Polymetallic bulk hydrogenation catalyst

Abstract

A multimetallic bulk catalyst and a method for synthesizing the same are provided. The multimetallic bulk catalyst contains nickel, molybdenum, tungsten, niobium, and optionally titanium and / or copper. The catalyst is useful for the hydroprocessing of hydrocarbon feedstocks, particularly hydrodesulfurization and hydrodenitrogenation.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of priority to U.S. Patent Application No. 63 / 149,736, filed on February 16, 2021, the disclosure of which is incorporated herein by reference.

[0002] This disclosure relates to a multimetal bulk catalyst for use in the hydroprocessing of hydrocarbon feedstocks, and additionally to a method for preparing such a catalyst.

Background Art

[0003] The hydroprocessing of hydrocarbon feedstocks generally includes all processes in which the hydrocarbon feedstock reacts with hydrogen in the presence of a catalyst and under hydroprocessing conditions (usually high temperature and high pressure). Hydroprocessing includes processes such as hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrocracking, hydrotreating, hydrogen isomerization, and hydrocracking.

[0004] Hydroprocessing catalysts typically include one or more sulfided Group 6 metals, together with one or more Group 8 - 10 non - noble metals as promoters, on an inert support such as alumina. Hydroprocessing catalysts particularly suitable for hydrodesulfurization, and additionally for hydrodenitrogenation, generally include molybdenum sulfide or tungsten sulfide, which is activated with a metal such as cobalt, nickel, iron, or a combination thereof.

[0005] In addition to supported catalysts, hydroprocessing using bulk catalysts (also called "non - supported" catalysts) is also known. Although bulk hydroprocessing catalyst compositions have higher catalytic activity than conventional supported hydroprocessing catalysts, there is a continuing need in the art for the development of novel bulk catalyst compositions with further improved hydroprocessing activity.

Summary of the Invention

[0006] In the first embodiment, a bulk catalyst precursor is provided comprising (a) 1 to 60 wt% Ni based on metal oxide, (b) 1 to 40 wt% Mo based on metal oxide, (c) 5 to 80 wt% W based on metal oxide, (d) 0.01 to 20 wt% Nb based on metal oxide, (e) 0 to 45 wt% Ti based on metal oxide, and (f) 0 to 10 wt% Cu based on metal oxide.

[0007] In a second embodiment, a sulfurized bulk catalyst is provided, characterized in that it is a sulfurized bulk catalyst precursor as described herein.

[0008] In a third aspect, a method for preparing a bulk catalyst precursor as described herein is provided, comprising: (a) combining in a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Nb-containing precursor, (v) optionally a Ti-containing precursor and / or a Cu-containing precursor, (vi) optionally an organic compound-based component, and (vii) a protic liquid; and (b) reacting the mixture under conditions sufficient to produce a precipitate of a bulk catalyst precursor, wherein the bulk catalyst precursor preparation step is carried out at a temperature of 200°C or lower.

[0009] A fourth aspect provides a method for preparing a bulk catalyst precursor as described herein, comprising: (a) combining in a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Nb-containing precursor, (v) optionally a Cu-containing precursor, (vi) optionally an organic compound-based component, and (vii) a protic liquid; (b) reacting the mixture under conditions sufficient to produce a precipitate of an intermediate bulk catalyst precursor; and (c) compounding the intermediate bulk catalyst precursor with a Ti-containing precursor to form a bulk catalyst precursor, wherein the bulk catalyst precursor preparation step is carried out at a temperature of 200°C or lower.

[0010] In a fifth aspect, a process for hydrogenating a hydrocarbon raw material is provided, comprising contacting the hydrocarbon raw material with hydrogen in the presence of a bulk catalyst under hydrogenation conditions to obtain at least one product, wherein the bulk catalyst is derived from or can be derived from a catalyst precursor comprising (a) 1 to 60 wt% Ni on a metal oxide basis, (b) 1 to 40 wt% Mo on a metal oxide basis, (c) 5 to 80 wt% W on a metal oxide basis, (d) 0.01 to 20 wt% Nb on a metal oxide basis, (e) 0 to 45 wt% Ti on a metal oxide basis, and (f) 0 to 10 wt% Cu on a metal oxide basis. In connection with the present invention, the following is further disclosed. [1] (a) Based on metal oxides, 1 to 60% by weight of Ni (b) Based on metal oxides, 1 to 40% by weight of Mo (c) Based on metal oxides, 5-80% by weight of W, (d) Based on metal oxides, 0.01 to 20% by weight of Nb, (e) 0 to 45% by weight of Ti, based on metal oxides, (f) 0-10% by weight of Cu on a metal oxide basis A bulk catalyst precursor containing [the specified element]. [2] The bulk catalyst precursor according to [1], further comprising an organic compound-based component. [3] The bulk catalyst precursor according to [2], wherein the organic compound-based component is selected from the group consisting of organic acids or their salts, sugars, sugar alcohols, or combinations thereof. [4] The bulk catalyst precursor according to [2], wherein the organic compound-based component is selected from the group consisting of glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetate, malic acid, fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose, sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, or combinations thereof. [5] The bulk catalyst precursor according to [2], wherein the molar ratio of Ni to the organic compound-based component is in the range of 3:1 to 20:1. [6] A bulk catalyst precursor as described in [1], wherein the molar ratio of Nb / (Ni+Mo+W+Ti+Cu) is in the range of 10:1 to 1:10. [7] A bulk catalyst precursor as described in [1], wherein the molar ratio of Ni / W is in the range of 10:1 to 1:10. [8] A bulk catalyst precursor as described in [1], wherein the molar ratio of W / Mo is in the range of 100:1 to 1:100. [9] The bulk catalyst precursor described in [1] is the bulk catalyst precursor of the following formula: A v [Ni1-a-b Nb a Cu b (OH) x (L) p y ] z [Mo m W 1-m O 4 ][Ti(OH) n O 2-n / 2 ] w During the ceremony, (i) A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, a phosphonium cation, or a combination thereof. (ii) L is an organic compound-based component, (iii)0 <a<1、0≦b<1、a+b<1、0≦y≦2 / p、0≦x<2、0≦v<2、0<z、0<m<1、0<n<4、0<w / (z+1)<10である。

[10] The bulk catalyst precursor according to [1], further comprising 1 to 15% by weight of a binder.

[11] One or more of the following characteristics: 50-250m 2 BET specific surface area per gram: 0.02~0.80 cm² 3 The void volume per g, and 1.00 to 3.00 cm³ 3 A bulk catalyst precursor according to [1] having a particle density of / g.

[12] A sulfurized bulk catalyst, characterized in that it is a sulfurized bulk catalyst precursor as described in [1].

