Polymetallic bulk hydrogenation catalyst

Abstract

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

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority and benefit to U.S. Provisional Application No. 63 / 213,324, filed on June 22, 2021, the disclosure of which is incorporated herein by reference.

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

Background Art

[0003] The hydrotreating of hydrocarbon feedstocks generally encompasses all processes in which a hydrocarbon feedstock reacts with hydrogen in the presence of a catalyst and under hydrotreating conditions, typically at high temperature and high pressure. Hydrotreating includes processes such as hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrocracking, hydrorefining, hydroisomerization, and hydrocracking.

[0004] Hydrotreating catalysts typically contain one or more sulfided Group 6 metals and one or more non - noble metals of Groups 8 - 10 as promoters on a refractory support such as alumina. Hydrotreating catalysts particularly suitable for hydrodesulfurization and hydrodenitrogenation generally contain molybdenum sulfide or tungsten sulfide promoted by metals such as cobalt, nickel, iron, or combinations thereof.

[0005] In addition to supported catalysts, hydrotreating using bulk catalysts (also referred to as "non - supported" catalysts) is also known. Bulk hydrotreating catalyst compositions have relatively high catalytic activity compared to conventional supported hydrotreating catalysts, but there is a continuing need in the art for the development of novel bulk catalyst compositions with even improved hydrotreating activity.

[0006] The most common base metals for hydrogenation applications are Ni, Co, Mo, and W. We have recently reported the use of titania, niobium, and copper to adjust the activity and selectivity of bulk catalysts for hydrogenation applications. Although the trivalent transition metal yttrium has not been well studied, it has been reported to be usable as a stabilizer for zirconia, titania, and niobia (see, for example, U.S. Patent No. 10,843,176). Combinations of Ni, Mo, W, and Y, and optionally one or more metals selected from Cu, Nb, and Ti, may, in some cases, yield interesting activity and selectivity for hydrogenation applications. [Overview of the project]

[0007] 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 30 wt% Y based on metal oxide, (e) 0 to 20 wt% Cu based on metal oxide, (f) 0 to 45 wt% Ti based on metal oxide, and (g) 0 to 20 wt% Nb based on metal oxide.

[0008] In a second embodiment, a sulfurized bulk catalyst is provided, characterized in that it is a sulfurized bulk catalyst precursor according to this specification.

[0009] In a third aspect, a method is provided for preparing a bulk catalyst precursor as described herein, the method comprising (a) mixing as a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Y-containing precursor, optionally (v) a Cu-containing precursor, a Ti-containing precursor, and / or a Nb-containing precursor, (vi) optionally an organic compound 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 step of preparing the bulk catalyst precursor is carried out at a temperature of 200°C or less.

[0010] A fourth aspect provides a method for preparing a bulk catalyst precursor as described herein, the method comprising: (a) mixing as a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Y-containing precursor, (v) optionally a Cu-containing precursor, a Ti-containing precursor, and / or a Nb-containing precursor, (vi) optionally an organic compound 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) synthesizing the intermediate bulk catalyst precursor with a Y-containing precursor to form a bulk catalyst precursor, wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200°C or less.

[0011] In a fifth embodiment, a process is provided for hydrogenating a hydrocarbon feedstock, the process comprising contacting the hydrocarbon feedstock 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 30 wt% Y on a metal oxide basis, (e) 0 to 20 wt% Cu on a metal oxide basis, (f) 0 to 45 wt% Ti on a metal oxide basis, and (g) 0 to 20 wt% Nb on a metal oxide basis. In connection with the present invention, the following content is further disclosed. [1] A bulk catalyst precursor comprising (a) 1 to 60% by weight of Ni based on the metal oxide, (b) 1 to 40% by weight of Mo based on the metal oxide, (c) 5 to 80% by weight of W based on the metal oxide, (d) 0.01 to 30% by weight of Y based on the metal oxide, (e) 0 to 20% by weight of Cu based on the metal oxide, (f) 0 to 45% by weight of Ti based on the metal oxide, (g) 0 to 20% by weight of Nb based on the metal oxide, said bulk catalyst precursor. [2] The bulk catalyst precursor according to [1], further comprising an organic compound-based component. [3] The organic compound-based component in the bulk catalyst precursor according to [2] is selected from the group consisting of organic acids or their salts, sugars, sugar alcohols, or combinations thereof. [4] The organic compound-based component in the bulk catalyst precursor according to [2] is selected from the group consisting of glyoxylic acid, pyruvic acid, lactic acid, malonic acid, oxaloacetic acid, 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] The bulk catalyst precursor according to [1], wherein the molar ratio of Y / (Ni + Mo + W + Cu + Ti + Nb) is in the range of 10:1 to 1:100. [7] The bulk catalyst precursor according to [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 [1], wherein the molar ratio of W / Mo is in the range of 100:1 to 1:100. [9] The bulk catalyst precursor has the formula A v [Ni 1-a-b-c Y a Cu b Nb c (OH) x (L) p y ] z [Mo m W 1-m O 4 [Ti(OH) n O 2-n / 2 ] w where 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) 0 < a < 1, 0 ≤ b < 1, 0 ≤ c < 1, a + b + c < 1, 0 < y ≤ 2 / p, 0 < x < 2, 0 ≤ v < 2, 0 < z, 0 < m < 1, 0 < n < 4, 0 ≤ w / (z + 1) < 10 for the bulk catalyst precursor according to [1].

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

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

[12] A sulfurized bulk catalyst characterized by being a sulfurized bulk catalyst precursor as described in [1].

