than 1000 Å (100 nm), more than about 15% to less than about 30% of the TPV, (f) in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm), containing 10% or more to less than 30% of the TPV, The supported catalyst, wherein the pore characteristics and contents are measured using mercury porosimetry. 2. The supported catalyst according to item 1, further characterized in that the support exhibits a d50 of 110 Å (11 nm) or more and about 170 Å (17 nm) or less, or the supported catalyst exhibits a d50 of about 125 Å (12.5 nm) or more and about 210 Å (21 nm) or less. 3. The supported catalyst according to item 1, further characterized in that more 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 according to item 1, further characterized in that about 12% or more to less than about 28% of the TPV of the supported catalyst is in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm). 5. The supported catalyst according to item 4, further characterized in that about 15% or more to less than about 25% of the TPV of the supported catalyst is in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm). 6. The supported catalyst according to item 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 according to item 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, terana, 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 according to item 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 according to item 8, further comprising phosphorus. 10. The following: (I) Hydroprocessing of petroleum feeds (II) Hydrocracking (HCR) of petroleum feedstock, (III) Hydrodearomatization (HDA) of petroleum feedstock, (IV) Hydrodesulfurization (HDS) of petroleum feedstock, (V) Hydrodenitrogenation (HDN) of petroleum feedstock, (VI) Hydrodemetallization (HDM) of petroleum feedstock, and (VII) A supported catalyst according to claim 1, useful in at least one process selected from the group consisting of hydrotreating of a filled hydrocarbon feed or a petroleum feedstock containing at least one component selected from the group consisting of components boiling above 600°F (315.6°C) and sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, sediment precursors, and mixtures thereof. 11. The supported catalyst according to claim 10, wherein the catalyst has been pre-impregnated, shaped, dried, and calcined. 12. The supported catalyst according to claim 10, further having 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 paraffin, aromatic, and naphthene 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 the supported catalyst according to claim 1 and recovering a product, the hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, and hydrocracking; (II) Hydrotreating a hydrocarbon feed containing at least one component selected from the group consisting of components boiling above 1000°F (537.8°C) and sulfur-containing compounds, nitrogen-containing compounds, metal-containing compounds, asphaltenes, carbon residues, sediment precursors, and mixtures thereof, the hydrotreating comprising contacting the feed with hydrogen and the supported catalyst according to claim 1 under isothermal or substantially isothermal hydrotreating conditions and recovering a treated product. (III) Hydroconverting a hydrocarbon feedstock having components with a boiling point above 600°F (315.6°C) to form a product with an increased proportion of components having a boiling point below about 600°F (315.6°C), comprising contacting the feed with hydrogen and the supported catalyst described in item 1 under isothermal or substantially isothermal hydrotreating conditions and recovering the product, and forming; (IV) Hydroconverting a feed, comprising contacting a feed comprising a hydrocarbon oil with hydrogen and the supported catalyst described in item 1 under conditions of a high temperature above about 600°F (315.6°C) and a pressure above about 500 p.s.i.g. (3.44 MPa) and recovering the product, and hydroconverting, a process selected from the group consisting of. 14. The process according to item 13, wherein the recovered product after treatment exhibits at least one of a decrease in the aromatic component content, an increase in the paraffin component content, a decrease in viscosity, and an increase in the viscosity index as compared to the untreated hydrocarbon feedstock. 15. A method for preparing a catalyst, wherein the catalyst is as follows: (I) Hydroprocessing of a petroleum feedstock, (II) Hydrocracking of a petroleum feedstock (HCR), (III) Hydrodearomatization of a petroleum feedstock (HDA), (IV) Hydrodesulfurization of a petroleum feedstock (HDS), (V) Hydrodenitrogenation of a petroleum feedstock (HDN), (VI) Hydrodemetallization of a petroleum feedstock (HDM), and (VI) For use in at least one process selected from the group consisting of hydrotreating a packed hydrocarbon feed 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, sediment precursors, and mixtures thereof. The method comprises impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the Periodic Table, at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9 or Group 10 (or Group VIII) of the Periodic Table, and optionally a phosphorus-containing compound and at least one organic chelating compound, wherein the Group VIB, Group VIIIB and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere, followed by drying and calcining the resulting impregnated support, wherein the support is (A) mixing an alumina-containing powder with water and optionally nitric acid to form a wet mixture, and (B) drying and calcining, prepared by shaping the wet mixture to form support particles suitable for use in a hydroprocessing reactor, The support has a total pore volume (TPV) of about 0.6 cc / g to about 1.1 cc / g, and the following pore size distribution and pore content corresponding to the 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 the values measured using mercury porosimetry: (i) 25% or more to 45% of the TPV in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm), (ii) more than 15% to less than 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and (iii) having a pore volume of 10% or more to less than 30% in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm), a method comprising a porous inorganic oxide. 16. The method according to item 15, wherein after step (B) for preparing the support, (C) the support particles are dried and calcined to form calcined pills. 17. The method according to item 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, pyruvaldehyde, glycolaldehyde, acetaldol, tartaric acid, ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, tetrapentylene glycol, polyethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and mixtures thereof. 18. The method according to item 17, wherein the organic chelating compound contains 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 and (a) about 25% or more to about 45% of the TPV in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), (b) more than about 15% to less than about 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), (c) a porous inorganic oxide carrier or support containing 10% or more to less than 30% of the 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 item 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, terana, 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 185 m 2 / g to about 425 m 2 / g, the porous inorganic oxide carrier or support according to item 20, having a total surface area determined by nitrogen adsorption using the BET technique. 24. The porous inorganic oxide carrier or support according to item 20, having pores with a diameter of less than 200 Å (20 nm) measured using the mercury intrusion method, in an amount of more than about 55% to about 75%. 25. The porous inorganic oxide carrier or support according to item 20, containing Al2O3 and SiO2, having about 85 wt% to about 98 wt% of Al2O3 and about 15 wt% to about 2 wt% of SiO2.

