Silica-alumina composite materials for hydrogenation applications

Abstract

A silica-alumina-based composite material for producing a hydrotreating catalyst is disclosed. The silica-alumina composite generally comprises at least two silica-aluminas, where the first silica-alumina is a modified first silica-alumina and the second silica-alumina is either unmodified or modified. The first silica-alumina is modified to contain silica domains and alumina domains, as well as an interphase between the silica and alumina. The second silica-alumina may also be simultaneously or separately modified to contain silica domains and alumina domains, as well as an interphase between the silica and alumina. The first and second silica-aluminas differ in one or more physical and / or chemical characteristics, such as the silica-to-alumina ratio, surface area, pore size, pore volume, silica domain size, or alumina domain size. The present invention can be used to make catalyst substrate materials and catalysts useful for upgrading hydrocarbon feedstocks to make fuels, lubricants, chemicals and other hydrocarbon-containing compositions.

Description

[Technical Field]

[0001] Field of Invention The present invention relates to a silica-alumina-based composite material for producing hydrogenation catalysts. The present invention can be used to produce catalyst base materials and catalysts that are useful for improving hydrocarbon raw materials for producing fuels, lubricants, chemicals, and other hydrocarbon-containing compositions. [Background technology]

[0002] Background of the Invention Solid-state acidic materials, such as crystalline zeolites and amorphous silica-alumina, play a crucial role in hydrogenation applications. Amorphous silica-alumina is widely used as an important acidic component for dispersing base metals (e.g., nickel, cobalt, tungsten, and molybdenum) as well as precious metals (e.g., palladium and platinum) in dual-function catalysts for hydrogenation. The pore structure and acidity of silica-alumina significantly influence the selectivity of hydrogenation processes for converting heavier molecules in crude oil into desired products (e.g., lubricants, clean fuels, and chemicals).

[0003] The acidity of silica-alumina is generally determined by the dispersion of Al2O3 in the SiO2 matrix, or conversely, the dispersion of SiO2 in the Al2O3 matrix. Numerous synthetic approaches have been reported to control the domain size and dispersion of the alumina and silica phases within the matrix material, including coprecipitation, coating, and pH swing. However, due to the characteristics of the amorphous structure, controlling the pore structure of silica-alumina materials during the synthesis process can sometimes be difficult.

[0004] While progress has been made in preparing substrate materials and catalysts for hydrogenation treatment from silica-alumina, there is a continuing need for improved and simplified processes for preparing such materials and catalysts, particularly processes that would lead to improvements in hydrogenation applications. [Overview of the project]

[0005] Summary of the Invention The present invention generally provides a novel approach to producing amorphous silica-alumina (ASA) composite materials having desired pore structure characteristics and acidity by combining at least two silica-alumina materials with certain different properties. The composite materials include modified silica-alumina, which can generally be produced by a mixing process involving the addition of a modifier. For example, a modifier such as nitric acid may be mixed with one or more silica-alumina materials using a kneading and / or extrusion process. Under such shear conditions, the nitric acid or other strong inorganic acid modifier, as well as the shear force applied by the kneading / extrusion process, is thought to modify the surfaces of the alumina and silica domains present in the silica-alumina, resulting in the formation of an interfacial phase between silica and alumina, thereby providing the composite material with the desired mesoporous structure.

[0006] The present invention broadly relates to silica-alumina composite materials, and more particularly to methods for producing silica-alumina composite materials used in the manufacture of hydrogenation catalysts. One of the objectives of the present invention is to improve catalyst performance, which generally also reduces capital and operating costs in hydrogenation applications. It is also desirable to provide commercial flexibility in preparing composite materials suitable for use as base materials for hydrogenation catalysts using silica-alumina materials from alternative sources.

[0007] In one embodiment, the present invention relates to a silica-alumina composite material suitable for use in the production of a substrate for a hydrogenation catalyst, wherein the material comprises at least two silica-alumina molecules, the first silica-alumina being a modified first silica-alumina, and the second silica-alumina being either unmodified or modified second silica-alumina. The first silica-alumina is modified to include silica domains and alumina domains, as well as a silica-alumina interface phase. The second silica-alumina may also be modified simultaneously or separately to include silica domains and alumina domains, as well as a silica-alumina interface phase. The first silica-alumina and the second silica-alumina differ in one or more physical and / or chemical characteristics, such as the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size.

[0008] The present invention relates to the production of a hydrogenation catalyst containing the composite material, a noble metal, a base metal, and optionally an accelerator, using the composite material, a method for producing the composite material, a method for producing the hydrogenation catalyst, and a method for using the hydrogenation catalyst in hydrogenation applications. In one embodiment, the silica-alumina composite material may be produced by a method comprising: combining a first silica-alumina and a second silica-alumina with optionally molecular sieves and / or an alumina support to form a base composition; adding a diluted strong acid aqueous solution to the base composition to form an extrudeable composition; and extruding, drying, and calcining the extrudeable composition to form a silica-alumina composite material. As described in relation to the composite material, the first silica-alumina and the second silica-alumina used in the method differ in one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size. The hydrogenation catalyst according to the present invention may be formed from a composite material by impregnating or attaching a catalytically active metal to the composite material, or by combining the catalytically active metal with the composite material. [Brief explanation of the drawing]

[0009] Simple description of the drawing The scope of the present invention is not limited by any representative drawings attached to this disclosure, but should be understood to be defined by the attached claims.

[0010] [Figure 1] As described in the examples, the results of comparing the pore size distribution (N2 PSD) in substrate samples for hydrogenation catalysts are shown.

[0011] [Figure 2] As described in the examples, the results of comparing the pore size distribution (Hg PSD) in substrate samples for hydrogenation catalysts are shown.

[0012] [Figure 3] As described in the examples, this shows the silica domain in silica-alumina sample-1 (ASA-1) when used with HCB-4, a substrate material for hydrogenation catalysts.

[0013] [Figure 4] As described in the examples, the results of comparing the silica domain size distribution of a hydrogenation catalyst substrate material having two amorphous silica-alumina molecules and a hydrogenation catalyst substrate material having one amorphous silica-alumina molecule are shown.

[0014] [Figure 5] As described in the examples, the results of comparing the particle size distribution of silica domains in the base materials HCB-2 and HCB-4 for hydrogenation catalysts are shown.

[0015] [Figure 6] As described in the examples, the catalytic activity of catalysts prepared with various hydrogenation catalyst substrate materials is shown.

[0016] [Figure 7]As described in the examples, the yield of heavy diesel in catalysts prepared with various hydrogenation catalyst substrate materials is shown.

[0017] [Figure 8] As described in the examples, the yield of the total distillate in catalysts prepared with various hydrogenation catalyst substrate materials is shown. [Modes for carrying out the invention]

[0018] Detailed description While this specification provides exemplary embodiments of one or more aspects, the disclosed processes and compositions formed therefrom may be carried out using any number of techniques. This disclosure, including any exemplary designs and embodiments described herein, is not limited to the exemplary or specific embodiments, drawings and techniques illustrated herein, and may be modified within the scope of the appended claims, along with the entire range of equivalents.

[0019] Unless otherwise indicated, the following terms, technical terms, and definitions apply to this disclosure. Where a term is used in this disclosure but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd ed (1997) may be applied, provided that such definition does not conflict with any other disclosure or applicable definition herein, or make any claim to which such definition applies unclear or unenforceable. To the extent that any definition or usage provided in any document incorporated herein by reference conflicts with any definition or usage provided herein, the definition or usage provided herein shall apply.