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

[14] The reacting mixture is To prepare a first mixture comprising a Ni-containing precursor, a Y-containing precursor, any Cu-containing precursor, any Nb-containing precursor, a protic liquid, and any organic compound component, To prepare a second mixture containing a Mo-containing precursor, a W-containing precursor, and a protic liquid, Optionally, a Ti-containing precursor may be added to the first mixture, the second mixture, or a combination thereof. Heating both the first mixture and the second mixture to a temperature between 60°C and 150°C, Mixing the first mixture and the second mixture together, 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) as a reaction mixture (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv)Y-containing precursor, (v) Optionally, a Cu-containing precursor and / or an Nb-containing precursor, (vi) Optionally, organic compound components, and (vii) Protic liquids, Mixing and (b) The mixture is reacted under conditions sufficient to produce a precipitate of the intermediate bulk catalyst precursor, (c) Synthesizing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor, The method for preparing the bulk catalyst precursor according to [1], wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200°C or lower.

[17] The reacting mixture is To prepare a first mixture comprising a Ni-containing precursor, a Y-containing precursor, any Cu-containing precursor, any Nb-containing precursor, a protic liquid, and any organic compound component, To prepare a second mixture containing a Mo-containing precursor, a W-containing precursor, and a protic liquid, Heating both the first mixture and the second mixture to a temperature between 60°C and 150°C, Mixing the first mixture and the second mixture together, 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 Ni-Mo-WY, Ni-Mo-WY-Cu, Ni-Mo-WY-Nb, or Ni-Mo-WY-Cu-Nb bulk catalyst precursor.

[20] The method according to

[13] or

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

[21] The organic compound component is selected from organic acids or their salts, sugars, sugar alcohols, or combinations thereof, according to the method in

[13] or

[16] .

[22] The organic compound 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, oxamidic 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, according to the method described in

[21] .

[23] The bulk catalyst precursor is synthesized in an amount of 0-40% by weight with a substance selected from the group consisting of a binder, a conventional hydrogenation catalyst, a decomposition compound, or a mixture thereof. Spray drying, (flash) drying, grinding, kneading, slurry mixing, dry or wet mixing, or a combination thereof. molding, Drying and / or heat treatment at temperatures below 200°C, or sulfide, The method according to

[13] or

[16] , further comprising one or more of the steps of

[13] .

[24] A process for hydrogenating a hydrocarbon feedstock, comprising contacting the hydrocarbon feedstock with hydrogen in the presence of a bulk catalyst under hydrogenation conditions that yield at least one product, The bulk catalyst is (a) 1 to 60% by weight of Ni based on metal oxides (b) 1 to 40% by weight of Mo based on metal oxides (c) 5-80% by weight of W based on metal oxides, (d) 0.01 to 30% by weight of Y based on metal oxides, (e) 0-20% by weight of Cu based on metal oxides (f) 0-45 wt% Ti based on metal oxides, (g) 0-20% by weight of Nb based on metal oxides The process is derived from or can be derived from a bulk catalyst precursor containing the following.

[25] The hydrogenation treatment is a process according to

[24] , selected from the group consisting of hydrogenation desulfurization, hydrogenation denitrification, hydrogenation deoxygenation, hydrogenation demetallation, hydrogenation dearomaticization, hydrogenation, hydrogenation cracking, hydrogenation purification, 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 duration of 0.1 to 10 hours. -1 The space velocity of liquid, and 100~15,000 SCF / B (17.8~2672 m 3 / m 3 The process described in

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

[0012] definition The term "bulk" may be used synonymously with "unsupported" when describing a mixed metal catalyst composition, meaning that the catalyst composition has a pre-fabricated, molded catalyst support, thereby not being in the conventional form of a catalyst where the catalyst support is added together with the metal via impregnation or precipitation.

[0013] The term “atmospheric pressure” is used herein to describe the air pressure on Earth when no external pressure correction measures are used. Typically, unless conducted at extreme ground altitudes, “atmospheric pressure” is approximately 1 atmosphere (or approximately 14.7 psi or 101 kPa).

[0014] The terms "weight %", "volume %", or "mol %" refer to the percentage of weight, volume, or moles of a component, respectively, relative to the total weight, volume, or moles of the substance containing the component. In a non-restrictive example, 10 moles of a component in 100 moles of a substance constitute 10 mol% of the component.

[0015] Bulk catalysts and bulk catalyst precursors A polymetallic bulk catalyst precursor composition is provided, comprising oxides of Ni, Mo, W, Y, and optionally Cu, Ti, and / or Nb. Before use for hydrogenation, the catalyst precursor may be sulfurized, thereby converting the metal to a metal sulfide. After sulfurization, the composition is defined as equivalent to / as the "catalyst" for the purposes of the appended claims.

[0016] The bulk catalyst and / or corresponding bulk catalyst precursor comprises nickel (Ni), molybdenum (Mo), tungsten (W), yttrium (Y), and optionally copper (Cu), titanium (Ti), and / or niobium (Nb) metals. The bulk catalyst and / or corresponding bulk catalyst precursor comprises 1 to 60% by weight, e.g., 5 to 40% or 20 to 60% by weight of Ni based on the metal oxide, 1 to 40% by weight, e.g., 1 to 25% or 3 to 20% by weight of Mo based on the metal oxide, 5 to 80% by weight, e.g., 10 to 35% or 20 to 75% by weight of W based on the metal oxide, and 0.01 to 30% by weight, e.g., 0.1 to 30% It may contain, by weight %, or 1 to 30 by weight %, of Y; 0 to 20 by weight based on metal oxides, for example, 0.1 to 20 by weight, or 1 to 20 by weight %, of Cu; 0 to 45 by weight based on metal oxides, for example, 2 to 45 by weight, 5 to 40 by weight, 10 to 35 by weight, or 20 to 30 by weight %, of Ti; and 0 to 10 by weight based on metal oxides, for example, 0.01 to 10 by weight, 0.1 to 10 by weight, or 1 to 10 by weight %, of Nb. Therefore, the bulk catalysts disclosed herein are named Ni-Mo-WY, Ni-Mo-WY-Cu, Ni-Mo-WY-Ti, Ni-Mo-WY-Nb, Ni-Mo-WY-Cu-Ti, Ni-Mo-WY-Cu-Nb, Ni-Mo-WY-Ti-Nb, or Ni-Mo-WY-Cu-Ti-Nb. Here, each metal is present in the amounts described above.