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

[0134] Furthermore, any numerical range described in the specification or claims, such as those representing particular sets of characteristics, units of measurement, conditions, physical states, or percentages, is intended to expressly incorporate by reference or otherwise into this specification any number within such range that is any subset of the numbers within such range. For example, lower limit R L and upper limit RU Whenever a numerical range having [a certain property] is disclosed, any number R falling within that range is always specifically disclosed. In particular, the following numbers R within the range are specifically disclosed. R = R L + k(R U - R L ), wherein k is a variable in the range of 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%. Further, any numerical range represented by any two values of R calculated above is also specifically disclosed.

[0135] In this specification, the present invention has been described with reference to specific embodiments, but it should be understood that these embodiments are merely illustrative of the principles and uses of the present invention. Therefore, it should be understood that numerous modifications can be made to the exemplary embodiments and other configurations can be devised without departing from the spirit and scope of the present invention as defined by the appended claims. This disclosure is not limited to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope of the present invention. In addition to those listed in this specification, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure is limited only by the terms of the appended claims together with the full scope of equivalents to which such claims are entitled. It should be understood that this disclosure is not limited to a particular method, reagent, compound, composition, or biological system, which can of course vary. It should also be understood that the terms used in this specification are for the purpose of describing particular embodiments only and are not intended to be limiting.

[0136] The embodiments illustratively described in this specification can be preferably practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising", "including", "containing", etc. should be read broadly and without limitation. Additionally, the terms and expressions used herein are used as terms of explanation rather than limitation, and in using such terms and expressions, it is not intended to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of" is understood to include these specifically recited elements, as well as these additional elements that do not materially affect the basic and novel features of the claimed technology. The phrase "consisting of" excludes any element not specified.

[0137]