[0020] The term "periodic table" refers to the IUPAC Periodic Table of the Elements version dated Jun. 22, 2007, and the family numbering of the periodic table is as described in Chemical and Engineering News, 63(5), 27 (1985).

[0021] The terms "hydrocarbon-containing," "hydrocarbon," and similar terms refer to compounds containing only carbon and hydrogen atoms. If a specific group is present in the hydrocarbon, other identifiers may be used to indicate the presence of that specific group (for example, "halogenated hydrocarbon" indicates the presence of one or more halogen atoms that replace an equal number of hydrogen atoms in the hydrocarbon).

[0022] Hydrogenation or hydrogenation refers to a process in which a carbonous raw material is brought into contact with hydrogen and a catalyst at a high temperature and pressure for the purpose of removing undesirable impurities and / or converting the carbonous raw material into a desired product. Such processes include, but are not limited to, methanation, water-gas shift reactions, hydrogenation, hydrogenation treatment, hydrogenated desulfurization, hydrogenated denitrification, hydrogenated demetallation, hydrogenated dearomaticization, hydrogenated isomerization, hydrogenated dewaxing, and hydrogenation cracking, including selective hydrogenation. Depending on the type of hydrogenation and reaction conditions, improvements in physical properties such as viscosity, viscosity index, saturation content, low-temperature properties, volatility, and reduced polarity may be observed in the hydrogenated product.

[0023] Hydrocracking refers to a process in which hydrogenation and dehydrogenation are accompanied by the cracking / decomposition of hydrocarbons, such as converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatic compounds and / or cycloparaffins (naphthenes) into acyclic branched paraffins.

[0024] The term "carrier," particularly when used in the context of "catalyst carrier," typically refers to a conventional material that supports a catalytic material, usually a solid with a large surface area. The carrier material may be inert or involved in the catalytic reaction, and may be porous or non-porous. Typical catalyst carriers include various types of carbon, alumina, silica, and silica-alumina, such as amorphous silicaaluminate, zeolites, alumina-boria, silica-alumina-magnesia, silica-alumina-titania, and materials obtained by adding other zeolites and other composite oxides to them.

[0025] A "molecular sieve" refers to a material that has a framework structure with uniform molecular dimensions for its pores, and depending on the type of molecular sieve, only certain molecules can reach the pore structure of that molecular sieve, while other molecules are excluded, for example, due to their size and / or reactivity. Zeolites, crystalline aluminophosphates, and crystalline silicoaluminophosphates are typical examples of molecular sieves.

[0026] The "middle distillates" typically include jet fuel, diesel fuel, and kerosene, which are cut points as shown below. [Table 0]

[0027] The SiO2 / Al2O3 ratio (SAR) is determined by inductively coupled plasma (ICP) elemental analysis. An infinite SAR means that the zeolite contains no aluminum, i.e., the molar ratio of silica to alumina is infinite.

[0028] Amorphous silica aluminate (ASA) refers to a synthetic material containing several alumina atoms arranged in a tetrahedral configuration, as shown by nuclear magnetic resonance imaging. ASA can be used as a catalyst or catalyst support. Amorphous silica alumina contains Brønsted acid (or protic) moieties with ionizable hydrogen atoms and Lewis acid (protic) electron-accepting moieties, and these different types of acidic moieties can be identified by the way to which specific chemical species (e.g., pyridine) bind.

[0029] Surface area: Determined by nitrogen adsorption at its boiling point. The BET surface area is calculated using a five-point method with P / P0 = 0.050, 0.088, 0.125, 0.163, and 0.200. The sample is first pretreated at 400°C for 6 hours in the presence of flowing dry nitrogen.

[0030] Pore ​​volume / micropore volume: Determined by nitrogen adsorption at its boiling point. Micropore volume is calculated using the t-plot method with P / P0 = 0.050, 0.088, 0.125, 0.163, and 0.200. The sample is first pretreated at 400°C for 6 hours in the presence of flowing dry nitrogen.

[0031] Pore ​​size: Determined by nitrogen adsorption at its boiling point. Mesopore size is calculated from nitrogen isotherms using the BJH method described in EP Barrett, LG Joyner and PP Halenda, “The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms.” J.Am.Chem.Soc.73,373-380,1951. The sample is first pretreated at 400°C for 6 hours in the presence of flowing dry nitrogen.

[0032] The total pore volume is calculated by P / P0 = 0.990 and by nitrogen adsorption at its boiling point. First, the sample is pretreated at 400°C for 6 hours in the presence of flowing dry nitrogen.

[0033] The particle density is obtained by applying the formula D = M / V, where M is the weight of the catalyst sample and V is the volume of the catalyst sample. The volume is determined by measuring the volume displacement by immersing the sample in mercury under a 28 mm Hg vacuum.

[0034] Unit cell size: Determined by powder X-ray diffraction.

[0035] Particle size distribution of silica domains: The sample was attached to a resin, its cross-section was cut, polished, and coated to ensure conductivity. A backscattered electron image and elemental map of the sample were obtained at 20kV and 20nA using a JEOL JXA 8230 electron probe microanalyzer (EPMA). Image segmentation was performed on the elemental map using ZEISS ZEN Intellesis software. After segmentation, the maximum Ferret diameter was determined as a structural parameter, and a histogram representing the particle size distribution of silica domains was created using this maximum Ferret diameter.

[0036] In this disclosure, compositions and methods or processes are often described in terms of "including" various components or steps, but unless otherwise stated, such compositions and methods may "essentially consist of" or "consist of" such components or steps.

[0037] The terms “a,” “an,” and “the” are intended to include plural alternatives, for example, at least one. For example, the disclosure of a transition metal or an alkali metal, unless otherwise specified, is intended to include one transition metal or alkali metal, a mixture of two or more transition metals or alkali metals, or a combination of two or more transition metals or alkali metals.

[0038] In the detailed descriptions and claims herein, all numerical values ​​are modified by "about" or "approximately," taking into account experimental errors and variations that a person skilled in the art would anticipate.

[0039] The present invention provides a silica-alumina composite material suitable for use in the production of a substrate for hydrogenation catalysts. The silica-alumina composite material comprises a first modified silica-alumina and a second modified silica-alumina, which are modified to include silica domains and alumina domains, as well as an interface phase between silica and alumina, wherein the first silica-alumina and the second silica-alumina differ in one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size.

[0040] The composite material may generally contain 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 30-60 wt.%, or 30-50 wt.% of the first silica-alumina, 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 25-60 wt.%, or 25-50 wt.%, 0-60 wt.%, 2-50 wt.%, 5-40 wt.%, 5-30 wt.%, 5-20 wt.%, or 5-15 wt.%, and 0-40 wt.%, 5-40 wt.%, 10-30 wt.%, or 15-30 wt.% of alumina.

[0041] The hydrogenation catalyst according to the present invention comprises a composite material in the range of approximately 40-100 wt.%, 40-99 wt.%, 50-99 wt.%, 60-99 wt.%, or 70-99 wt.%, a noble metal in the range of 0.1-5 wt.%, 0.1-4 wt.%, 0.1-3 wt.%, 0.1-2 wt.%, or 0.1-1 wt.%, and a base metal in the range of 0-40 wt.%, 5-40 wt.%, 5-30 wt.%, 10-40 wt.%, 10-30 wt.%, or 10-20 wt. The base metal content is in the range of 20-40 wt.% or 20-30 wt.%, and the total base metal content is arbitrarily in the range of 0-40 wt.%, 5-40 wt.%, 5-30 wt.%, 10-40 wt.%, 10-30 wt.%, 10-20 wt.%, 20-40 wt.%, or 20-30 wt.%, and includes an accelerator in the range of 0-30 wt.%, 0-20 wt.%, 0-10 wt.%, 5-30 wt.%, 5-20 wt.%, 10-30 wt.%, or 10-20 wt.%. Suitable precious metals include, for example, Pt and Pd, and suitable base metals include Ni, Mo, Co, and W. Combinations of precious and base metals may also be used. Suitable accelerators are described in Zhan's U.S. Patent No. 8,637,419B2.