[0017] The molar ratios of metals in the bulk catalyst and / or the corresponding bulk catalyst precursor can, in principle, vary over a wide range. The molar ratio of Y / (Ni+Mo+W+Cu+Ti+Nb) in the bulk catalyst and / or the corresponding bulk catalyst precursor can be in the range of 10:1 to 1:100, or 3:1 to 1:3. The molar ratio of Ni / W in the bulk catalyst and / or the corresponding bulk catalyst precursor can be in the range of 10:1 to 1:10. The molar ratio of W / Mo in the bulk catalyst and / or the corresponding catalyst precursor can be in the range of 100:1 to 1:100.

[0018] The bulk catalyst precursor is a hydroxide and may be characterized by having the following chemical formula: A v [Ni 1-a-b-c Y a Cu b Nb c (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 component, and (iii)O <a<1、0≦b<1、0≦c<1、a+b+c<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。

[0019] The bulk catalyst precursor may consist of at least 55% by weight (at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight) of oxides of Ni, Mo, W, and Y before being sulfided to form the bulk catalyst. In any embodiment, the bulk catalyst and / or the corresponding bulk catalyst precursor may contain 40% by weight or less of a binder substance. The binder substance may be added to improve the physical and / or thermal properties of the catalyst.

[0020] The bulk catalyst and / or the corresponding bulk catalyst precursor may further contain an organic compound 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 component is present, the molar ratio of nickel to the organic compound component in the composition may be in the range of 3:1 to 20:1.

[0021] The bulk catalyst and / or corresponding bulk catalyst precursor have a BET specific surface area of ​​at least 20 m². 2 / g, or at least 50m 2 / g, or at least 75m 2 / g, or at least 100m 2 It may be / g. In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor has a BET surface area of ​​250 m². 2 / g or less, or 200m 2 / g or less, or 175m 2 / g or less, or 150m 2 / g or less, or 125m 2 It may be less than or equal to / g. Each of the above lower limits of the BET specific surface area is clearly considered in relation to each of the above upper limits. The term "BET specific surface area" means the specific surface area determined from nitrogen adsorption data according to the method of S. Brunauer, PHEmmett and E. Teller (J. Am. Chem. Soc. 1938, 60, 309-331).

[0022] The bulk catalyst and / or the corresponding bulk catalyst precursor have a pore volume of at least 0.02 cm³. 3 / g, or at least 0.03cm 3 / g, or at least 0.04cm 3 / g, or at least 0.05cm 3 / g, or at least 0.06cm 3 / g, or at least 0.08cm 3 / g, or at least 0.09cm 3 / g, or at least 0.10cm 3 / g, or at least 0.11cm 3 / g, or at least 0.12cm 3 / g, or at least 0.13cm 3 / g, or at least 0.14cm 3 / g, or at least 0.15cm 3 It may be / g. In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor has a pore volume of 0.80 cm³. 3 Less than / g, or 0.70cm 3 Less than / g, or 0.60cm 3 Less than / g, or 0.50cm 3 Less than / g, or 0.45cm 3 Less than / g, or 0.40cm 3 Less than / g, or 0.35cm 3 Less than / g, or 0.30cm 3 It may be less than / g. Each of the above lower limits for pore volume is clearly considered in relation to each of the above upper limits. The pore volume was determined 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).

[0023] The bulk catalyst and / or the corresponding bulk catalyst precursor have a particle density of at least 1.00 g / cm³. 3 (For example, at least 1.10 g / cm³) 3 , or at least 1.20 g / cm³ 3, or at least 1.30 g / cm³ 3 , or at least 1.40 g / cm³ 3 , or at least 1.50 g / cm³ 3 , or at least 1.60 g / cm³ 3 ) may be. In any embodiment, the self-supporting catalyst and / or the corresponding self-supporting catalyst precursor has a particle density of 3.00 g / cm³ 3 Below (for example, 2.90 g / cm³) 3 The following, or 2.80 g / cm³ 3 The following, or 2.70 g / cm³ 3 The following, or 2.60 g / cm³ 3 The following, or 2.50 g / cm³ 3 The following, or 2.40 g / cm³ 3 The following, or 2.30 g / cm³ 3 The following, or 2.20 g / cm³ 3 The following are possible. Each of the above lower limits of particle density is clearly considered in relation to each of the above upper limits. The particle density (D) 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 volumetric displacement by placing the sample in a column of mercury under a 28 mmHg vacuum.

[0024] Bulk catalysts and / or corresponding bulk catalyst precursors may be characterized by poor crystallinity as having broad diffraction peaks of low intensity via powder X-ray diffraction. As used herein, a broad diffraction peak means a peak with a total width at half maximum (FWHM) greater than 1° (on a 2-theta scale).