Table 10

[0138] Other embodiments are described in the following claims. The present invention includes the following aspects. [1] A supported catalyst comprising at least one metal from Group 6 (or Group VIB) of the Periodic Table of the Elements and at least one metal from Group 8, Group 9, or Group 10 (or Group VIIIB) of the Periodic Table of the Elements, and optionally containing phosphorus, Calculated as an oxide and based on the total weight of the catalyst composition, the Group 6 metal constitutes about 30% to about 45% by weight, and the total of the metal components of Group 6 and Group 8, Group 9, or Group 10 or mixtures thereof constitutes about 35% to about 55% by weight, The metal, and phosphorus if present, are supported on and / or within a porous inorganic oxide support or carrier, and the support before incorporating the metal and phosphorus if present has a total pore volume (TPV) of about 0.8 cc / g to about 1.5 cc / g, and (a) about 25% or more to about 45% of the TPV in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), (b) more than about 15% to less than about 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), (c) including 10% or more to less than 30% of the TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), The supported catalyst, (d) about 35% or more to about 60% of the TPV in pores having a diameter of 100 (Å) (10 nm) to 200 Å (20 nm), (e) more than about 15% to less than about 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), (f) including 10% or more to less than 30% of the TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm), A supported catalyst in which the pore characteristics and content are measured using mercury porosimetry. [2] The support exhibits a d of 110 Å (11 nm) or more and about 170 Å (17 nm) or less, 50 or the supported catalyst exhibits a d50 of about 125 Å (12.5 nm) or more and about 210 Å (21 nm) or less, the supported catalyst according to 1. [3] More than about 17% to less than about 28% of the TPV of the supported catalyst is within pores having a diameter of 200 Å to less than 1000 Å, the supported catalyst according to 1 or 2. [4] The supported catalyst according to any one of 1 to 3, wherein about 12% or more to 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] The supported catalyst according to 4, wherein about 15% or more to less than about 25% of the TPV is in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm). [6] The supported catalyst according to any one of 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] The supported catalyst according to any one of 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, thoria, 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] The supported catalyst according to any one of 1 to 7, 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] The supported catalyst according to 8, further comprising phosphorus.

[10] The following: Hydroprocessing of petroleum feedstock, Hydrocracking (HCR) of petroleum feedstock, Hydrodearomatization (HDA) of petroleum feedstock, Hydrodesulfurization (HDS) of petroleum feedstock, Hydrodenitrogenation (HDN) of petroleum feedstock, Hydrodemetallization (HDM) of petroleum feedstock, or The supported catalyst according to 1, which is useful in at least one process that is hydrotreating of a filled hydrocarbon feed or petroleum feedstock containing at least one component selected from the group consisting of components boiling above 600°F (315.6°C) and sulfur - containing compounds, nitrogen - containing compounds, metal - containing compounds, asphaltenes, carbon residues, precipitate precursors, and mixtures thereof.

[11] The supported catalyst according to 10, wherein the catalyst has been pre - impregnated, shaped, dried, and calcined.

[12] The catalyst has a d of about 125 Å (12.5 nm) or more and about 210 Å (21 nm) or less 50 The supported catalyst according to claim 10 or 11, showing

[13] A process for treating a hydrocarbon feedstock containing at least one of paraffin, aromatic, and naphthene components to produce a treated product, said process comprising: (I) Hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, said process comprising contacting a feedstock in at least one reactor with hydrogen under hydroprocessing or hydrocracking conditions using the supported catalyst according to claim 1, and recovering the product, including hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking; (II) Hydrotreating the hydrocarbon feedstock containing a component 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, said process comprising contacting the feedstock with hydrogen and the supported catalyst according to claim 1 under isothermal or substantially isothermal hydrotreating conditions and recovering the treated product, including hydrotreating; (III) Hydroconverting the hydrocarbon feedstock having components boiling above 600°F (315.6°C) to form a product with an increased proportion of components boiling below 600°F (315.6°C), said process comprising contacting the feedstock with hydrogen and the supported catalyst according to claim 1 under isothermal or substantially isothermal hydrotreating conditions and recovering the product, including forming; (IV) Hydroconverting the feedstock, said process comprising contacting the feedstock containing hydrocarbon oil with hydrogen and the supported catalyst according to claim 1 under conditions of a temperature above about 600°F (315.6°C) and a pressure above about 500 p.s.i.g. (3.44 MPa) and recovering the product, including hydroconverting, a process selected from the group consisting of.