[0042] The present invention further provides a method for producing a silica-alumina composite material suitable for use as a substrate for hydrogenation catalysts or for producing a substrate for hydrogenation catalysts, the method comprising: combining a first silica-alumina and a second silica-alumina with a molecular sieve and / or an alumina support to form a substrate composition, wherein the first silica-alumina and the second silica-alumina differ in one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size; adding a diluted strong acid aqueous solution, preferably nitric acid, to the substrate composition to form an extrudeable composition; and extruding, drying, and calcining the extrudeable composition to form a silica-alumina composite material.

[0043] The composite material and the catalyst(s) made from the composite material may be used in a method of hydrogenating hydrocarbon feedstock. Generally, such a method involves contacting a hydrogenating catalyst with a hydrocarbon feedstock and hydrogen under hydrogenating conditions, wherein the hydrogenating catalyst comprises at least one metal attached to the composite material according to the present invention. In such a hydrogen cracking process, the catalyst can beneficially improve catalytic activity and yield equivalent heavy diesel yield and total fraction yield compared to hydrogenating catalysts that differ only in containing either the first silica-alumina or the second silica-alumina, rather than both.

[0044] The modified first silica-alumina is modified by contacting the first silica-alumina with a strong acid, preferably nitric acid, under extrusion conditions. Typically, the extrusion conditions include a temperature of less than about 200°F. The first and second silica-alumina typically include amorphous silica-alumina, and more specifically, amorphous silica-alumina, respectively. The second silica-alumina may also include modified second silica-alumina containing silica domains and alumina domains, as well as an interface phase between silica and alumina. The modified second silica-alumina may also be modified by contacting the second silica-alumina with a strong acid, preferably nitric acid, either separately from or simultaneously with the first silica-alumina, and / or together with the first silica-alumina, under similar extrusion conditions.

[0045] The composite material of the present invention may further include molecular sieves and / or alumina carriers. Suitable sieves include, for example, Y zeolite, preferably Y zeolite having a unit cell size of 24.15 Å to 24.45 Å, and optionally further including β zeolite.

[0046] The first silica-alumina and / or the second silica-alumina may generally include one or more of the following physical characteristics:

[0047] The alumina content ranges from 10 to 98 wt.%, 10 to 80 wt.%, 20 to 80 wt.%, 30 to 80 wt.%, 30 to 70 wt.%, 40 to 70 wt.%, 50 to 70 wt.%, 50 to 80 wt.%, 60 to 80 wt.%, 10 to 50 wt.%, 10 to 40 wt.%, 20 to 40 wt.%, 40 to 98 wt.%, 50 to 98 wt.%, 60 to 98 wt.%, 70 to 98 wt.% or 80 to 98 wt.%.

[0048] The surface area by nitrogen adsorption is 300 to 700 m 2 / g, 300 to 650 m 2 / g, 300 to 600 m 2 / g, 320 to 600 m 2 / g, 320 to 550 m 2 / g, 320 to 500 m 2 / g, 350 to 700 m 2 / g, 350 to 650 m 2 / g, 350 to 600 m 2 / g, 350 to 600 m 2 / g, 350 to 550 m 2 / g, 350 to 500 m 2 / g, 400 to 700 m 2 / g, 400 to 650 m 2 / g, 400 to 600 m 2 / g, 400 to 550 m 2 / g, 450 to 700 m 2 / g, 450 to 650 m 2 / g, 450 to 600 m 2 / g or 450 to 550 m 2 / g.

[0049] The pore volume by nitrogen adsorption is 0.7 to 2.50 m 2 / g, 0.7 to 2.2 m 2 / g, 0.7 to 2.0 m 2 / g, 0.7 to 1.8 m 2 / g, 0.7 to 1.6 m 2 / g, 0.7 to 1.4 m 2 / g, 0.7 to 1.2 m 2 / g, 0.7 to 1.0 m 2 / g、0.7~0.9m 2 / g、0.75~2.50m 2 / g、0.75~2.2m 2 / g、0.75~2.0m 2 / g、0.75~1.8m 2 / g、0.75~1.6m 2 / g、0.75~1.4m 2 / g、0.75~1.2m 2 / g、0.75~1.0m 2 / g、0.75~0.9m 2 / g、0.85~2.50m 2 / g、0.85~2.2m 2 / g、0.85~2.0m 2 / g、0.85~1.8m 2 / g、0.85~1.6m 2 / g、0.85~1.4m 2 / g、0.85~1.2m 2 / g、0.85~1.0m 2 / g、0.85~0.9m 2 / g、0.9~2.50m 2 / g、0.9~2.2m 2 / g、0.9~2.0m 2 / g、0.9~1.8m 2 / g、0.9~1.6m 2 / g、0.9~1.4m 2 / g、0.9~1.2m 2 / g、0.9~1.0m 2 / g、1.0~2.50m 2 / g、1.0~2.2m 2 / g、1.0~2.0m 2 / g、1.0~1.8m 2 / g、1.0~1.6m 2 / g、1.0~1.4m 2 / g、1.0~1.2m 2 / g、1.0~2.50m 2 / g、1.1~2.2m 2 / g、1.1~2.0m 2 / g、1.1~1.8m 2 / g、1.1~1.6m 2 / g、1.1~1.4m 2 / g、1.1~1.2m2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m 2 / g or 1.4-1.6m 2 It must be within the range of / g

[0050] Diameter D at 50% pore volume 50 However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[0051] The composite material containing the first silica-alumina and the second silica-alumina may further include one or more of the following physical characteristics:

[0052] The particle density is in the range of 0.6 - 1.0 g / mL, 0.64 - 1.0 g / mL, 0.68 - 1.0 g / mL, 0.72 - 1.0 g / mL, 0.76 - 1.0 g / mL, 0.8 - 1.0 g / mL, 0.84 - 1.0 g / mL, 0.88 - 1.0 g / mL, 0.6 - 0.96 g / mL, 0.64 - 0.96 g / mL, 0.68 - 0.96 g / mL, 0.72 - 0.96 g / mL, 0.76 - 0.96 g / mL, 0.8 - 0.96 g / mL, 0.84 - 0.96 g / mL, 0.88 - 0.96 g / mL, 0.6 - 0.92 g / mL, 0.64 - 0.92 g / mL, 0.68 - 0.92 g / mL, 0.72 - 0.92 g / mL, 0.76 - 0.92 g / mL, 0.8 - 0.92 g / mL, 0.84 - 0.92 g / mL, 0.6 - 0.88 g / mL, 0.64 - 0.88 g / mL, 0.68 - 0.88 g / mL, 0.72 - 0.88 g / mL, 0.76 - 0.88 g / mL, 0.8 - 0.88 g / mL, 0.6 - 0.84 g / mL, 0.64 - 0.84 g / mL, 0.68 - 0.84 g / mL, 0.72 - 0.84 g / mL, 0.76 - 0.84 g / mL, 0.8 - 0.84 g / mL, 0.6 - 0.8 g / mL, 0.64 - 0.8 g / mL, 0.68 - 0.8 g / mL, 0.72 - 0.8 g / mL, 0.76 - 0.8 g / mL, 0.6 - 0.76 g / mL, 0.64 - 0.76 g / mL, 0.68 - 0.76 g / mL or 0.72 - 0.76 g / mL