[0025] Preparation of bulk catalysts and catalyst precursors The bulk catalyst precursor of the present invention 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, and furthermore, the catalyst precursor is prepared in a manner in which it remains a hydroxide before sulfidation to form the bulk catalyst.

[0026] 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, and molybdenum and tungsten precursor compounds in solution, as a reaction mixture to obtain a precipitate or co-gel. The precipitation or co-gelation is carried out at a temperature and pH at which the metal precursor precipitates or forms a co-gel.

[0027] If titanium is present, it can be introduced via either an in-situ or ex-situ route. In the in-situ route, a Ti-containing precursor compound may be added to the reaction mixture to precipitate titanium during coprecipitation or co-gelation of Ni-Mo-WY oxide, Ni-Mo-WY-Cu oxide, or Ni-Mo-WY-Nb or Ni-Mo-WY-Cu-Nb oxide. In the ex-situ route, one or more titanium precursor compounds may be synthesized with a precipitate or co-gel of Ni-Mo-WY oxide, Ni-Mo-WY-Cu oxide, or Ni-Mo-WY-Nb or Ni-Mo-WY-Cu-Nb oxide.

[0028] In any embodiment, the in-situ addition of titanium may include (a) mixing as a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Y-containing precursor, (v) a Ti-containing precursor, (vi) optionally a Cu-containing precursor and / or a Nb-containing precursor, (vii) optionally an organic compound component, and (viii) a protic liquid, and (b) reacting the mixture under conditions sufficient to produce a precipitation of a bulk catalyst precursor. The reaction mixture can be obtained by (1) preparing a first mixture containing a Ni-containing precursor, a Y-containing precursor, an optional Nb-containing precursor, and / or an optional Cu-containing precursor, a protic liquid, and an optional organic compound component; (2) preparing a second mixture containing 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 between 60°C and 150°C; and (5) mixing the first and second mixtures together. After the reaction steps, the resulting bulk catalyst precursor may be separated from the liquid, for example, by filtration or spray drying, if necessary.

[0029] In any embodiment, the ex-situ addition of titanium may include (a) mixing as a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Y-containing precursor, (v) optionally a Cu-containing precursor or a Nb-containing precursor, (vi) optionally an organic compound 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) synthesizing 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 Y-containing precursor, an optional Cu-containing precursor, and / or an optional Nb-containing precursor, a protic liquid, and an optional organic compound 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 between 60°C and 150°C; and (4) mixing the first and second mixtures together. After the reaction steps, the resulting intermediate bulk catalyst precursor may be separated from the liquid, for example, by filtration or spray drying, if necessary.

[0030] The temperature at which the catalyst precursor is formed may 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. The reaction may also be carried out under hydrothermal conditions, where the reaction temperature is above the boiling point of the protic liquid. Typically, such conditions create a pressure above atmospheric pressure, and the reaction then proceeds, preferably in an autoclave, preferably under its own pressure, i.e., without further pressure being added. An autoclave is a device capable of withstanding pressure, intended 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.

[0031] Reaction times under both atmospheric and hydrothermal conditions are selected to be long enough to substantially complete the reaction. Reaction times can be very short (e.g., less than one hour for highly reactive reactants). Clearly, longer reaction times, perhaps 24 hours, may be required for less reactive starting materials. In some situations, reaction time may be inversely proportional to temperature.

[0032] Generally, the reaction mixture is maintained at its natural pH throughout the reaction process. The pH can be maintained in the range of 0–12 (e.g., 3–9 or 5–8). The pH can be altered to increase or decrease the rate of precipitation or co-gelation, depending on the desired properties of the product.

[0033] Metal precursors can be added to the reaction mixture in a 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.

[0034] 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., diamolybdate, phosphomolybdate).

[0035] 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 tungstate (e.g., ammonium tungstate, ammonium metatungstate, ammonium paratungstate), and heteropolytungstates (e.g., silitungstic acid, phosphotungstic acid).

[0036] Typical examples of nickel-containing precursor compounds include nickel acetate, nickel acetylacetonate, nickel bromide, nickel carbonate, nickel hydroxycarbonate, nickel bicarbonate, nickel chloride, nickel nitrate, and nickel sulfate.

[0037] Typical examples of Y-containing precursor compounds include yttrium(III) nitrate, yttrium(III) acetate, yttrium(III) acetylacetonate, yttrium(III) hydroxide, yttrium(III) chloride, yttrium(III) bromide, yttrium(III) carbonate, yttrium(III) phosphate, yttrium(III) sulfate, yttrium(III) isopropoxide, and yttrium(III) butoxide.

[0038] Typical examples of copper-containing precursor compounds include copper(II) acetate, copper(II) acetylacetonate, copper(II) hydroxide, copper(II) chloride, copper(II) bromide, copper(II) carbonate, copper(II) nitrate, copper(II) phosphate, and copper(II) sulfate.

[0039] Typical examples of Nb-containing precursor compounds include niobium oxalate, ammonium niobium oxalate, niobium chloride, niobium bromide, niobium ethoxide, niobium n-propoxide, and niobium isopropoxide.

[0040] Any titanium-containing compound suitable for the preparation of the bulk catalyst of the type described herein can be used as a Ti-containing precursor compound. The Ti-containing precursor is tetravalent titanium (Ti 4+ ) containing compounds, trivalent titanium (Ti 3+ ) may contain compounds or combinations thereof.

[0041] Typical Ti-containing precursor compounds include TiO2 nanoparticles, colloidal TiO2, fumed TiO2, titanium hydroxide, organotitanium compounds, titanium halides, and water-soluble titanium salts.