[13] A method for preparing a bulk catalyst precursor as described in [1], (a) In the reaction mixture, (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv)Nb-containing precursor, (v) Depending on the case, Ti-containing precursor and / or Cu-containing precursor, (vi) Depending on the case, organic compound-based components, as well as (vii) Protic liquids Combining them, (b) Reacting the mixture under conditions sufficient to produce a precipitate of the bulk catalyst precursor, The method wherein the preparation step of the bulk catalyst precursor is carried out at a temperature of 200°C or lower.

[14] The reaction mixture To prepare a first mixture comprising a Ni-containing precursor, an Nb-containing precursor, an optionally Cu-containing precursor, a protic liquid, and optionally an organic compound-based component, To prepare a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid, Depending on the circumstances, a Ti-containing precursor may be added to the first mixture, the second mixture, or a combination thereof. Heat both the first and second mixtures to a temperature of 60°C to 150°C, The first and second mixtures are combined with each other, The method described in

[13] , which is prepared by

[13] .

[15] The Ti-containing precursor is TiO 2 Nanoparticles, colloidal TiO 2 fumed TiO 2 The method according to

[14] , selected from titanium hydroxide, organotitanium compounds, titanium halides, organotitanium halides, water-soluble titanium salts, or combinations thereof.

[16] A method for preparing a bulk catalyst precursor as described in [1], (a) In the reaction mixture, (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv)Nb-containing precursor, (v) Depending on the case, Cu-containing precursor, (vi) Depending on the case, organic compound-based components, as well as (vii) Protic liquids Combining them, (b) The mixture is reacted under conditions sufficient to produce a precipitate of the intermediate bulk catalyst precursor, (c) Composite the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor, The method wherein the preparation step of the bulk catalyst precursor is carried out at a temperature of 200°C or lower.

[17] The reaction mixture To prepare a first mixture comprising a Ni-containing precursor, an Nb-containing precursor, an optionally Cu-containing precursor, a protic liquid, and optionally an organic compound-based component, To prepare a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid, Heat both the first and second mixtures to a temperature of 60°C to 150°C, The first and second mixtures are combined with each other, The method described in

[16] , which is prepared by

[16] .

[18] The Ti-containing precursor is TiO 2 Nanoparticles, fumed TiO 2 , or a combination thereof, as described in

[16] .

[19] The method according to

[16] , wherein the intermediate bulk catalyst precursor is a Ni-Mo-W-Nb or Ni-Mo-W-Nb-Cu bulk catalyst precursor.

[20] The method according to

[13] or

[16] , wherein the reaction is carried out at one or more temperatures, either (a) under atmospheric pressure in the range of 60°C to 100°C, or (b) above 100°C under self-pressure.

[21] The method according to

[13] or

[16] , wherein the organic compound-based component is selected from organic acids or salts thereof, sugars, sugar alcohols, or combinations thereof.

[22] The method according to

[21] , wherein the organic compound-based component is selected from glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetate, malic acid, fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose, sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, or a combination thereof.

[23] A step of compounding the bulk catalyst precursor with a material selected from the group consisting of a binder material, a conventional hydrogenation catalyst, a cracking compound, or a mixture thereof, in an amount of 0 to 40% by weight. Processes involving spray drying, (flash) drying, milling, kneading, slurry mixing, drying or wet mixing, or a combination thereof. molding process, A process of drying and / or heat treatment at a temperature of 200°C or lower, Sulfurization process The method described in

[13] or

[16] , further comprising one or more of the above.

[24] A hydrogenation process for hydrocarbon raw materials, comprising contacting the hydrocarbon raw materials with hydrogen in the presence of a bulk catalyst under hydrogenation conditions to obtain at least one product, wherein the bulk catalyst is (a) Based on metal oxides, 1 to 60% by weight of Ni (b) Based on metal oxides, 1 to 40% by weight of Mo (c) Based on metal oxides, 5-80% by weight of W, (d) Based on metal oxides, 0.01 to 20% by weight of Nb, (e) 0 to 45% by weight of Ti, based on metal oxides, (f) 0-10% by weight of Cu on a metal oxide basis The process is derived from or can be derived from a bulk catalyst precursor containing the following.

[25] The process according to

[24] , wherein the hydrogenation treatment is selected from the group consisting of hydrogenation desulfurization, hydrogenation denitrification, hydrogenation deoxygenation, hydrogenation demetallation, hydrogenation dearomaticization, hydrogenation, hydrogenation, hydrogenation cracking, hydrogenation treatment, hydrogen isomerization, and hydrogenation cracking.

[26] The hydrogenation treatment conditions are a temperature of 200°C to 450°C, a pressure of 250 to 5000 psig (1.7 to 34.6 MPa), and a treatment time of 0.1 to 10 hours. -1 The liquid space velocity, and 100~15,000 SCF / B (17.8~2672 m 3 / m 3 The process described in

[24] , which includes the hydrogen gas rate of ). [Modes for carrying out the invention]

[0011] definition The term "bulk" can be used synonymously with "unsupported" when describing a mixed metal catalyst composition, meaning that the catalyst composition is not a conventional catalyst form having a pre-formed molded catalyst support (on which the metal is later supported by impregnation), i.e., it is not a substrate catalyst.

[0012] The term “atmospheric pressure” is used herein to describe the pressure on Earth without the use of external pressure change measures. Generally, unless conducted at extreme altitudes on Earth, “atmospheric pressure” is approximately 1 atmosphere (or approximately 14.7 psi, or approximately 101 kPa).

[0013] The terms "weight percentage" and "weight %" can be used interchangeably and, unless otherwise specified, refer to the weight percentage of a given component relative to the total weight of the composition. That is, unless otherwise specified, the weight % value is based on the total weight of the composition. It should be understood that the sum of the weight % values ​​for all components in the disclosed composition or formulation equals 100.

[0014] Bulk catalysts and bulk catalyst precursors The present invention provides a polymetallic bulk catalyst precursor composition comprising oxides of Ni, Mo, W, Nb, and optionally Ti and / or Cu. Before use for hydrogenation, the catalyst precursor can be sulfurized to convert the metals into metal sulfides. After sulfurization, the composition is referred to as the "catalyst" and the corresponding "catalyst" for the purposes of the following claims.