[0053] The surface area by nitrogen adsorption is 300 - 700 m 2 / g, 300 - 650 m 2 / g, 300 - 600 m 2 / g, 320 - 600 m 2 / g, 320 - 550 m 2 / g, 320 - 500 m 2 / g, 350 - 700 m 2 / g, 350 - 650 m 2 / g, 350 - 600 m 2 / g, 350 - 600 m 2 / g, 350 - 550 m 2 / g, 350 - 500 m 2 / g, 400 - 700 m 2 / g, 400 - 650 m 2 / g, 400 - 600 m2 / g, 400-550m 2 / g, 450-700m 2 / g, 450~650m 2 / g, 450~600m 2 / g or 450-550m 2 It must be within the range of / g

[0054] Pore ​​volume due to nitrogen adsorption is 0.7~2.50 m³ 2 / g, 0.7~2.2m 2 / g, 0.7~2.0m 2 / g, 0.7~1.8m 2 / g, 0.7~1.6m 2 / g, 0.7~1.4m 2 / g, 0.7~1.2m 2 / g, 0.7~1.0m 2 / g, 0.7~0.9m 2 / g, 0.75~2.50m 2 / g, 0.75~2.2m 2 / g, 0.75~2.0m 2 / g, 0.75~1.8m 2 / g, 0.75~1.6m 2 / g, 0.75~1.4m 2 / g, 0.75~1.2m 2 / g, 0.75~1.0m 2 / g, 0.75~0.9m 2 / g, 0.85~2.50m 2 / g, 0.85~2.2m 2 / g, 0.85~2.0m 2 / g, 0.85~1.8m 2 / g, 0.85~1.6m 2 / g, 0.85~1.4m 2 / g, 0.85~1.2m 2 / g, 0.85~1.0m 2 / g, 0.85~0.9m 2 / g, 0.9~2.50m 2 / g, 0.9~2.2m 2 / g, 0.9~2.0m 2 / g, 0.9~1.8m 2 / g, 0.9~1.6m 2 / g, 0.9~1.4m2 / g, 0.9~1.2m 2 / g, 0.9~1.0m 2 / g, 1.0~2.50m 2 / g, 1.0~2.2m 2 / g, 1.0~2.0m 2 / g, 1.0~1.8m 2 / g, 1.0~1.6m 2 / g, 1.0~1.4m 2 / g, 1.0~1.2m 2 / g, 1.0~2.50m 2 / g, 1.1~2.2m 2 / g, 1.1~2.0m 2 / g, 1.1~1.8m 2 / g, 1.1~1.6m 2 / g, 1.1~1.4m 2 / g, 1.1~1.2m 2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m 2 / g or 1.4-1.6m 2 It must be within the range of / g

[0055] Diameter D at 50% pore volume 50However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[0056] Further details relating to the present invention and the scope of this disclosure can be determined from the appended claims.

[0057] The above description of one or more embodiments of the present invention is primarily illustrative and may include variations, which are recognized to be incorporated into the essence of the invention. In determining the scope of the invention, refer to the following claims.

[0058] For the purposes of U.S. patent practice and, where permitted, in other patent offices, any patents and publications referenced in the above description of the present invention are incorporated herein by reference to the extent that any information contained herein is consistent with and / or supplements the above disclosures. [Examples]

[0059] example The typical amorphous silica-alumina used in the examples according to the present invention are shown in Table 1, and each of them is commercially available. [Table 1]

[0060] Using the amounts of amorphous silica-alumina and nitric acid shown in Table 2, hydrogenation catalyst substrates HCB-1 to HCB-7 were prepared according to the present invention. The synthesis and characteristics of each HCB sample are described below. [Table 2]

[0061] Synthesis and Characterization of Hydrogenation Catalyst Substrate-1 (HCB-1) Hydrogenation catalyst substrate-1 was prepared as follows: 37 parts by weight of silica-alumina sample-1, 30 parts by weight of silica-alumina sample-5, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into a 1 / 16” asymmetrical quadrilateral shape and dried overnight at 250°F (121°C). The dried extruded body was calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0062] Synthesis and Characterization of Hydrogenation Catalyst Substrate-2 (HCB-2) Hydrogenation catalyst substrate-2 was prepared as follows: 37 parts by weight of silica-alumina sample-1, 30 parts by weight of silica-alumina sample-5, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (3 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16” asymmetrical quadrilaterals and dried overnight at 250°F (121°C). The dried extruded body was calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0063] Synthesis and Characterization of Hydrogenation Catalyst Substrate-3 (HCB-3) Hydrogenation catalyst substrate-3 was prepared as follows: 34 parts by weight of silica-alumina sample-3, 33 parts by weight of silica-alumina sample-4, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into a 1 / 16” asymmetrical quadrilateral shape and dried overnight at 250°F (121°C). The dried extruded body was calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0064] Synthesis and Characterization of Hydrogenation Catalyst Substrate-4 (HCB-4) Hydrogenation catalyst substrate-4 was prepared as follows: 67 parts by weight of silica-alumina sample-1, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into a 1 / 16” asymmetrical quadrilateral shape and dried overnight at 250°F (121°C). The dried extruded body was calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0065] Synthesis and Characterization of Hydrogenation Catalyst Substrate-5 (HCB-5) Hydrogenation catalyst substrate-5 was prepared as follows: 67 parts by weight of silica-alumina sample-5, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16” asymmetrical quadrilateral shapes and dried overnight at 250°F (121°C). The dried extruded bodies were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0066] Synthesis and Characterization of Hydrogenation Catalyst Substrate-6 (HCB-6) Hydrogenation catalyst substrate-6 was prepared as follows: 67 parts by weight of silica-alumina sample-4, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16” asymmetrical quadrilateral shapes and dried overnight at 250°F (121°C). The dried extruded bodies were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0067] Synthesis and Characterization of Hydrogenation Catalyst Substrate-7 (HCB-7) The hydrogenation catalyst substrate-7 was prepared as follows: 67 parts by weight of silica-alumina sample-2, 25 parts by weight of pseudo-boehmite alumina powder, and 8 parts by weight of zeolite Y were thoroughly mixed. A dilute nitric acid aqueous solution (2 wt.%) on a dry oxide basis was added to the mixed powder to form an extrudeable paste. The paste was extruded into 1 / 16” asymmetrical quadrilateral shapes and dried overnight at 250°F (121°C). The dried extruded bodies were calcined at 1100°F (593°C) for 1 hour while purging excess dry air, and then cooled to room temperature.

[0068] Table 3 summarizes the physical properties of the hydrogenation catalyst substrates HCB-1 to HCB-7. [Table 3]

[0069] Within the broader scope of this disclosure, and in certain embodiments according to the examples shown herein, a suitable hydrogenation catalyst may be prepared according to the composition ranges of Table 4. [Table 4]

[0070] Results and Discussion Pore ​​size distribution The effect of using two amorphous silica-alumina (ASA) molecules on the nitrogen pore size distribution (N2PSD) was investigated by comparing the pore size distribution (PSD) of hydrogenation catalyst substrate samples HCB-4 and HCB-5, each containing one amorphous silica-alumina molecule, with that of hydrogenation catalyst substrate sample HCB-2, which contains two amorphous silica-alumina molecules. Figure 1 shows the nitrogen PSD for these HCB samples. HCB-4, with one ASA molecule, has smaller pore sizes compared to HCB-5, which also contains one ASA molecule (and has larger pore sizes). Sample HCB-2, with two ASA molecules (synthesized using ASA-1 and ASA-5), has an even wider PSD range, covering almost the entire range shown by the individual amorphous silica-alumina molecules ASA-1 and ASA-5.