[0042] Titanium dioxide nanoparticles may be any type of titanium dioxide. Titanium dioxide may have a high content of anatate and / or rutile. For example, titanium dioxide may contain at least 50, or at least 55, or at least 60, or at least 65, or at least 70, or at least 75, or at least 80, or at least 85, or at least 90, or at least 95, or at least 98, or at least 99% by weight of anatate and / or rutile. In some embodiments, titanium dioxide is essentially composed of anatate and / or rutile. Titanium dioxide particles preferably have a median particle size (D50) of less than 100 nm (e.g., 3 to 50 nm). Titanium dioxide nanoparticles can be introduced into a composition as a solution prepared by dispersion of a dispersant, a water or solvent-containing paste, or a powder. Examples of dispersants used to prepare solutions include water, alcohols (e.g., methanol, ethanol, isopropanol, n-butanol, isobutanol), and ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone).

[0043] Representative organotitanium compounds include titanium alkoxides (wherein each R is a different C1-C4 alkyl group) and titanium acyl compounds with the general structure Ti(OR)4. 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 include those characterized by the general formula Ti(OR')2(acac)2 (wherein each R' is a different C1-C4 alkyl group, and "acac" is acetylacetonate).

[0044] Titanium halides represented by the formula TiX4 or TiX3 (wherein X is chloro, bromo, iodine, or fluoro, or a mixture thereof) may be used as titanium precursors. In one embodiment, the titanium halide is titanium tetrachloride, titanium tetrabromide, or a combination thereof.

[0045] This disclosure also intends to explore the use of organotitanium halides such as chlorotitanium triisopropoxide [Ti(Oi-Pr)3Cl] as Ti-containing precursor compounds.

[0046] Typical water-soluble titanium salts include titanium nitrate and titanium sulfate.

[0047] The organic compound component may be an organic compound suitable for forming a metal-ligand complex in solution. The organic compound component may be selected from organic acids or their salts, sugars, sugar alcohols, or combinations thereof.

[0048] 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, oxamidic acid, serine, aspartic acid, glutamic acid, iminodiacetic acid, and ethylenediaminetetraacetic acid.

[0049] Typical sugars include fructose, glucose, galactose, mannose, sucrose, lactose, maltose, and their derivatives.

[0050] Representative sugar alcohols include erythritol, xylitol, mannitol, sorbitol, and their derivatives.

[0051] 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 may be water alone or a mixture of water and alcohol.

[0052] Additional processing Before being used in the hydrogenation process, the bulk catalyst precursor may be subjected to one or more of the following processes: (i) synthesis with a substance selected from the group consisting of a binder, a conventional hydrogenation catalyst, a decomposition compound, or a mixture thereof; (ii) spray drying, (flash) drying, grinding, kneading, slurry mixing, drying or wet mixing, or a combination thereof; (iii) molding; (iv) drying and / or heat treatment; and (v) sulfidation. The list of these processes from (i) to (v) is for convenience only and is not a description that restricts these processes to being carried out in this order. These processes are described in more detail below.

[0053] Additional processing step (i) - Synthesis with further substances If desired, additional substances selected from the group consisting of binders, conventional hydrogenation catalysts, decomposition compounds, or mixtures thereof may be added during or after the preparation of the bulk catalyst precursor as described above. Preferably, the substances are added after the preparation of the bulk catalyst precursor and before spray drying or any alternative technique, or, if spray drying or any alternative technique is not applied, before molding. Optionally, the bulk metal precursor prepared as described above may be subjected to solid-liquid separation before forming a complex with the substance. After solid-liquid separation, a washing step may be optionally included. Furthermore, after any solid-liquid separation and drying steps and before complex formation with the substance, the bulk catalyst particles may be heat-treated.

[0054] In all of the modifications of the process described above, the phrase “synthesizing a bulk catalyst precursor with a substance” means adding the substance to bulk metal particles, or vice versa, and mixing the resulting composition. 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.

[0055] By synthesizing the bulk catalyst precursor with additional 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 in the range of at least 0.5 μm (e.g., at least 1 μm, or at least 2 μm), but less than or equal to 5000 μm (e.g., less than or equal to 1000 μm, or less than or equal to 500 μm, or less than or equal to 150 μm). The median particle size of the catalyst precursor may be in the range of 1 to 150 μm (e.g., 2 to 150 μm).

[0056] By synthesizing bulk metal particles with a material, bulk metal particles embedded within this material, or vice versa, are obtained. Typically, the morphology of the bulk metal particles is essentially maintained within the resulting bulk catalyst composition.

[0057] The binder substance used may be any substance conventionally used as a binder in hydrogenation catalysts. Examples of binder substances include silica, silica-alumina (e.g., conventional silica-alumina, silica-coated alumina, and alumina-coated silica), alumina (e.g., boehmite, pseudo-boehmite, 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 may be applied in this manner or after decomposition.

[0058] 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 The pore volume of alumina, when measured by nitrogen adsorption, is 0.1 to 1.5 cm³. 3 It could be in the range of / g.

[0059] Generally, the binders added have lower or no catalytic activity than the bulk metal particles. A binder amount of 0 to 40% by weight of the total composition may be appropriate depending on the intended catalytic application. 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, or 3 to 20% by weight, or 4 to 12% by weight).

[0060] Additional processing steps (ii) - spray drying, (flash) drying, grinding, kneading, slurry mixing, drying, or wet mixing A bulk catalyst precursor containing any of the above (further) substances may be subjected to spray drying, (flash) drying, grinding, kneading, slurry mixing, drying, or wet mixing, or a combination thereof, with wet mixing and kneading, or slurry mixing and spray drying being preferred.