[0015] The bulk catalyst and / or the corresponding bulk catalyst precursor comprises nickel (Ni), molybdenum (Mo), tungsten (W), niobium (Nb), and optionally titanium (Ti), and / or copper (Cu) metal. The bulk catalyst and / or the corresponding bulk catalyst precursor may contain 1 to 60% by weight, e.g., 5 to 40% by weight, or 20 to 60% by weight, Ni, on a metal oxide basis; 1 to 40% by weight, e.g., 1 to 25% by weight, or 3 to 20% by weight, Mo, on a metal oxide basis; 5 to 80% by weight, e.g., 10 to 35% by weight, or 20 to 75% by weight, W, on a metal oxide basis; 0.01 to 20% by weight, e.g., 0.1 to 20% by weight, or 1 to 20% by weight, Nb, on a metal oxide basis; 0 to 45% by weight, e.g., 2 to 45% by weight, 5 to 40% by weight, 10 to 35% by weight, or 20 to 30% by weight, Ti, on a metal oxide basis; and 0 to 10% by weight, e.g., 0.01 to 10% by weight, 0.1 to 10% by weight, or 1 to 10% by weight, Cu, on a metal oxide basis. Therefore, the bulk catalysts disclosed herein have the nomenclature Ni-Mo-W-Nb, Ni-Mo-W-Nb-Ti, Ni-Mo-W-Nb-Cu, or Ni-Mo-W-Nb-Ti-Cu, where each metal is present in the amounts described above.

[0016] The molar ratios of metals in bulk catalysts and / or their corresponding bulk catalyst precursors can, in principle, vary within a wide range. The molar ratio of Nb / (Ni+Mo+W+Ti+Cu) in bulk catalysts and / or their corresponding bulk catalyst precursors can be in the range of 10:1 to 1:10, or 3:1 to 1:3. The molar ratio of Ni / W in bulk catalysts and / or their corresponding bulk catalyst precursors can be in the range of 10:1 to 1:10. The molar ratio of W / Mo in bulk catalysts and / or their corresponding catalyst precursors can be in the range of 100:1 to 1:100.

[0017] The bulk catalyst precursor is a hydroxide and can be characterized by having the following chemical formula: A v [Ni 1-a-b Nb a Cu b(OH) x (L) p y ] z [Mo m W 1-m O4][Ti(OH) n O 2-n / 2] w In the formula, (i)A is an alkali metal cation, a rare earth metal cation, an ammonium cation, an organic ammonium cation, a phosphonium cation, or a combination thereof; (ii)L is an organic compound-based component; and (iii)O <a<1;0≦b<1;a+b<1;0≦y≦2 / p;0≦x<2;0≦v<2;0<z;0<m<1;0<n<4;0<w / (z+1)<10である。

[0018] Prior to forming a bulk catalyst by sulfidation, the bulk catalyst precursor may consist of at least 55% by weight (at least 60% by weight, at least 70%, at least 80% by weight, or at least 90% by weight) of oxides of Ni, Mo, W, and Nb. In any embodiment, the bulk catalyst and / or the corresponding bulk catalyst precursor may contain 40% by weight or less of a binder material. The addition of the binder material can improve the physical and / or thermal properties of the catalyst.

[0019] The bulk catalyst and / or the corresponding bulk catalyst precursor may further comprise an organic compound-based component, which may be based on or derived from at least one organic complexing agent used in the preparation of the bulk catalyst and / or the corresponding bulk catalyst precursor. If an organic compound-based component is present, the molar ratio of nickel in the composition to the organic compound-based composition may be in the range of 3:1 to 20:1.

[0020] The bulk catalyst and / or the corresponding bulk catalyst precursor shall be at least 20m 2 / g, at least 50m 2 / g, at least 75m 2 / g, at least 100m 2It can have a BET specific surface area of ​​1 / g. In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor may have a BET specific surface area of ​​250m 2 / g or less, 200m 2 / g or less, 175m 2 / g or less, 150m 2 / g or less, or 125m 2 It is possible to have a BET surface area of ​​less than or equal to / g. The lower limits for the BET specific surface area mentioned above are explicitly considered in combination with the upper limits mentioned above. The term "BET specific surface area" means the specific surface area measured from nitrogen adsorption data according to the method of S. Brunauer, P. Hemmett and E. Teller (J. Am. Chem. Soc. 1938, 60, 309-331).

[0021] The bulk catalyst and / or the corresponding bulk catalyst precursor shall be at least 0.02 cm 3 / g, at least 0.03cm 3 / g, at least 0.04cm 3 / g, at least 0.05cm 3 / g, at least 0.06cm 3 / g, at least 0.08cm 3 / g, at least 0.09cm 3 / g, at least 0.10cm 3 / g, at least 0.11cm 3 / g, at least 0.12cm 3 / g, at least 0.13cm 3 / g, at least 0.14cm 3 / g, at least 0.15cm 3 It can have a void volume of 0.80 cm² / g. In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor may have a void volume of 0.80 cm² / g. 3 / g or less, 0.70cm 3 / g or less, 60cm 3 / g or less, 50cm 3 / g or less, 0.45cm 3 / g or less, 0.40cm 3 / g or less, 0.35cm 3 / g or less, 0.30cm3 The void volume may be less than or equal to / g. The above lower limits for void volume are explicitly defined in combination with the above upper limits. The void volume is measured from nitrogen adsorption data according to the procedure described by E.P. Barrett, L.G. Joyner and P.P. Halenda (J. Am. Chem. Soc. 1951, 73, 373-380).

[0022] The bulk catalyst and / or the corresponding bulk catalyst precursor shall be at least 1.00 g / cm³ 3 (For example, at least 1.10 g / cm³) 3 at least 1.20 g / cm³ 3 at least 1.30 g / cm³ 3 at least 1.40 g / cm³ 3 at least 1.50 g / cm³ 3 Or at least 1.60 g / cm³ 3 ) can have a particle density of . In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor may be 3.00 g / cm³. 3 (For example, 2.90 g / cm³) 3 Below 2.80g / cm 3 Below, 2.70g / cm 3 Below 2.60g / cm 3 Below 2.50g / cm 3 The following, or 2.40 g / cm³ 3 Below, 2.30 g / cm³ or less, or 2.20 g / cm³ 3 The particle density can be as follows. The lower limit of the particle density is explicitly determined in combination with the upper limit of the particle density. The particle density (D) is obtained by applying the formula D = M / V [wherein 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 mmHg vacuum.

[0023] Bulk catalysts and / or corresponding bulk catalyst precursors can be characterized by powder X-ray diffraction as insufficiently crystalline materials with low-intensity, broad diffraction peaks. As used herein, broad diffraction peaks mean peaks with a full width at half maximum (FWHM) greater than 1° (on a 2θ scale).

[0024] Preparation of bulk catalysts and catalyst precursors This bulk catalyst precursor is a hydroxide, and the steps prior to sulfidation to form the bulk catalyst are carried out at a temperature of 200°C or lower. The catalyst precursor is prepared in a manner in which it remains as a hydroxide before sulfidation to form the bulk catalyst.