[0071] Figure 2 shows a broader pore size distribution obtained by using two ASAs, as determined by mercury pore size determination (Hg PSD). In the hydrogenation catalyst substrate HCB-2, a bimodal PSD is observed, and the positions of the two peaks in this bimodal distribution correspond to the positions obtained with a single ASA sample, HCB-4 and HCB-5.

[0072] Elemental mapping of silicon Elemental mapping of silicon was performed using an electron probe microanalyzer (EPMA). This elemental map allows for the visual identification of silica and alumina domains (within the instrument's resolution limits), and subsequent measurement allows for the acquisition of particle size distribution based on characteristic dimensions, such as particle size. Figure 3 shows the silica domains in silica-alumina sample-1 (ASA-1) used with HCB-4; these domains are within the measurable range by the backscattered electron image obtained from EPMA analysis. In contrast, the size of the silica and alumina domains in sample-5 (ASA-5) is so small that they cannot be measured by the backscattered electron image.

[0073] Particle size and interfacial phase formation To determine the effects of using two amorphous silica-alumina substrates for a hydrogenation catalyst compared to using a single ASA substrate, and of modifying one or both ASAs with a strong acid such as nitric acid, the particle size of silica domains was investigated. Figure 4 shows that the particle size of silica domains in HCB-1 is smaller and the particle size distribution is narrower compared to HCB-4 synthesized using only one silica-alumina ASA material (ASA-1). As a result of using two ASAs (ASA-1 and ASA-5 in this case), as shown in Figures 1 and 2, silica-alumina composite materials with smaller particles were obtained, although the pore size distribution was wider.

[0074] The use of higher concentrations of nitric acid was also investigated, and it was shown that it further promoted the formation of the interfacial phase between the alumina domain and the silica domain, resulting in a further reduction in particle size. Figure 5 shows, for example, that when the nitric acid was increased to 3 wt% (on a dry oxide basis), the smaller particles with a particle size of approximately less than 14 micrometers, which were observed in HCB-4 or HCB-1 in Figure 4, completely disappeared in HCB-2.

[0075] Performance of hydrocracking catalysts The hydrocracking performance of catalysts containing the composite material for the base material of this disclosure was investigated using typical feedstocks for a hydrocracking reactor. Table 6 shows the physical properties of the petroleum feedstocks used to evaluate the performance of the hydrocracking catalysts prepared using the base material for the hydrocracking catalyst of this disclosure. In each test, the total pressure was 2300 PSIG (partial pressure at reactor inlet: 2100 PSIA H2), the H2-to-oil ratio was 5000 SCFB, and the LHSV was 1.0h. -1 Under these process conditions, the catalyst was brought into contact with the raw materials. [Table 6]

[0076] Figure 6 shows the catalytic activity of catalysts prepared using the various hydrogenation catalyst substrate materials according to this disclosure, in contact with the above-mentioned raw materials. In catalyst substrate composite materials with two ASAs, particularly those based on HCB-1 and HCB-2, improved catalytic activity was observed compared to catalyst HCB materials HCB-5, HCB-6, and HCB-7 with one ASA, as indicated by the increased hydrogenation (HCR) conversion rate of the raw materials shown in Table 6 at the same temperature.