[0061] These techniques can be applied either before or after the addition of any of the above (further) substances (if any such addition is present), after solid-liquid separation, before and after heat treatment, and after re-wetting.

[0062] Preferably, the catalyst precursor is synthesized with any of the above substances and subjected to any of the above techniques. It is believed that the degree of mixing of the catalyst precursor particles with any of the above substances can be improved by applying any of the above techniques, such as spray drying, (flash) drying, grinding, kneading, slurry mixing, drying or wet mixing, or a combination thereof. This applies when the substance is added before or after the application of any of the above methods. However, it is generally preferable to add the substance before step (ii). If the substance is added after step (ii), the resulting composition can be completely mixed by any conventional technique before any further processing steps such as molding. An advantage of spray drying is that no wastewater flow occurs when this technique is applied.

[0063] Spray drying can be performed at an outlet temperature in the range of 100°C to 200°C (for example, 120°C to 180°C).

[0064] Dry mixing means mixing dry catalyst precursor particles with any of the above-mentioned substances in a dry state. Wet mixing generally involves mixing a wet filter cake containing catalyst precursor particles with any of the above-mentioned substances, which may be powder or wet filter cake, to form a homogeneous paste.

[0065] Additional processing step (iii) - Molding If desired, a bulk catalyst precursor containing any of the above (further) substances may optionally be molded after step (ii) has been applied. Molding includes extrusion, pelletizing, beading, and / or spray drying. Note that when the bulk catalyst composition is used in a slurry reactor, fluidized bed, moving bed, or expanding bed, spray drying or beading is generally applied. In stationary bed or boiling bed applications, the bulk catalyst composition is generally extruded, pelletized, and / or beaded. In the latter case, any additives typically used to facilitate molding more than conventionally may be added at any stage before or 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 pesticide the alumina and increase the mechanical strength of the extruded material.

[0066] If the molding process includes extrusion, beading, and / or spray drying, the molding process is preferably carried out in the presence of a liquid such as water. In extrusion and / or beading, the amount of liquid in the molding mixture, expressed as loss on ignition, can be in the range of 20% to 80%.

[0067] Additional processing step (iv) - Drying and / or heat treatment Preferably, after any drying step exceeding 100°C, the resulting molded bulk catalyst composition may be heat-treated as needed. However, heat treatment is not essential to the process of this disclosure. "Heat treatment" as used in this disclosure means a treatment carried out at a temperature of 100°C to 200°C for various periods of 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 water vapor.

[0068] Throughout the entire processing steps described above, the amount of liquid must be controlled. If the amount of liquid is too low before the bulk catalyst composition is subjected to spray drying, additional liquid must be added. Conversely, if the amount of liquid is too high before the bulk catalyst composition is extruded, the amount of liquid must be reduced using solid-liquid separation techniques such as filtration, decantation, or evaporation, and if necessary, the resulting material may be dried and then re-wetted to some extent. Properly controlling the amount of liquid throughout the entire processing steps described above is within the scope of the art.

[0069] Additional processing step (v) - sulfidation Tetrametallic bulk catalysts are generally used in their sulfide form. Catalytic sulfidation can be carried out by any method effective 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 immediately after its preparation or after any one of the additional processing steps (i) to (iv). The sulfidation process can be carried out in the liquid phase and the gas phase.

[0070] 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 composition has been placed in the hydrogenation treatment apparatus).

[0071] Use in hydrogenation treatment The bulk catalyst precursors of the present disclosure are particularly useful for hydrotreating hydrocarbon feedstocks. Hydrotreating includes processes such as hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrocracking, hydrorefining, hydroisomerization, and hydrocracking.

[0072] A wide range of petroleum and chemical hydrocarbon feedstocks can be hydrotreated according to the present disclosure. Hydrocarbon feedstocks include those obtained or derived from crude mineral oils, tar sands, coal liquefaction, shale oil, and hydrocarbon synthesis, such as atmospheric distillation residues, hydrocracking products, raffinates, hydrotreated oils, atmospheric and vacuum gas oils, coker gas oils, atmospheric and vacuum residues, decanted oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, bio-renewable feedstocks, and mixtures thereof. Suitable feedstocks range from relatively light distillation fractions such as gas oils, lubricating oils, and residues to heavy feedstocks. Examples of light fraction feedstocks include naphtha (typical boiling range of about 25°C to about 210°C), diesel oil (typical boiling range of about 150°C to about 400°C), kerosene or jet fuel (typical boiling range of about 150°C to about 250°C), etc. Examples of heavy feedstocks include vacuum (or heavy) gas oil (typical boiling range of about 315°C to about 610°C), raffinates, lubricating oils, cycle oils, waxy oils, etc. Preferred hydrocarbon feedstocks have a boiling range of about 150°C to about 650°C (e.g., about 150°C to about 450°C).

[0073] Hydrotreating 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), a liquid hourly space velocity (LHSV) of 0.1 to 10 h -1 or 0.5 to 5 h -1 and a hydrogen feed rate of 100 to 15,000 SCF / B (17.8 to 2672 m 3 / m 3 ) or 500 to 10,000 SCF / B (89 to 1781 m 3 / m 3) may contain hydrogen gas rates.

[0074] The hydrogenation treatment according to this disclosure may be carried out in one or more reaction zones using any suitable reactor system, such as one or more stationary, moving, or fluidized bed reactors. A stationary reactor may include one or more vessels, one or more layers of catalyst in each vessel, and various combinations of hydrogenation catalysts in one or more vessels. [Examples]

[0075] The following exemplary examples are intended to be non-limiting.