[0025] In one embodiment, the first step in preparing the bulk catalyst precursor is a precipitation or co-gelation step, which involves reacting nickel and niobium precursor compounds in solution, as well as molybdenum and tungsten precursor compounds in solution, in the reaction mixture to obtain a precipitate or co-gel. Precipitation or co-gelation is carried out at a temperature and pH at which the metal precursors precipitate or form a co-gel.

[0026] If titanium is present, it can be introduced via either an in-situ or ex-situ route. In the in-situ route, titanium can be precipitated by adding a Ti-containing precursor compound to the reaction mixture during the co-precipitation or co-gelation of Ni-Mo-W-Nb oxide or Ni-Mo-W-Nb-Cu oxide. In the ex-situ route, one or more titanium precursor compounds can be compounded with the precipitate or co-gel of Ni-Mo-W-Nb oxide or Ni-Mo-W-Nb-Cu oxide.

[0027] In any embodiment, the in-situ addition of titanium may include (a) combining in the reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Nb-containing precursor, (v) a Ti-containing precursor, (vi) optionally a Cu-containing precursor, (vii) optionally an organic compound-based component, and (viii) a protic liquid, and (b) reacting the mixture under conditions sufficient to produce a precipitation of the bulk catalyst precursor. The reaction mixture can be obtained by (1) preparing a first mixture comprising a Ni-containing precursor, a Nb-containing precursor, optionally a Cu-containing precursor, a protic liquid, and optionally an organic compound-based component; (2) preparing a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid; (3) adding a Ti-containing precursor to the first mixture, the second mixture, or a combination thereof; (4) heating both the first and second mixtures to a temperature of 60°C to 150°C; and (5) combining the first and second mixtures with each other. After the reaction steps, if necessary, the obtained bulk catalyst precursor can be separated from the liquid, for example, by filtration or spray drying.

[0028] In any embodiment, the ex-situ addition of titanium may include (a) combining in the reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Nb-containing precursor, (v) optionally a Cu-containing precursor, (vi) optionally an organic compound-based component, and (vii) a protic liquid; (b) reacting the mixture under conditions sufficient to produce a precipitate of an intermediate bulk catalyst precursor; and (c) compounding the intermediate bulk catalyst precursor with a Ti-containing precursor to form a bulk catalyst precursor. The reaction mixture can be obtained by (1) preparing a first mixture containing a Ni-containing precursor, a Nb-containing precursor, an optionally Cu-containing precursor, a protic liquid, and optionally an organic compound-based component; (2) preparing a second mixture containing a Mo-containing precursor, a W-containing precursor, and a protic liquid; (3) heating both the first and second mixtures to a temperature of 60°C to 150°C; and (4) combining the first and second mixtures. After the reaction steps, if necessary, the resulting intermediate bulk catalyst can be separated from the liquid, for example, by filtration or spray drying.

[0029] The temperature at which the catalyst precursor is formed can be in the range of 60°C to 150°C. When the temperature is below the boiling point of the protic liquid, for example, 100°C for water, the process is generally carried out at atmospheric pressure. This reaction can also be carried out under hydrothermal conditions where the reaction temperature exceeds the boiling point of the protic liquid. Typically, such conditions result in a pressure above atmospheric pressure, after which the reaction is carried out preferably in an autoclave, preferably under its own pressure, i.e., without the application of further pressure. An autoclave is a pressure-resistant apparatus designed to heat a liquid above its boiling point. In any embodiment, the bulk catalyst precursor formation process is carried out at one or more temperatures, either (a) in the range of 50°C to 100°C under atmospheric pressure, or (b) above 100°C under its own pressure.

[0030] The reaction time is chosen to be long enough to substantially complete the reaction, both under atmospheric pressure and hydrothermal reaction conditions. The reaction time can be very short (e.g., less than one hour with highly reactive reactants). Clearly, longer reaction times, perhaps up to 24 hours, may be required for less reactive raw materials. In some situations, the reaction time may vary inversely with temperature.

[0031] Generally, the reaction mixture is maintained at its natural pH throughout the reaction process. The pH can be maintained within the range of 0–12 (e.g., 3–9, or 5–8). By changing the pH, the rate of precipitation or co-gelation can be increased or decreased depending on the desired properties of the product.

[0032] Metal precursors can be added to the reaction mixture in solution, suspension, or a combination thereof. When soluble salts are added in this manner, they dissolve in the reaction mixture and then precipitate or co-gel.

[0033] Typical examples of Mo-containing precursor compounds include molybdenum (di and tri) oxides, molybdic acid, alkali metal molybdate (e.g., sodium molybdate, potassium molybdate), ammonium molybdate (e.g., ammonium molybdate, ammonium dimolybdate, ammonium heptamolybdate), and heteropolymolybdates (e.g., silicomolybdate, phosphomolybdate).

[0034] Typical examples of W-containing precursor compounds include tungsten (di and tri) oxides, tungstic acid, alkali metal tungstates (e.g., sodium tungstate, potassium tungstate, sodium metatungstate, sodium polytungstate), ammonium tungstates (e.g., ammonium tungstate, ammonium metatungstate, ammonium paratungstate), and heteropolytungstates (e.g., silicotungstic acid, phosphotungstic acid).

[0035] Typical examples of nickel-containing precursor compounds include nickel acetate, nickel acetylacetate, nickel bromide, nickel carbonate, nickel hydroxycarbonate, nickel bicarbonate, nickel chloride, nickel nitrate, and nickel sulfate.

[0036] Typical examples of Nb-containing precursor compounds include niobium oxalate, niobium ammonium oxalate, niobium chloride, niobium bromide, niobium ethoxide, niobium n-propoxide, and niobium isopropoxide.

[0037] Typical examples of copper-containing precursor compounds include copper(II) acetate, copper(II) acetylacetate, copper(II) hydroxide, copper(II) chloride, copper(II) bromide, copper(II) carbonate, copper(II) nitrate, copper(II) phosphate, and copper(II) sulfate.

[0038] Any titanium-containing compound suitable for the preparation of the types of bulk catalysts described herein can be used as a Ti-containing precursor compound. The Ti-containing precursor is tetravalent titanium (Ti 4+ ) Compounds containing trivalent titanium (Ti 3+ ) may include compounds containing these, or combinations thereof.

[0039] Typical Ti-containing precursor compounds include TiO2 nanoparticles, colloidal TiO2, fumed TiO2, titanium hydroxide, organotitanium compounds, titanium halides, and water-soluble titanium salts.