[0077] Figure 7 shows the yield of heavy diesel obtained from catalysts prepared using various hydrogenation catalyst base materials, in contact with the above-mentioned raw materials. Figure 8 shows the yield of the total fraction obtained from catalysts prepared using various hydrogenation catalyst base materials, in contact with the above-mentioned raw materials. When catalyst base material composites with two ASAs, particularly those based on HCB-1 and HCB-2, were compared with catalyst HCB materials HCB-5, HCB-6, and HCB-7, which have one ASA, it was observed that their HCR selectivity was equivalent, as shown by the yields of heavy diesel and total fraction obtained from the hydrocracking of the raw materials in Table 6. The following is further disclosed regarding the present invention. [1] A silica-alumina composite material suitable for use in the production of a substrate for a hydrogenation catalyst, comprising a modified first silica-alumina and a second silica-alumina, wherein the first silica-alumina and the second silica-alumina differ in one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size. [2] The material according to [1], wherein the modified first silica-alumina is modified by contacting the first silica-alumina with a strong acid, preferably nitric acid, under extrusion conditions. [3] The material according to either [1] or [2], wherein the first silica-alumina and the second silica-alumina include amorphous silica-alumina, or both are amorphous silica-alumina. [4] The material according to any one of [1] to [3], wherein the second silica-alumina is a modified second silica-alumina comprising silica domains and alumina domains, as well as an interfacial phase between silica and alumina. [5] The material according to [4], wherein the modified second silica-alumina is modified by contacting the second silica-alumina with a strong acid, preferably nitric acid, under extrusion conditions. [6] The material according to any one of [1] to [5] further comprising a molecular sieve and / or an alumina carrier. [7] The material according to [6], wherein the molecular sieve comprises Y zeolite, preferably Y zeolite with a unit cell size of 24.15 Å to 24.45 Å, and optionally further comprises β zeolite. [8] The first silica-alumina is used in amounts of 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 30-60 wt.%, or 30-50 wt.%, The aforementioned second silica-alumina is used in amounts of 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 25-60 wt.%, or 25-50 wt.%, Molecular sieves are used in concentrations of 0-60 wt.%, 2-50 wt.%, 5-40 wt.%, 5-30 wt.%, 5-20 wt.%, or 5-15 wt.%, Alumina in concentrations of 0-40 wt.%, 5-40 wt.%, 10-30 wt.%, or 15-30 wt.%, The materials listed in any of [1] to [7], including [1]. [9] The material according to any one of [1] to [8], wherein the first silica-alumina and / or the second silica-alumina comprises one or more of the following: The alumina content must be within the range of 10-98 wt.%, 10-80 wt.%, 20-80 wt.%, 30-80 wt.%, 30-70 wt.%, 40-70 wt.%, 50-70 wt.%, 50-80 wt.%, 60-80 wt.%, 10-50 wt.%, 10-40 wt.%, 20-40 wt.%, 40-98 wt.%, 50-98 wt.%, 60-98 wt.%, 70-98 wt.%, or 80-98 wt.%. The surface area due to nitrogen adsorption is 300-700 m². 2 / g, 300-650m 2 / g, 300-600m 2 / g, 320-600m 2 / g, 320~550m 2 / g, 320-500m 2 / g, 350-700m 2 / g, 350~650m 2 / g, 350-600m 2 / g, 350-600m 2 / g, 350~550m 2 / g, 350-500m 2 / g, 400-700m 2 / g, 400~650m 2 / g, 400-600m 2 / g, 400-550m 2 / g, 450-700m 2 / g, 450~650m 2 / g, 450~600m 2 / g or 450-550m 2 It must be within the range of / g Pore ​​volume due to nitrogen adsorption is 0.7~2.50 m³ 2 / g, 0.7~2.2m 2 / g, 0.7~2.0m 2 / g, 0.7~1.8m 2 / g, 0.7~1.6m 2 / g, 0.7~1.4m 2 / g, 0.7~1.2m 2 / g, 0.7~1.0m 2 / g, 0.7~0.9m 2 / g, 0.75~2.50m 2 / g, 0.75~2.2m 2 / g, 0.75~2.0m 2 / g, 0.75~1.8m 2 / g, 0.75~1.6m 2 / g, 0.75~1.4m 2 / g, 0.75~1.2m 2 / g, 0.75~1.0m 2 / g, 0.75~0.9m 2 / g, 0.85~2.50m 2 / g, 0.85~2.2m 2 / g, 0.85~2.0m 2 / g, 0.85~1.8m 2 / g, 0.85~1.6m 2 / g, 0.85~1.4m 2 / g, 0.85~1.2m 2 / g, 0.85~1.0m 2 / g, 0.85~0.9m 2 / g, 0.9~2.50m 2 / g, 0.9~2.2m 2 / g, 0.9~2.0m 2 / g, 0.9~1.8m 2 / g, 0.9~1.6m 2 / g, 0.9~1.4m 2 / g, 0.9~1.2m 2 / g, 0.9~1.0m 2 / g, 1.0~2.50m 2 / g, 1.0~2.2m 2 / g, 1.0~2.0m 2 / g, 1.0~1.8m 2 / g, 1.0~1.6m 2 / g, 1.0~1.4m 2 / g, 1.0~1.2m 2 / g, 1.0~2.50m 2 / g, 1.1~2.2m 2 / g, 1.1~2.0m 2 / g, 1.1~1.8m 2 / g, 1.1~1.6m 2 / g, 1.1~1.4m2 / g, 1.1~1.2m 2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m 2 / g or 1.4-1.6m 2 It must be within the range of / g Diameter D at 50% pore volume 50 However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[10] The materials listed in any of [1] to [9] below, including one or more of the following: Particle density is 0.6~0.1.0g / mL, 0.64~1.0g / mL, 0.68~1.0g / mL, 0.72~1.0g / mL, 0.76~1.0g / mL, 0.8~ 1.0g / mL, 0.84~1.0g / mL, 0.88~1.0g / mL, 0.6~0.96g / mL, 0.64~0.96g / mL, 0.68~0.96g / mL, 0 .72~0.96g / mL, 0.76~0.96g / mL, 0.8~0.96g / mL, 0.84~0.96g / mL, 0.88~0.96g / mL, 0.6~0.92 g / mL, 0.64~0.92g / mL, 0.68~0.92g / mL, 0.72~0.92g / mL, 0.76~0.92g / mL, 0.8~0.92g / mL, 0. 84~0.92g / mL, 0.6~0.88g / mL, 0.64~0.88g / mL, 0.68~0.88g / mL, 0.72~0.88g / mL, 0.76~0.88 g / mL, 0.8~0.88g / mL, 0.6~0.84g / mL, 0.64~0.84g / mL, 0.68~0.84g / mL, 0.72~0.84g / mL, 0.7 The concentration must be within the range of 6-0.84 g / mL, 0.8-0.84 g / mL, 0.6-0.8 g / mL, 0.64-0.8 g / mL, 0.68-0.8 g / mL, 0.72-0.8 g / mL, 0.76-0.8 g / mL, 0.6-0.76 g / mL, 0.64-0.76 g / mL, 0.68-0.76 g / mL, or 0.72-0.76 g / mL. The surface area due to nitrogen adsorption is 300-700 m². 2 / g, 300-650m 2 / g, 300-600m 2 / g, 320-600m 2 / g, 320~550m 2 / g, 320-500m 2 / g, 350-700m 2 / g, 350~650m 2 / g, 350-600m 2 / g, 350-600m 2 / g, 350~550m 2 / g, 350-500m 2 / g, 400-700m 2 / g, 400~650m 2 / g, 400-600m 2 / g, 400-550m 2 / g, 450-700m 2 / g, 450~650m 2 / g, 450~600m 2 / g or 450-550m 2 It must be within the range of / g Pore ​​volume due to nitrogen adsorption is 0.7~2.50 m³ 2 / g, 0.7~2.2m 2 / g, 0.7~2.0m 2 / g, 0.7~1.8m 2 / g, 0.7~1.6m 2 / g, 0.7~1.4m 2 / g, 0.7~1.2m 2 / g, 0.7~1.0m 2 / g, 0.7~0.9m 2 / g, 0.75~2.50m 2 / g, 0.75~2.2m 2 / g, 0.75~2.0m 2 / g, 0.75~1.8m 2 / g, 0.75~1.6m 2 / g, 0.75~1.4m 2 / g, 0.75~1.2m 2 / g, 0.75~1.0m 2 / g, 0.75~0.9m 2 / g, 0.85~2.50m 2 / g, 0.85~2.2m 2 / g, 0.85~2.0m 2 / g, 0.85~1.8m 2 / g, 0.85~1.6m 2 / g, 0.85~1.4m 2 / g, 0.85~1.2m 2 / g, 0.85~1.0m 2 / g, 0.85~0.9m 2 / g, 0.9~2.50m 2 / g, 0.9~2.2m 2 / g, 0.9~2.0m 2 / g, 0.9~1.8m 2 / g, 0.9~1.6m 2 / g, 0.9~1.4m 2 / g, 0.9~1.2m 2 / g, 0.9~1.0m2 / g, 1.0~2.50m 2 / g, 1.0~2.2m 2 / g, 1.0~2.0m 2 / g, 1.0~1.8m 2 / g, 1.0~1.6m 2 / g, 1.0~1.4m 2 / g, 1.0~1.2m 2 / g, 1.0~2.50m 2 / g, 1.1~2.2m 2 / g, 1.1~2.0m 2 / g, 1.1~1.8m 2 / g, 1.1~1.6m 2 / g, 1.1~1.4m 2 / g, 1.1~1.2m 2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m 2 / g or 1.4-1.6m 2 It must be within the range of / g Diameter D at 50% pore volume 50 However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[11] The materials listed in any of [1] to

[10] are in the range of approximately 40-100 wt.%, 40-99 wt.%, 50-99 wt.%, 60-99 wt.%, or 70-99 wt.%, Precious metals in the ranges of 0.1-5 wt.%, 0.1-4 wt.%, 0.1-3 wt.%, 0.1-2 wt.%, or 0.1-1 wt.%, The base metal content is in the range of 0-40 wt.%, 5-40 wt.%, 5-30 wt.%, 10-40 wt.%, 10-30 wt.%, 10-20 wt.%, 20-40 wt.%, or 20-30 wt.%, and the base metal content is arbitrarily in the range of 0-40 wt.%, 5-40 wt.%, 5-30 wt.%, 10-40 wt.%, 10-30 wt.%, 10-20 wt.%, 20-40 wt.%, or 20-30 wt.%, The accelerator is in the range of 0-30 wt.%, 0-20 wt.%, 0-10 wt.%, 5-30 wt.%, 5-20 wt.%, 10-30 wt.%, or 10-20 wt.%, A hydrogenation catalyst containing [specific components].

[12] A method for producing a silica-alumina composite material suitable for use as a substrate for hydrogenation catalysts, or for producing a substrate for hydrogenation catalysts, The method involves combining a first silica-alumina and a second silica-alumina, optionally with molecular sieves and / or an alumina support, to form a base composition. In the first silica-alumina and the second silica-alumina, one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size are different, and the formation is as described above. A diluted strong acid aqueous solution, preferably nitric acid, is added to the aforementioned base composition to form an extrudeable composition. The extrudeable composition is extruded, dried, and calcined to form the silica-alumina composite material. The method comprising the above.

[13] The method according to

[12] , wherein the first silica-alumina and the second silica-alumina include amorphous silica-alumina or amorphous silica-alumina.

[14] The method according to

[12] , wherein the base material composition comprises the first silica-alumina, the second silica-alumina, Y zeolite, and alumina, and optionally further comprises β zeolite.