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

[15] A method for preparing a catalyst, said catalyst comprising: (I) Hydroprocessing of petroleum feeds, (II) Hydrocracking of petroleum feedstocks (HCR), (III) Hydrodesulfurization of hydrocarbons, (IV) Hydrodenitrogenation of hydrocarbons, (V) Hydrodearomatization (HDA) of petroleum feedstocks, (VI) Hydrodemetallization of hydrocarbons, and (VII) For use in at least one process selected from the group consisting of hydrotreating of a charged hydrocarbon feed 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, sediment precursors, and mixtures thereof, wherein the method comprises impregnating a porous inorganic oxide support with an aqueous solution comprising at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 6 (or Group VIB) of the Periodic Table of the Elements, at least one catalyst or catalyst precursor selected from the group consisting of compounds of Group 8, Group 9, or Group 10 (or Group VIII) of the Periodic Table of the Elements, and optionally a phosphorus-containing compound and at least one organic chelating compound, wherein the Group VIB, Group VIIIB, and phosphorus compounds are thermally decomposable or thermally oxidizable to their corresponding oxides in the presence of an oxygen-containing atmosphere, impregnating, and then drying and calcining the obtained impregnated support, wherein the support is prepared by mixing an alumina-containing powder with water and optionally nitric acid to form a wet mixture, and forming the wet mixture into support particles suitable for use in a hydroprocessing reactor, and drying and calcining, wherein 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 prior to incorporating metals and phosphorus if present: 25% or more to 45% of the TPV in pores having a diameter of 100 Å (10 nm) to 200 Å (20 nm), more than 15% to less than 30% of the TPV in pores having a diameter of 200 Å (20 nm) to less than 1000 Å (100 nm), and A method comprising a porous inorganic oxide having a pore volume of 10% or more to less than 30% in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

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

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

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

[19] The method according to any one of 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, and about 25% or more to about 45% of the TPV in pores having a diameter of 100 angstroms (Å) (10 nm) to 200 Å (20 nm), more than about 15% to less than about 30% of the TPV 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 10% or more to less than 30% of the TPV in pores having a diameter of 1000 Å (100 nm) to 30,000 Å (3,000 nm).

[21] The porous inorganic oxide carrier or support according to 20, wherein the support is silica, silica gel, silica-alumina, alumina, alumina having silica-alumina dispersed therein, silica coated with alumina, alumina coated with silica, titania, titania-alumina, zirconia, boria, thoria, 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.

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

[23] About 185 m 2 / g to about 425 m 2 / g, having a total surface area determined by nitrogen adsorption using the BET technique, of the porous inorganic oxide carrier or support according to any one of 20 to 22.

[24] The porous inorganic oxide carrier or support according to any one of 20 to 23, having pores with a diameter of less than 200 Å (20 nm) measured using the mercury intrusion method, of more than about 55% to about 75%.

[25] About 85 wt% to about 98 wt% of Al 2 O 3 And about 15 wt% to about 2 wt% of SiO 2 Having, of Al 2 O 3 And SiO 2 Including, of the porous inorganic oxide carrier or support according to any one of 20 to 24.

Claims

Claim 1: A supported catalyst for the hydrotreating of hydrocarbon feedstocks, comprising at least one metal from Group 6 (or Group VIB) of the Periodic Table of the Elements and at least one metal from Group 8, Group 9, or Group 10 (or Group VIIIB) of the Periodic Table of the Elements, optionally comprising phosphorus, calculated as the oxide and based on the total weight of the catalyst composition, the Group 6 metal constituting 30 to 45% by weight, and the total of the metal components of Group 6 and Group 8, Group 9, or Group 10 or mixtures thereof constituting 35 to 55% by weight, wherein said metals, and phosphorus if present, are supported on and / or within a porous inorganic oxide support or carrier, said support or carrier being silica - alumina, and said support or carrier prior to incorporating said metals and phosphorus if present having a total pore volume (TPV) of 0.8 cc / g to 1.5 cc / g, and (a) 25% or more to 45% or less of the TPV in pores having a diameter of 100 angstroms (Å) (10 nm) or more to 200 Å (20 nm) or less, (b) more than 15% to less than 30% of the TPV in pores having a diameter of 200 Å (20 nm) or more to less than 1000 Å (100 nm), (c) 10% or more to less than 30% of the TPV in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less, wherein said supported catalyst (d) 35% or more to 60% or less of the TPV in pores having a diameter of 100 (Å) (10 nm) or more to 200 Å (20 nm) or less, (e) more than 15% to less than 30% of the TPV in pores having a diameter of 200 Å (20 nm) or more to less than 1000 Å (100 nm), (f) 10% or more to less than 30% of the TPV in pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less, and the pore characteristics and contents are measured using mercury porosimetry. A supported catalyst.