[0076] 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.

[0077] Preparation of Solution B: In separate 500 mL beakers, 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. The final pH after addition 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.

[0078] Example 2 (Comparison) Synthesis of bulk catalyst precursors [Ni(7.5)-Mo(1)-W(3)] Preparation of Solution A: 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.

[0079] Preparation of Solution B: In separate 500 mL beakers, 128.3 g of nickel nitrate and 5.8 g of maleic acid were dissolved in 100 g of deionized water.

[0080] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0081] 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.

[0082] Preparation of Solution B: In separate 500 mL beakers, 110.3 g of nickel nitrate and 5.8 g of maleic acid were dissolved in 100 g of deionized water.

[0083] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0084] Example 4 (Comparison) 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. Next, the solution was heated to 80°C.

[0085] Preparation of Solution B: In separate 500 mL beakers, 188 g of nickel nitrate, 16 g of ammonium niobate oxalate, and 10 g of maleic acid were dissolved in 100 g of deionized water.

[0086] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0087] Example 5 (Comparison) 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. Next, the solution was heated to 80°C.

[0088] Preparation of Solution B: In separate 500 mL beakers, 166 g of nickel nitrate, 32 g of ammonium niobate oxalate, 8 g of copper(II) nitrate, and 9 g of maleic acid were dissolved in 100 g of deionized water.

[0089] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0090] Example 6 Synthesis of bulk catalyst precursors [Ni(6.2)-Mo(1)-W(3)-Y(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. Next, the solution was heated to 80°C.

[0091] Preparation of Solution B: In separate 500 mL beakers, 174 g of nickel nitrate, 40 g of yttrium(III) nitrate hexahydrate, and 9 g of maleic acid were dissolved in 100 g of deionized water.

[0092] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0093] Example 7 Synthesis of bulk catalyst precursors [Ni(6.5)-Mo(1)-W(3)-Nb(0.5)-Y(0.1)] 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. Next, the solution was heated to 80°C.

[0094] Preparation of Solution B: In separate 500 mL beakers, 174 g of nickel nitrate, 4 g of yttrium(III) nitrate hexahydrate, 16 g of ammonium(V) niobate hydrate, and 10 g of maleic acid were dissolved in 100 g of deionized water.

[0095] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0096] Example 8 Synthesis of bulk catalyst precursors [Ni(6.5)-Mo(1)-W(3)-Y(0.1)] 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. Next, the solution was heated to 80°C.

[0097] Preparation of Solution B: In separate 500 mL beakers, 174 g of nickel nitrate, 4 g of yttrium(III) nitrate hexahydrate, and 10 g of maleic acid were dissolved in 100 g of deionized water.

[0098] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0099] Example 9 Synthesis of bulk catalyst precursors [Ni(6.5)-Mo(1)-W(3)-Nb(0.5)-Y(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. Next, the solution was heated to 80°C.

[0100] Preparation of Solution B: In separate 500 mL beakers, 174 g of nickel nitrate, 20 g of yttrium(III) nitrate hexahydrate, 16 g of ammonium(V) niobate hydrate, and 10 g of maleic acid were dissolved in 100 g of deionized water.

[0101] Solution B was added to solution A over a period of 15 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after the addition 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.

[0102] Example 10 Synthesis of bulk catalyst precursors [Ni(4.5)-Mo(1)-W(3)-Y(1)-Nb(1)-Cu(0.3)-Ti(5.5)] 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. Next, the solution was heated to 80°C.

[0103] Preparation of Solution B: In separate 1 L beakers, 389 g of nickel nitrate, 113 g of yttrium nitrate hexahydrate, 60 g of ammonium niobate oxalate, 14 g of copper nitrate trihydrate, and 20 g of maleic acid were dissolved in 800 g of deionized water.

[0104] Solution B was added to solution A over 30 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration. The filter cake and 87 g of TiO2 (Venator Hombikat 8602) were mixed to form a homogeneous phase and stirred at 80°C for 2 hours. The mixture was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0105] Example 11 Synthesis of bulk catalyst precursors [Ni(4.5)-Mo(1)-W(3)-Y(1)-Cu(1)-Ti(5.5)] 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. Next, the solution was heated to 80°C.

[0106] Preparation of Solution B: In separate 1 L beakers, 389 g of nickel nitrate, 113 g of yttrium nitrate hexahydrate, 46 g of copper nitrate trihydrate, and 20 g of maleic acid were dissolved in 800 g of deionized water.

[0107] Solution B was added to solution A over 30 minutes. The pH was monitored during the addition. A green precipitate formed immediately after the addition of solution B. The final pH after addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours. After aging, the product was collected by filtration. The filter cake and 87 g of TiO2 (Venator Hombikat 8602) were mixed to form a homogeneous phase and stirred at 80°C for 2 hours. The mixture was collected by filtration, washed with deionized water, and dried in an oven at 130°C.

[0108] Example 12 Extrusion Production Before evaluating the catalyst, the catalyst precursor was molded and extruded. The dried catalyst precursor was pulverized into a fine powder (<100 mesh), mixed with an appropriate amount of binder and water to create an extrudeable mixture, which was then extruded using a carver press.