[15] The aforementioned base material composition The first silica-alumina is used in amounts of 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 30-60 wt.%, or 30-50 wt.%, The aforementioned second silica-alumina is used in amounts of 1-90 wt.%, 10-80 wt.%, 20-70 wt.%, 25-60 wt.%, or 25-50 wt.%, Molecular sieves are used in concentrations of 0-60 wt.%, 2-50 wt.%, 5-40 wt.%, 5-30 wt.%, 5-20 wt.%, or 5-15 wt.%, Alumina in concentrations of 0-40 wt.%, 5-40 wt.%, 10-30 wt.%, or 15-30 wt.%, A method of any of

[12] to

[14] , including the method described in

[12] to

[14] .

[16] The method according to any one of

[12] to

[15] , wherein the first silica-alumina and / or the second silica-alumina comprises one or more of the following: The alumina content must be within the range of 10-98 wt.%, 10-80 wt.%, 20-80 wt.%, 30-80 wt.%, 30-70 wt.%, 40-70 wt.%, 50-70 wt.%, 50-80 wt.%, 60-80 wt.%, 10-50 wt.%, 10-40 wt.%, 20-40 wt.%, 40-98 wt.%, 50-98 wt.%, 60-98 wt.%, 70-98 wt.%, or 80-98 wt.%. The surface area due to nitrogen adsorption is 300-700 m². 2 / g, 300-650m 2 / g, 300-600m 2 / g, 320-600m 2 / g, 320~550m 2 / g, 320-500m 2 / g, 350-700m 2 / g, 350~650m 2 / g, 350-600m 2 / g, 350-600m 2 / g, 350~550m 2 / g, 350-500m 2 / g, 400-700m 2 / g, 400~650m 2 / g, 400-600m 2 / g, 400-550m 2 / g, 450-700m 2 / g, 450~650m 2 / g, 450~600m2 / g or 450-550m 2 It must be within the range of / g Pore ​​volume due to nitrogen adsorption is 0.7~2.50 m³ 2 / g, 0.7~2.2m 2 / g, 0.7~2.0m 2 / g, 0.7~1.8m 2 / g, 0.7~1.6m 2 / g, 0.7~1.4m 2 / g, 0.7~1.2m 2 / g, 0.7~1.0m 2 / g, 0.7~0.9m 2 / g, 0.75~2.50m 2 / g, 0.75~2.2m 2 / g, 0.75~2.0m 2 / g, 0.75~1.8m 2 / g, 0.75~1.6m 2 / g, 0.75~1.4m 2 / g, 0.75~1.2m 2 / g, 0.75~1.0m 2 / g, 0.75~0.9m 2 / g, 0.85~2.50m 2 / g, 0.85~2.2m 2 / g, 0.85~2.0m 2 / g, 0.85~1.8m 2 / g, 0.85~1.6m 2 / g, 0.85~1.4m 2 / g, 0.85~1.2m 2 / g, 0.85~1.0m 2 / g, 0.85~0.9m 2 / g, 0.9~2.50m 2 / g, 0.9~2.2m 2 / g, 0.9~2.0m 2 / g, 0.9~1.8m 2 / g, 0.9~1.6m 2 / g, 0.9~1.4m 2 / g, 0.9~1.2m 2 / g, 0.9~1.0m 2 / g, 1.0~2.50m 2 / g, 1.0~2.2m 2 / g, 1.0~2.0m 2 / g, 1.0~1.8m 2 / g, 1.0~1.6m 2 / g, 1.0~1.4m 2 / g, 1.0~1.2m 2 / g, 1.0~2.50m 2 / g, 1.1~2.2m 2 / g, 1.1~2.0m 2 / g, 1.1~1.8m 2 / g, 1.1~1.6m 2 / g, 1.1~1.4m 2 / g, 1.1~1.2m 2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m 2 / g or 1.4-1.6m 2 It must be within the range of / g Diameter D at 50% pore volume 50 However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[17] The method according to any one of

[12] to

[16] , wherein the silica-alumina composite material comprises one or more of the following: Particle density is 0.6~0.1.0g / mL, 0.64~1.0g / mL, 0.68~1.0g / mL, 0.72~1.0g / mL, 0.76~1.0g / mL, 0.8~ 1.0g / mL, 0.84~1.0g / mL, 0.88~1.0g / mL, 0.6~0.96g / mL, 0.64~0.96g / mL, 0.68~0.96g / mL, 0 .72~0.96g / mL, 0.76~0.96g / mL, 0.8~0.96g / mL, 0.84~0.96g / mL, 0.88~0.96g / mL, 0.6~0.92 g / mL, 0.64~0.92g / mL, 0.68~0.92g / mL, 0.72~0.92g / mL, 0.76~0.92g / mL, 0.8~0.92g / mL, 0. 84~0.92g / mL, 0.6~0.88g / mL, 0.64~0.88g / mL, 0.68~0.88g / mL, 0.72~0.88g / mL, 0.76~0.88 g / mL, 0.8~0.88g / mL, 0.6~0.84g / mL, 0.64~0.84g / mL, 0.68~0.84g / mL, 0.72~0.84g / mL, 0.7 The concentration must be within the range of 6-0.84 g / mL, 0.8-0.84 g / mL, 0.6-0.8 g / mL, 0.64-0.8 g / mL, 0.68-0.8 g / mL, 0.72-0.8 g / mL, 0.76-0.8 g / mL, 0.6-0.76 g / mL, 0.64-0.76 g / mL, 0.68-0.76 g / mL, or 0.72-0.76 g / mL. The surface area due to nitrogen adsorption is 300-700 m². 2 / g, 300-650m 2 / g, 300-600m 2 / g, 320-600m 2 / g, 320~550m 2 / g, 320-500m2 / g, 350-700m 2 / g, 350~650m 2 / g, 350-600m 2 / g, 350-600m 2 / g, 350~550m 2 / g, 350-500m 2 / g, 400-700m 2 / g, 400~650m 2 / g, 400-600m 2 / g, 400-550m 2 / g, 450-700m 2 / g, 450~650m 2 / g, 450~600m 2 / g or 450-550m 2 It must be within the range of / g Pore ​​volume due to nitrogen adsorption is 0.7~2.50 m³ 2 / g, 0.7~2.2m 2 / g, 0.7~2.0m 2 / g, 0.7~1.8m 2 / g, 0.7~1.6m 2 / g, 0.7~1.4m 2 / g, 0.7~1.2m 2 / g, 0.7~1.0m 2 / g, 0.7~0.9m 2 / g, 0.75~2.50m 2 / g, 0.75~2.2m 2 / g, 0.75~2.0m 2 / g, 0.75~1.8m 2 / g, 0.75~1.6m 2 / g, 0.75~1.4m 2 / g, 0.75~1.2m 2 / g, 0.75~1.0m 2 / g, 0.75~0.9m 2 / g, 0.85~2.50m 2 / g, 0.85~2.2m 2 / g, 0.85~2.0m 2 / g, 0.85~1.8m 2 / g, 0.85~1.6m 2 / g, 0.85~1.4m 2 / g, 0.85~1.2m 2 / g, 0.85~1.0m 2 / g, 0.85~0.9m 2 / g, 0.9~2.50m 2 / g, 0.9~2.2m 2 / g, 0.9~2.0m 2 / g, 0.9~1.8m 2 / g, 0.9~1.6m 2 / g, 0.9~1.4m 2 / g, 0.9~1.2m 2 / g, 0.9~1.0m 2 / g, 1.0~2.50m 2 / g, 1.0~2.2m 2 / g, 1.0~2.0m 2 / g, 1.0~1.8m 2 / g, 1.0~1.6m 2 / g, 1.0~1.4m 2 / g, 1.0~1.2m 2 / g, 1.0~2.50m 2 / g, 1.1~2.2m 2 / g, 1.1~2.0m 2 / g, 1.1~1.8m 2 / g, 1.1~1.6m 2 / g, 1.1~1.4m 2 / g, 1.1~1.2m 2 / g, 1.2~2.5m 2 / g, 1.2~2.0m 2 / g, 1.2~1.8m 2 / g, 1.2~1.6m 2 / g, 1.2~1.4m 2 / g, 1.3~2.5m 2 / g, 1.3~2.0m 2 / g, 1.3~1.8m 2 / g, 1.3~1.6m 2 / g, 1.3~1.4m 2 / g, 1.4~2.5m 2 / g, 1.4~2.0m 2 / g, 1.4~1.8m2 / g or 1.4-1.6m 2 It must be within the range of / g Diameter D at 50% pore volume 50 However, 3~35nm, 3~20nm, 3~15nm, 3~10nm, 3~8nm, 3~7nm, 4~25nm, 4~20nm, 4~15nm, 4~10nm, 4~8nm, 4~7nm, 5~25nm, 5~20nm, 5~15nm, 5~10nm, 5~8nm, 5~7nm, 6~25nm, 6~25nm, 6~20nm, 6~15nm, 6~ The wavelength must be within the range of 10nm, 6-8nm, 8-25nm, 8-20nm, 8-15nm, 8-10nm, 10-25nm, 10-20nm, 10-15nm, 10-13nm, 12-25nm, 12-20nm, 12-15nm, 14-25nm, 14-20nm, 14-18nm, 16-25nm, 16-20nm, or 16-18nm.