[0040] Titanium dioxide nanoparticles may be any type of titanium dioxide. Titanium dioxide may have a high content of anatase and / or rutile. For example, titanium dioxide may contain at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or even more, at least 99% by weight of anatase and / or rutile. In some embodiments, titanium dioxide is essentially composed of anatase and / or rutile. Titanium dioxide particles preferably have a median particle size (D50) of 100 nm (e.g., 3-50 nm). Titanium dioxide nanoparticles can be introduced into a composition as a sol prepared by dispersion in a dispersant, as a paste containing water or a solvent, or as a powder. Examples of dispersants used to prepare the sol include water, alcohols (e.g., methanol, ethanol, isopropanol, n-butanol, isobutanol), and ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone).

[0041] Representative organotitanium compounds include titanium alkoxides with the general structure Ti(OR)4 [wherein each R is independently a C1-C4 alkyl and a titanium acyl compound]. Representative titanium alkoxides include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-tert-butoxide. Representative titanium acyl compounds include titanium acetylacetonate, titanium oxyacetylacetonate, and titanium acetate. Other representative organotitanium compounds are those characterized by the general formula Ti(OR')2(acac)2 [wherein each R' is independently a C1-C4 alkyl and "acac" is acetylacetonate].

[0042] Titanium halides represented by the formula TiX4 or TiX3 [wherein X is chloro, bromo, iodine, or fluoro, or a mixture thereof] can be used as titanium precursors. In one embodiment, the titanium halide is titanium tetrachloride, titanium tetrabromide, or a combination thereof.

[0043] This disclosure also conceives of the use of organotitanium halides, such as chlorotitannate triisopropoxide [Ti(Oi-Pr)3Cl], as Ti-containing precursor compounds.

[0044] Typical water-soluble titanium salts include titanium nitrate and titanium sulfate.

[0045] The organic compound-based component can be an organic compound suitable for forming a metal ligand complex in solution. The organic compound-based component can be selected from organic acids or their salts, sugars, sugar alcohols, or combinations thereof.

[0046] Representative organic acids include glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetate, malic acid, fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid.

[0047] Typical sugars include fructose, glucose, galactose, mannose, sucrose, lactose, maltose, and their derivatives.

[0048] Representative sugar alcohols include erythritol, xylitol, mannitol, sorbitol, and their derivatives.

[0049] The protic liquid can be any protic liquid that does not interfere with the reaction of the metal compound. Examples include water, carboxylic acids, and alcohols (e.g., methanol, ethanol, ethylene glycol). The protic liquid can be water alone, or a mixture of water and alcohol.

[0050] Additional processing The bulk catalyst precursor may be subjected to one or more of the following process steps before being used in the hydrogenation process: (i) compounding with a material selected from the group consisting of binder materials, conventional hydrogenation catalysts, cracking compounds, or mixtures thereof; (ii) spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing, or a combination thereof; (iii) molding; (iv) drying and / or heat treatment; and (v) sulfidation. The enumeration of these process steps as (i) to (v) is for convenience only. This notation does not indicate that these processes are limited to those carried out in this sequence. These process steps are described in more detail below.

[0051] Additional process step (i) - Compounding with further materials If desired, additional materials selected from the group consisting of binder materials, conventional hydrogenation catalysts, cracking compounds, or mixtures thereof may be added during or after the preparation of the bulk catalyst precursor as described above. Preferably, the materials are added after the preparation of the bulk catalyst precursor and before spray drying or any alternative technique, or, if spray drying or an alternative technique is not applied, before molding. Optionally, the bulk metal precursor prepared as described above may be subjected to solid-liquid separation before compounding with the material. After solid-liquid separation, a washing step may be included as an option. Furthermore, the bulk catalyst particles may be heat-treated after the optional solid-liquid separation and drying steps and before compounding with the material.

[0052] In all of the process alternatives described above, the phrase "compounding of bulk catalyst precursor with material" means that the material is added to bulk metal particles, or bulk metal particles are added to material, and the resulting composition is mixed. The mixing is preferably carried out in the presence of a liquid ("wet mixing"). This improves the mechanical strength of the final bulk catalyst composition.

[0053] By compounding the bulk catalyst precursor with further materials and / or incorporating materials during the preparation of the catalyst precursor, a bulk catalyst with particularly high mechanical strength can be obtained, especially when the median particle size of the bulk metal particles is at least 0.5 μm (e.g., at least 1 μm, at least about 2 μm) and in the range of 5000 μm or less (e.g., 1000 μm or less, 500 μm or less, 150 μm or less). The particle size of the catalyst precursor can be in the range of 1 to 150 μm (e.g., 2 to 150 μm).

[0054] By compounding bulk metal particles with a material, bulk metal particles embedded in the material, or the material embedded in bulk metal particles, are obtained. Typically, the morphology of the bulk metal particles is essentially maintained within the resulting bulk catalyst composition.

[0055] The binder material to be applied can be any material conventionally used as a binder in hydrogenation catalysts. Examples include silica, silica-alumina (e.g., conventional silica-alumina, silica-coated alumina, and alumina-coated silica), alumina (e.g., boehmite, pseudoboehmite, or gibbsite), titania, titania-coated alumina, zirconia, hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titania, titania-coated alumina, zirconia, bentonite, or mixtures thereof. These binders can be applied as is or after decapsulation.

[0056] When alumina is used as a binder, the surface area of ​​the alumina, as measured by the BET method, is 50-600 m².2 / g (for example, 100-450m) 2 It can be in the range of / g). The void volume of alumina, when measured by nitrogen adsorption, is 0.1~1.5cm 3 It can be within the range of / g.

[0057] Generally, the binder material added has lower catalytic activity than the bulk metal particles, or has no catalytic activity at all. Depending on the intended catalyst application, the amount of binder can be preferably 0 to 40% by weight of the total composition. However, to take advantage of the high activity obtained from the bulk metal particles of this disclosure, the amount of binder added is generally in the range of 0.1 to 30% by weight of the total composition (e.g., 1 to 20% by weight, 3 to 20% by weight, or 4 to 12% by weight).

[0058] Additional process steps (ii) - spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing A bulk catalyst precursor, optionally containing any of the above-mentioned (further) materials, can be subjected to spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing, or a combination thereof, with a preferred combination being wet mixing and kneading, or slurry mixing and spray drying.

[0059] These techniques can be applied before or after adding any of the above (further) materials (if any), after solid-liquid separation, before or after heat treatment, and after re-wetting.