[0109] Example 13 Characterization of bulk catalyst precursors The particle density (D), BET surface area (SA), and pore volume (PV) of the bulk catalyst precursors of Examples 1 to 11 were measured. The results are shown in Table 1 below. yttrium This indicates that the addition of [substance] may reduce particle density. [Table 1]

Claims

1. A bulk catalyst precursor for use in the hydrogenation treatment of hydrocarbon raw materials, (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) 20 to 75% by weight of W based on metal oxides (d) 1 to 30% by weight of Y based on metal oxides (e) 0 to 20% by weight of Cu based on metal oxides (f) 0 to 45% by weight of Ti based on metal oxides (g) 0 to 20% by weight of Nb based on metal oxides Includes, 50-250m ２ BET specific surface area per g: 0.02–0.80 cm² ３ Pore ​​volume per g, and 1.00 to 3.00 g / cm³ ３ The bulk catalyst precursor having one or more of the particle density characteristics.

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

3. The bulk catalyst precursor according to claim 2, wherein the organic compound 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 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, oxamidic 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 component is in the range of 3:1 to 20:

1.

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

7. A sulfurized bulk catalyst characterized by being a sulfurized bulk catalyst precursor according to claim 1.

8. A method for preparing the bulk catalyst precursor described in claim 1, (a) as a reaction mixture (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv) Y-containing precursor, (v) Optionally, a Cu-containing precursor, a Ti-containing precursor, and / or an Nb-containing precursor, (vi) Optionally, organic compound components, and (vii) Protic liquid, Mixing and (b) Reacting the mixture under conditions sufficient to produce a precipitate of the bulk catalyst precursor, The method wherein steps (a) and (b) for preparing the bulk catalyst precursor are carried out at a temperature of 200°C or lower.

9. The reacting mixture is To prepare a first mixture containing a Ni-containing precursor, a Y-containing precursor, an arbitrary Cu-containing precursor, an arbitrary Nb-containing precursor, a protic liquid, and an arbitrary organic compound component, To prepare a second mixture containing a Mo-containing precursor, a W-containing precursor, and a protic liquid, Optionally, a Ti-containing precursor may be added to the first mixture, the second mixture, or a combination thereof. Heating both the first mixture and the second mixture to a temperature between 60°C and 150°C, Mixing the first mixture and the second mixture together, The method according to claim 8, which is prepared by

10. The Ti-containing precursor is TiO ２ Nanoparticles, colloidal TiO ２ Fumed TiO ２ The method according to claim 9, which is selected from titanium hydroxide, organotitanium compounds, titanium halides, organotitanium halides, water-soluble titanium salts, or combinations thereof.

11. (a) as a reaction mixture (i) Ni-containing precursor, (ii) Mo-containing precursor, (iii) W-containing precursor, (iv) Y-containing precursor, (v) Optionally, a Cu-containing precursor and / or an Nb-containing precursor, (vi) Optionally, organic compound components, and (vii) Protic liquid, Mixing and (b) Reacting the mixture under conditions sufficient to produce a precipitate of an intermediate bulk catalyst precursor, (c) Synthesizing the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor, The method for preparing the bulk catalyst precursor according to claim 1, wherein the above steps (a), (b), and (c) for preparing the bulk catalyst precursor are carried out at a temperature of 200°C or lower.

12. The reacting mixture is To prepare a first mixture containing a Ni-containing precursor, a Y-containing precursor, an arbitrary Cu-containing precursor, an arbitrary Nb-containing precursor, a protic liquid, and an arbitrary organic compound component, To prepare a second mixture containing a Mo-containing precursor, a W-containing precursor, and a protic liquid, Heating both the first mixture and the second mixture to a temperature between 60°C and 150°C, Mixing the first mixture and the second mixture together, The method according to claim 11, which is prepared by...

13. The Ti-containing precursor is TiO ２ Nanoparticles, fumed TiO ２ The method according to claim 11, or a combination thereof.

14. The method according to claim 11, wherein the intermediate bulk catalyst precursor is Ni-Mo-W-Y, Ni-Mo-W-Y-Cu, Ni-Mo-W-Y-Nb, or Ni-Mo-W-Y-Cu-Nb bulk catalyst precursor.

15. The method according to claim 8 or 11, wherein the reaction is carried out at one or more temperatures, either (a) in the range of 60°C to 100°C under atmospheric pressure, or (b) at temperatures exceeding 100°C under self-pressure.

16. The method according to claim 8 or claim 11, wherein the organic compound component is selected from organic acids or their salts, sugars, sugar alcohols, or combinations thereof.

17. The method according to claim 16, wherein the organic compound 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, oxamidic 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.

18. A process for hydrogenating a hydrocarbon feedstock, comprising contacting the hydrocarbon feedstock with hydrogen in the presence of a bulk catalyst under hydrogenation conditions that yield at least one product, 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) 20 to 75% by weight of W based on metal oxides (d) 1 to 30% by weight of Y based on metal oxides (e) 0 to 20% by weight of Cu based on metal oxides (f) 0 to 45% by weight of Ti based on metal oxides (g) 0 to 20% by weight of Nb based on metal oxides Derived from a bulk catalyst precursor containing, The bulk catalyst precursor is 50 to 250 m ２ / g of BET specific surface area, 0.02 to 0.80 cm ３ / g of pore volume, and 1.00 to 3.00 g / cm ３ of the characteristics of particle density, and has one or more of the above, the process.

19. The process according to claim 18, wherein the hydrogenation treatment is selected from the group consisting of hydrogenation desulfurization, hydrogenation denitrification, hydrogenation deoxygenation, hydrogenation demetallation, hydrogenation dearomaticization, hydrogenation, hydrogenation cracking, hydrogenation purification, hydrogen isomerization, and hydrogenation cracking.

20. 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 space velocity of the liquid, and 100 to 15,000 SCF / B (17.8 to 2672 m ３ / m ３ The process according to claim 18, comprising a hydrogen gas rate of ).

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