2. The carrier or support has a d of 110 Å (11 nm) or more and 170 Å (17 nm) or less ５０ or the supported catalyst has a d50 of 125 Å (12.5 nm) or more and 210 Å (21 nm) or less, where d50 is the median pore diameter measured by mercury porosimetry. The supported catalyst according to claim 1.

3. The supported catalyst according to claim 1 or 2, wherein more than 17% to less than 28% of the TPV of said supported catalyst is within pores having a diameter of 200 Å or more to less than 1000 Å.

4. The supported catalyst according to any one of claims 1 to 3, wherein 12% or more to less than 28% of the TPV of said supported catalyst is within pores having a diameter of 1000 Å (100 nm) or more to 30,000 Å (3,000 nm) or less. **Claim 5**: The supported catalyst according to claim 4, wherein 15% or more and less than 25% of the TPV of the supported catalyst is in pores having a diameter of 1000 Å (100 nm) or more and 30,000 Å (3,000 nm) or less. **Claim 6**: The supported catalyst according to any one of claims 1 to 5, wherein 40% or more and 55% or less of the TPV of the supported catalyst is in pores having a diameter of 100 Å (10 nm) or more and 200 Å (20 nm) or less. **Claim 7** The supported catalyst according to any one of claims 1 to 6, wherein the Group 6 metal is Mo, and the Group 8, Group 9, or Group 10 metal is selected from the group consisting of Co, Ni, and mixtures thereof. **Claim 8** The supported catalyst according to any one of claims 1 to 6, wherein the Group 6 metal is Mo, and the Group 8, Group 9, or Group 10 metal is Ni. **Claim 9** The supported catalyst according to claim 7 or 8, further comprising phosphorus. **Claim 10** The following: Hydrotreating of a petroleum feedstock, Hydrocracking (HCR) of a petroleum feedstock, Hydrodearomatization (HDA) of a petroleum feedstock, Hydrodesulfurization (HDS) of a petroleum feedstock, Hydrodenitrogenation (HDN) of a petroleum feedstock, Hydrodemetallization (HDM) of a petroleum feedstock, or The supported catalyst according to claim 1, useful in at least one process which is a hydrotreating of a filled hydrocarbon feedstock or a petroleum feedstock containing at least one component selected from the group consisting of 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, sediment precursors, and mixtures thereof. **Claim 11** The catalyst has a d of 125 Å (12.5 nm) or more and 210 Å (21 nm) or less ５０ The supported catalyst according to claim 10, which exhibits ５０ . **Claim 12** A process for treating a hydrocarbon feedstock containing at least one of paraffin, aromatic, and naphthene components to produce a treated product, the process comprising: (I) performing at least one selected from the group consisting of hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking, the process comprising contacting a hydrocarbon feedstock in at least one reactor with hydrogen under hydrotreating or hydrocracking conditions using the supported catalyst according to claim 1 and recovering a product, and performing at least one selected from the group consisting of hydrodemetallization, hydrodenitrogenation, hydrodesulfurization, hydrodearomatization, and hydrocracking. (II) hydrotreating the hydrocarbon feedstock containing a component that boils above 1000°F and at least one component selected from the group consisting of a sulfur-containing compound, a nitrogen-containing compound, a metal-containing compound, asphaltene, carbon residue, a precipitate precursor, and mixtures thereof, by contacting the hydrocarbon feedstock with hydrogen and the supported catalyst according to claim 1 under isothermal hydrotreating conditions and recovering the treatment product. (III) hydrocracking the hydrocarbon feedstock having a component with a boiling point above 600°F (315.6°C) to form a product in which the proportion of components with a boiling point below 600°F (315.6°C) is increased, by contacting the hydrocarbon feedstock with hydrogen and the supported catalyst according to claim 1 under isothermal hydrotreating conditions and recovering the product. (IV) hydrocracking the hydrocarbon feedstock, by contacting the hydrocarbon feedstock containing hydrocarbon oil with hydrogen and the supported catalyst according to claim 1 under conditions of a high temperature above 600°F (315.6°C) and a pressure above 500 p.s.i.g. (3.44 MPa) and recovering the product. A process selected from the group consisting of:

13. The process according to claim 12, wherein the treated product exhibits at least one of a decrease in the aromatic component content, an increase in the paraffin component content, a decrease in viscosity, and an increase in the viscosity index, compared to the untreated hydrocarbon feedstock.

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