[0060] The catalyst precursor is preferably compounded with any of the above materials and subjected to any of the above techniques. It is believed that the degree of mixing between the catalyst precursor particles and any of the above materials is improved by applying any of the above techniques: spray drying, (flash) drying, milling, kneading, slurry mixing, drying or wet mixing, or a combination thereof. This applies to cases where the material is added before, after, or before applying any of the above methods. However, it is generally preferred to add the material before step (ii). If the material is added after step (ii), the resulting composition can be fully mixed by any conventional technique before any further process steps such as molding. The advantage of spray drying is that it does not produce wastewater flow when applied.

[0061] Spray drying can be performed at an outlet temperature in the range of 100-200°C (e.g., 120-180°C).

[0062] Dry mixing refers to mixing dry catalyst precursor particles with any of the above materials in a dry state. Wet mixing generally involves mixing a wet filtrate containing catalyst precursor particles with any of the above materials, either as a powder or a wet filtrate, to form a homogeneous paste.

[0063] Additional process step (iii) - molding If so desired, a bulk catalyst precursor, optionally containing one of the (further) materials described above, may be molded after optionally applying step (ii). Molding includes extrusion, pelletizing, beading, and / or spray drying. Note that when the bulk catalyst composition is applied in a slurry reactor, fluidized bed, moving bed, or expansion bed, spray drying or beading is generally applied. In the case of fixed bed or boiling bed applications, the bulk catalyst composition is generally extruded, pelletized, and / or beaded. In the latter case, any additives conventionally used to facilitate molding may be added before or at any stage during the molding process. These additives may include aluminum stearate, surfactants, graphite, starch, methylcellulose, bentonite, polyethylene glycol, polyethylene oxide, or mixtures thereof. Furthermore, when alumina is used as a binder, it may be desirable to add an acid such as nitric acid before the molding process to plastinate the alumina and increase the mechanical strength of the extruded product.

[0064] If shaping involves extrusion, beading, and / or spray drying, the shaping process is preferably carried out in the presence of a liquid such as water. With respect to extrusion and / or beading, the amount of liquid in the shaping mixture, expressed as loss on ignition, can be in the range of 20% to 80%.

[0065] Additional process step (iv) - Drying and / or heat treatment Preferably, after an optional drying step at over 100°C, the resulting molded bulk catalyst composition may be heat-treated if desired. However, heat treatment is not essential to the process of this disclosure. According to this disclosure, “heat treatment” means a treatment carried out at a temperature of 100 to 200°C for a time ranging from 0.5 to 48 hours in an inert gas such as nitrogen, or in an oxygen-containing gas such as air or pure oxygen. The heat treatment may be carried out in the presence of a water stream.

[0066] In all of the above process steps, the amount of liquid must be controlled. Before the bulk catalyst composition is subjected to spray drying, the amount of liquid is very small, and additional liquid must be added. Conversely, before the bulk catalyst composition is extruded, the amount of liquid is too large, and it is necessary to reduce the amount of liquid using solid-liquid separation techniques such as filtration, decantation, or evaporation. If necessary, the resulting material can be dried and then re-wetted to a certain extent. Adjusting the amount of liquid appropriately for all of the above process steps is within the scope of those skilled in the art.

[0067] Additional process step (v) - sulfurization Tetravalent metal bulk catalysts are generally used in their sulfide form. The sulfidation of the catalyst can be carried out by any method efficient for producing the catalyst in sulfide form, including conventional sulfidation methods. Sulfidation can be carried out by contacting the catalyst precursor with a sulfur-containing compound, such as elemental sulfur, hydrogen sulfide, dimethyl disulfide, or an organic or inorganic polysulfide, either after its preparation or directly after any one of the additional process steps (i) to (iv). The sulfidation process can be carried out in the liquid and gas phases.

[0068] Sulfidation can generally be carried out in situ and / or ex situ. Preferably, sulfidation is carried out in situ (i.e., sulfidation is carried out in the hydrogenation reactor after the bulk catalyst precursor has been loaded into the hydrogenation unit).

[0069] Use in hydrogenation treatment The bulk catalyst precursors of this disclosure are particularly useful for the hydrogenation of hydrocarbon raw materials. Hydrogenation includes processes such as hydrodesulfurization, hydrodenitrification, hydrodemetallation, hydrodesaromatherapy, hydrogenation, hydrocracking, hydrogenation, hydrogen isomerization, and hydrogenation cracking.

[0070] A wide range of petroleum and chemical hydrocarbon raw materials can be hydrotreated in accordance with this disclosure. Hydrocarbon raw materials include crude petroleum, tar sands, coal liquefaction, shale oil, and those obtained from or derived from hydrocarbon synthesis, such as reduced crude materials, hydrocracking products, raffinates, hydrogenated oils, air and vacuum gas oils, coking equipment gas oils, waiting and vacuum residues, deasphalt oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, biorenewable raw materials, and mixtures thereof. Suitable raw materials range from relatively light distillation distillates to heavy raw materials, such as gas oils, lubricating oils, and residues. Examples of light distillation raw materials include naphtha (typically with a boiling point range of about 25°C to about 210°C), diesel (typically with a boiling point range of about 150°C to about 400°C), kerosene, or jet fuel (typically with a boiling point range of about 150°C to about 250°C). Examples of heavy raw materials include vacuum (or heavy) gas oils (typically with a boiling point range of approximately 315°C to 610°C), raffinates, lubricants, cycle oils, and wax oils. Preferred hydrocarbon raw materials have a boiling point range of approximately 150°C to 650°C (for example, approximately 150°C to 450°C).

[0071] Hydrogenation treatment conditions include a temperature of 200°C to 450°C, or 315°C to 425°C; a pressure of 250 to 5000 psig (1.7 to 34.6 MPa), or 300 to 3000 psig (2.1 to 20.7 MPa); and a treatment time of 0.1 to 10 hours. -1 , or 0.5-5 hours -1 Liquid space velocity (LHSV); and 100-15,000 SCF / B (17.8-2672 m 3 / m 3 ), or 500-10,000 SCF / B (89-1781m 3 / m 3 The hydrogen gas velocity can be increased.

[0072] Hydrogenation treatment according to this disclosure can be carried out in one or more reaction zones using any suitable reactor system, such as one or more fixed-bed, moving-bed, or fluidized-bed reactors. A fixed-bed reactor may include one or more vessels, one or more bed catalysts in each vessel, and various combinations of hydrogenation catalysts in one or more vessels.

[0073] example The following illustrative examples (implementations) are intended to be non-limiting.

[0074] Example 1 (Comparison) Synthesis of bulk catalyst precursors [Ni(2.5)-Mo(1)-W(1)] Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g of ammonium metatungstate were added to 2000 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. Next, the solution was heated to 80°C.