[18] A silica-alumina composite material prepared by any of the methods described in

[12] to

[17] .

[19] A method for hydrogenating a hydrocarbon-containing raw material, comprising contacting a hydrogenation catalyst with the hydrocarbon-containing raw material and hydrogen under hydrogenation conditions, wherein the hydrogenation catalyst comprises at least one metal attached to a material described in any of [1] to

[10] or

[18] , or the hydrogenation catalyst is the catalyst described in

[11] .

[20] The method according to

[19] , comprising a hydrocracking process carried out under hydrocracking conditions that improve catalytic activity and yield equivalent heavy diesel yield and total distillate yield compared to a hydrocracking catalyst that differs only in that the catalyst comprises either the first silica-alumina or the second silica-alumina, rather than both the first silica-alumina and the second silica-alumina.

Claims

1. A silica-alumina composite material suitable for use in the production of a substrate for hydrogenation catalysts, comprising a modified first silica-alumina and a second silica-alumina, wherein the first silica-alumina and the second silica-alumina differ in one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size, The aforementioned composite material The first silica-alumina is 30 to 50 wt.%, The second silica-alumina is present in an amount of 25 to 50 wt.%, The first silica-alumina and / or the second silica-alumina comprises one or more of the following: The alumina content must be in the range of 10 to 98 wt.%; The surface area due to nitrogen adsorption is 300-600 m². ２ It must be within the range of / g; The pore volume due to nitrogen adsorption is in the range of 0.7 to 2.0 mL / g; Diameter D at 50% pore volume ５０ However, it must be in the range of 4 to 20 nm. The composite material includes one or more of the following: The particle density must be in the range of 0.6 to 0.96 g / mL; The surface area due to nitrogen adsorption is 300-600 m². ２ It must be within the range of / g; The pore volume due to nitrogen adsorption is in the range of 0.7 to 2.0 mL / g; Diameter D at 50% pore volume ５０ However, it is in the range of 4 to 20 nm, and moreover, The modified first silica-alumina is a product obtained by contacting the first silica-alumina with a strong acid, nitric acid, under extrusion conditions. Both the first silica-alumina and the second silica-alumina are amorphous silica-alumina. The second silica-alumina is a modified second silica-alumina comprising silica domains and alumina domains, as well as an interfacial phase between silica and alumina. The composite material wherein the modified second silica-alumina is a product obtained by contacting the second silica-alumina with a strong acid, nitric acid, under extrusion conditions.

2. The material according to claim 1, further comprising a molecular sieve and / or an alumina carrier.

3. The material according to claim 2, wherein the molecular sieve comprises a Y zeolite having a unit cell size of 24.15 Å to 24.45 Å, and optionally further comprises a β zeolite.

4. The material according to any one of claims 1 to 3 is in the range of 50 to 99 wt.%, Precious metals in the range of 0.1 to 3 wt.% Base metals in the range of 10 to 30 wt.% The accelerator is in the range of 0-20 wt.%. A hydrogenation catalyst containing [specific components].

5. A method for producing a silica-alumina composite material suitable for use as a substrate for hydrogenation catalysts, or for producing a substrate for hydrogenation catalysts, The first silica-alumina and the second silica-alumina are optionally combined with molecular sieves and / or alumina carriers to form a base composition, In the first silica-alumina and the second silica-alumina, one or more characteristics selected from the silica-to-alumina ratio, surface area, pore diameter, pore volume, silica domain size, or alumina domain size are different, and the formation is as described above. Adding nitric acid, which is a diluted strong acid aqueous solution, to the aforementioned base composition to form an extrudeable composition, The extrudeable composition is extruded, dried, and calcined to form the silica-alumina composite material. Includes, The aforementioned base material composition The first silica-alumina is 30 to 50 wt.%, The second silica-alumina is present in an amount of 25 to 50 wt.%, The first silica-alumina and / or the second silica-alumina comprises one or more of the following: The alumina content must be in the range of 10 to 98 wt.%; The surface area due to nitrogen adsorption is 300-600 m². ２ It must be within the range of / g; The pore volume due to nitrogen adsorption is in the range of 0.7 to 2.0 mL / g; Diameter D at 50% pore volume ５０ However, it must be in the range of 4 to 20 nm. The silica-alumina composite material comprises one or more of the following: The particle density must be in the range of 0.6 to 0.96 g / mL; The surface area due to nitrogen adsorption is 300-600 m². ２ It must be within the range of / g; The pore volume due to nitrogen adsorption is in the range of 0.7 to 2.0 mL / g; Diameter D at 50% pore volume ５０ However, it is in the range of 4 to 20 nm, and moreover, The modified first silica-alumina is a product obtained by contacting the first silica-alumina with a strong acid, nitric acid, under extrusion conditions. Both the first silica-alumina and the second silica-alumina are amorphous silica-alumina. The second silica-alumina is a modified second silica-alumina comprising silica domains and alumina domains, as well as an interfacial phase between silica and alumina. The method wherein the modified second silica-alumina is a product obtained by contacting the second silica-alumina with a strong acid, nitric acid, under extrusion conditions.

6. The method according to claim 5, wherein the base material composition comprises the first silica-alumina, the second silica-alumina, Y-zeolite, and alumina, and optionally further comprises β-zeolite.

7. A silica-alumina composite material which is a product of the method described in claim 5 or 6.

8. A method for hydrogenating a hydrocarbon-containing raw material, comprising contacting a hydrogenation catalyst with the hydrocarbon-containing raw material and hydrogen under hydrogenation conditions, wherein the hydrogenation catalyst comprises at least one metal attached to a material according to any one of claims 1 to 3 or 7, or the hydrogenation catalyst is the catalyst according to claim 4.

9. The method according to claim 8, comprising a hydrocracking process carried out under hydrocracking conditions that improve catalytic activity and yield the same heavy diesel yield and total distillate yield compared to a hydrocracking catalyst that differs only in that the catalyst comprises either the first silica-alumina or the second silica-alumina, rather than both the first silica-alumina and the second silica-alumina.

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