[0075] Preparation of Solution B: In a separate 500 mL beaker, 184.5 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water. Solution B was added to Solution A over 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of Solution B. After addition, the final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0076] Example 2 (Comparison) Synthesis of bulk catalyst precursors [Ni(7.5)-Mo(1)-W(3)] 10.4 g of ammonium heptamolybdate and 44.8 g of ammonium metatungstate were added to 2000 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. Next, the solution was heated to 80°C.

[0077] Preparation of Solution B: In a separate 500 mL beaker, 128.3 g of nickel nitrate and 5.8 g of maleic acid were dissolved in 100 g of deionized water.

[0078] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0079] Example 3 (Comparison) Synthesis of bulk catalyst precursors [Ni(3.8)-Mo(1)-W(1.1)] Preparation of Solution A: 17.6 g of ammonium heptamolybdate and 27.8 g of ammonium metatungstate were added to 2000 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. Next, the solution was heated to 80°C.

[0080] Preparation of Solution B: In a separate 500 mL beaker, 110.3 g of nickel nitrate and 5.8 g of maleic acid were dissolved in 100 g of deionized water.

[0081] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0082] Example 4 Synthesis of bulk catalyst precursors [Ni-Mo-W-Nb] Preparation of Solution A: 35 g of ammonium heptamolybdate and 151 g of ammonium metatungstate were added to 2500 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0083] Preparation of Solution B: In a separate 1 L beaker, 389 g of nickel nitrate, 60 g of ammonium oxalate niobate, and 20 g of maleic acid were dissolved in 800 g of deionized water.

[0084] Solution B was added to solution A over a period of 30 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0085] Example 5 Synthesis of bulk catalyst precursors [Ni-Mo-W-Nb-Ti] Ex-situ with addition of Ti Preparation of Solution A: 35 g of ammonium heptamolybdate and 151 g of ammonium metatungstate were added to 2500 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0086] Preparation of Solution B: In a separate 1 L beaker, 389 g of nickel nitrate, 60 g of ammonium oxalate niobate, and 20 g of maleic acid were dissolved in 800 g of deionized water.

[0087] Solution B was added to solution A over a period of 30 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was recovered by filtration. The filtrate and 87 g of TiO2 (Venator Hombikat 8602) were mixed to form a homogeneous phase, which was stirred at 80°C for 2 hours. The mixture was recovered by filtration, washed with deionized water, and dried in an oven at 130°C.

[0088] Example 6 Synthesis of bulk catalyst precursors [Ni(6.5)-Mo(1)-W(3)-Nb(1)] Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g of ammonium metatungstate were added to 1875 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0089] Preparation of Solution B: In a separate 500 mL beaker, 175 g of nickel nitrate, 32 g of ammonium oxalate niobate, and 9 g of maleic acid were dissolved in 100 g of deionized water.

[0090] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0091] Example 7 Synthesis of bulk catalyst precursors [Ni(7)-Mo(1)-W(3)-Nb(0.5)] Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g of ammonium metatungstate were added to 1875 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0092] Preparation of Solution B: In a separate 500 mL beaker, 188 g of nickel nitrate, 16 g of ammonium oxalate niobate, and 10 g of maleic acid were dissolved in 100 g of deionized water.

[0093] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0094] Example 8 Synthesis of bulk catalyst precursors [Ni(6)-Mo(1)-W(3)-Nb(1.5)] Preparation of Solution A: 18 g of ammonium heptamolybdate and 66 g of ammonium metatungstate were added to 1875 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0095] Preparation of Solution B: In a separate 500 mL beaker, 175 g of nickel nitrate, 47 g of ammonium oxalate niobate hydrate, and 9 g of maleic acid were dissolved in 100 g of deionized water.

[0096] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0097] Example 9 Synthesis of bulk catalyst precursors [Ni(6.2)-Mo(1)-W(3)-Nb(1)-Cu(0.3)] Preparation of Solution A: 18 g of ammonium heptamolybdate and 79 g of ammonium metatungstate were added to 1875 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0098] Preparation of Solution B: In a separate 500 mL beaker, 166 g of nickel nitrate, 32 g of ammonium oxalate niobate, 8 g of copper(II) nitrate, and 9 g of maleic acid were dissolved in 100 g of deionized water.

[0099] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. Immediately after adding solution B, a green precipitate formed. After addition, the final pH was 6.0–7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0100] Example 10 Fabrication of extruded products Before evaporating the catalyst, the catalyst precursor was molded into an extruded body. The dried catalyst precursor was pulverized into a fine powder (<100 mesh), mixed with an appropriate amount of binder and water to prepare an extrudeable mixture, which was then extruded using a Carver press.

[0101] Example 11 Characterization of bulk catalyst precursors The particle density (D), BET surface area (SA), and void volume (PV) of bulk catalyst precursors for Examples 1-7 and 9 were measured. The results are shown in Table 1 below. This table shows that it is possible to reduce the particle density by adding niobium. [Table 1]

[0102] Example 12 Catalyst Evaluation - Hydrocracking of Diesel / Tetralin Blends A parallel test unit (hte GmbH) was used to screen the ring-opening activity of the catalysts prepared in Examples 2-3 and 6 using a feedstock of 70 vol% straight-run diesel / 30 vol% tetralin blend. The reactor was loaded with three catalyst layers: 60 vol% Ni-Mo hydrogenated catalyst, 30 vol% test catalyst, and 10 vol% Ni-Mo hydrogenated catalyst. All three catalysts were pre-sulfurized before the tetralin test. After sulfurizing the catalysts at 450°F / 800psi for 24 hours, the temperature was increased to 650°F at 25°F / h and maintained at 65°F / 800psi for 10 hours.

[0103] The characteristics of the straight-run diesel / tetralin blend raw materials are summarized in Table 2. [Table 2]

[0104] Temperature 700°F, hydrogen pressure 2300 psi, 1 hour -1 Catalyst tests were conducted at LHSV and a hydrogen gas rate of 3500 SCF / B. The activity of these three catalysts was compared in Table 3. The yield of the ring-opening reaction was quantified based on online gas chromatography (GC) equipped with a flame ionization detector. The results showed that the catalyst of Example 6 had significantly higher ring-opening activity and yielded a higher API degree than the catalysts of Examples 2 and 3. The results suggest that this improvement is likely due to the addition of niobium. [Table 3]

Claims

1. (a) 5 to 40% by weight of Ni, based on metal oxides (b) 3 to 20% by weight of Mo, based on metal oxides (c) Based on metal oxides, 20 to 75% by weight of W (d) 1 to 20% by weight of Nb, based on metal oxides (e) 0 to 45% by weight of Ti, based on metal oxides, (f) 0 to 10% by weight of Cu based on metal oxides A bulk catalyst precursor for use in the hydrogenation of hydrocarbon raw materials, including [specific component].

2. The bulk catalyst precursor according to claim 1, further comprising an organic compound-based component.

3. The bulk catalyst precursor according to claim 2, wherein the organic compound-based component is selected from the group consisting of organic acids or their salts, sugars, sugar alcohols, or combinations thereof.

4. The bulk catalyst precursor according to claim 2, wherein the organic compound-based component is selected from the group consisting of glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetate, malic acid, fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose, sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, or combinations thereof.

5. The bulk catalyst precursor according to claim 2, wherein the molar ratio of Ni to the organic compound-based component is in the range of 3:1 to 20:

1.

6. The bulk catalyst precursor according to claim 1, wherein the molar ratio of Nb / (Ni+Mo+W+Ti+Cu) is in the range of 10:1 to 1:

10.

7. The bulk catalyst precursor according to claim 1, wherein the molar ratio of Ni / W is in the range of 10:1 to 1:

10.

8. The bulk catalyst precursor according to claim 1, wherein the molar ratio of W / Mo is in the range of 100:1 to 1:

100.

9. The bulk catalyst precursor according to claim 1, wherein the bulk catalyst precursor is for use in a ring-opening reaction by hydrogenation treatment of a tetralin hydrocarbon raw material.

10. The bulk catalyst precursor according to claim 1, further comprising 1 to 15% by weight of a binder.

11. One or more of the following characteristics: 50-250m ２ BET specific surface area per g: 0.02–0.80 cm² ３ The void volume per g, and 1.00 to 3.00 cm ３ A bulk catalyst precursor according to claim 1, having a particle density of / g.

12. A sulfurized bulk catalyst, characterized in that it is a sulfurized bulk catalyst precursor according to claim 1.

13. A method for preparing a bulk catalyst precursor according to claim 1, (a) In the reaction mixture, (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv) Nb-containing precursor, (v) Depending on the case, Ti-containing precursor and / or Cu-containing precursor, (vi) Depending on the case, organic compound-based components, and (vii) Protic liquids Combining them, (b) Reacting the mixture under conditions sufficient to produce a precipitate of the bulk catalyst precursor, The method wherein the preparation step of the bulk catalyst precursor is carried out at a temperature of 200°C or lower.

14. The reaction mixture To prepare a first mixture comprising a Ni-containing precursor, an Nb-containing precursor, an optional Cu-containing precursor, a protic liquid, and an optional organic compound-based component, To prepare a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid, Depending on the circumstances, a Ti-containing precursor may be added to the first mixture, the second mixture, or a combination thereof. Heat both the first and second mixtures to a temperature of 60°C to 150°C, The first and second mixtures are combined with each other, The method according to claim 13, which is prepared by...

15. The Ti-containing precursor is TiO ２ Nanoparticles, colloidal TiO ２ , Humed TiO ２ The method according to claim 14, wherein titanium hydroxide, organotitanium compounds, titanium halides, organotitanium halides, water-soluble titanium salts, or combinations thereof are selected.

16. A method for preparing a bulk catalyst precursor according to claim 1, (a) In the reaction mixture, (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv) Nb-containing precursor, (v) Depending on the case, Cu-containing precursor, (vi) Depending on the case, organic compound-based components, and (vii) Protic liquids Combining them, (b) The mixture is reacted under conditions sufficient to produce a precipitate of the intermediate bulk catalyst precursor, (c) Composite the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor, The method wherein the preparation step of the bulk catalyst precursor is carried out at a temperature of 200°C or lower.

17. The reaction mixture To prepare a first mixture comprising a Ni-containing precursor, an Nb-containing precursor, an optional Cu-containing precursor, a protic liquid, and an optional organic compound-based component, To prepare a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid, Heat both the first and second mixtures to a temperature of 60°C to 150°C, The first and second mixtures are combined with each other, The method according to claim 16, which is prepared by...

18. The Ti-containing precursor is TiO ２ Nanoparticles, fumed TiO ２ The method according to claim 16, or a combination thereof.

19. The method according to claim 16, wherein the intermediate bulk catalyst precursor is a Ni-Mo-W-Nb or Ni-Mo-W-Nb-Cu bulk catalyst precursor.

20. The method according to claim 13 or 16, wherein the reaction is carried out at one or more temperatures, either (a) under atmospheric pressure in the range of 60°C to 100°C, or (b) above 100°C without the application of further pressure.

21. The method according to claim 13 or 16, wherein the organic compound-based component is selected from organic acids or their salts, sugars, sugar alcohols, or combinations thereof.

22. The method according to claim 21, wherein the organic compound-based component is selected from glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetate, malic acid, fumaric acid, maleic acid, tartaric acid, gluconic acid, citric acid, oxamic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, fructose, glucose, galactose, mannose, sucrose, lactose, maltose, erythritol, xylitol, mannitol, sorbitol, or a combination thereof.

23. A step of compounding the bulk catalyst precursor with a material selected from the group consisting of a binder material, a hydrogenation catalyst, or a mixture thereof, in an amount of 0 to 40% by weight. Processes involving spray drying, drying, milling, kneading, slurry mixing, drying or wet mixing, or a combination thereof. molding process, A process of drying and / or heat treatment at a temperature of 200°C or lower, Sulfurization process The method according to claim 13 or 16, further comprising one or more of the above.

24. A hydrogenation process for hydrocarbon raw materials, comprising contacting the hydrocarbon raw materials with hydrogen in the presence of a bulk catalyst under hydrogenation conditions to obtain at least one product, wherein the bulk catalyst is (a) 5 to 40% by weight of Ni, based on metal oxides (b) 3 to 20% by weight of Mo, based on metal oxides (c) Based on metal oxides, 20 to 75% by weight of W (d) 1 to 20% by weight of Nb, based on metal oxides (e) 0 to 45% by weight of Ti, based on metal oxides, (f) 0 to 10% by weight of Cu based on metal oxides The process is derived from or can be derived from a bulk catalyst precursor containing the following.

25. The process according to claim 24, wherein the hydrogenation treatment is selected from the group consisting of hydrogenation desulfurization, hydrogenation denitrification, hydrogenation deoxygenation, hydrogenation demetallation, hydrogenation dearomaticization, hydrogenation, hydrogenation, hydrogenation cracking, hydrogenation treatment, hydrogen isomerization, and hydrogenation cracking.

26. The hydrogenation treatment conditions are a temperature of 200°C to 450°C, a pressure of 250 to 5000 psig (1.7 to 34.6 MPa), a liquid hourly space velocity of 0.1 to 10 h －１ , and a hydrogen gas velocity of 100 to 15,000 SCF / B (17.8 to 2672 m ３ / m ３ ), and the process according to claim 24.

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