Tetrametallic bulk hydroprocessing catalysts

Abstract

To provide bulk catalysts comprising oxides of nickel, molybdenum, tungsten and titanium, and methods for synthesizing bulk catalysts.SOLUTION: The catalysts are useful for hydroprocessing, particularly hydrodesulfurization and hydrodenitrogenation, of hydrocarbon feedstocks. The bulk catalyst precursor is not calcined and comprises hydroxides.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and benefit of U.S. Provisional Application No. 63 / 019,479, filed May 4, 2020.

[0002] Field The present disclosure relates to quaternary metallic bulk catalysts for use in the hydroprocessing of hydrocarbon feedstocks, and methods for preparing such catalysts. [Background technology]

[0003] background Hydroprocessing of hydrocarbon feedstocks generally encompasses any process in which a hydrocarbon feedstock is reacted with hydrogen in the presence of a catalyst under hydrotreating conditions, usually at elevated temperatures and pressures. Hydroprocessing includes processes such as hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrogenolysis, hydrofinishing, hydroisomerization, and hydrocracking.

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

[0005] In addition to supported catalysts, hydrotreating using bulk catalysts (also called "unsupported" catalysts) is also known. Although bulk hydrotreating catalyst compositions have relatively high catalytic activity compared to conventional supported hydrotreating catalysts, there is a continuing need in the art to develop new bulk catalyst compositions with even improved hydrotreating activity. Summary of the Invention

[0006] summary In a first aspect, there is provided a bulk catalyst precursor comprising: (a) 1 to 60 wt % Ni, calculated as metal oxide; (b) 1 to 40 wt % Mo, calculated as metal oxide; (c) 5 to 80 wt % W, calculated as metal oxide; and (d) 2 to 45 wt % Ti, calculated as metal oxide.

[0007] In a second aspect, there is provided a sulfided bulk catalyst, characterized as being a bulk catalyst precursor described herein that has been sulfided.

[0008] In a third aspect, there is provided 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 Ti-containing precursor; (v) optionally an organic compound-based component; and (vi) a protic liquid; and (b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor, wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200° C. or less.

[0009] In a fourth aspect, there is provided 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) an optional organic compound-based component, and (v) a protic liquid; (b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor; and (c) composite the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor, wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200° C. or less.

[0010] In a fifth aspect, there is provided a method for hydrotreating a hydrocarbon feedstock, comprising contacting the hydrocarbon feedstock with hydrogen in the presence of a bulk catalyst under hydrotreating conditions to obtain at least one product, wherein the bulk catalyst is derived or derivable from a catalyst precursor comprising: (a) 1 to 60 wt. % Ni, calculated as metal oxide; (b) 1 to 40 wt. % Mo, calculated as metal oxide; (c) 5 to 80 wt. % W, calculated as metal oxide; and (d) 2 to 45 wt. % Ti, calculated as metal oxide. [Brief explanation of the drawings]

[0011] Brief description of the drawings [Figure 1] FIG. 1 is a quaternary phase diagram using fractional coordinates of the vertices defining the polyhedral Ni—Mo—W—Ti composition space, according to one embodiment of the present disclosure.

[0012] [Figure 2] FIG. 1 is a quaternary phase diagram using fractional coordinates of the vertices defining the polyhedral Ni—Mo—W—Ti composition space, according to one embodiment of the present disclosure.

[0013] [Figure 3] 1 is an isotherm plot of N 2 physisorption performed at 77 K on the Ni—Mo—W—Ti catalyst precursor of Example 4.

[0014] [Figure 4] 1 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image obtained for the Ni—Mo—W—Ti catalyst precursor of Example 4.

[0015] [Figure 5] 1 is an isotherm plot of N 2 physisorption performed at 77 K on the Ni—Mo—W—Ti catalyst precursor of Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0016] Detailed Description Definition of Terms The term "bulk" can be used synonymously with "unsupported" when describing a mixed metal catalyst composition, meaning that the catalyst composition is not a catalyst in the traditional catalyst form, having a preformed and shaped catalyst support on which metals are then supported by impregnation or deposition.

[0017] As used herein, the term "atmospheric pressure" is used to describe the pressure of the atmosphere without the use of external pressure-altering means. Generally, unless practiced at extreme Earth altitudes, "atmospheric pressure" is about 1 atmosphere (about 14.7 psi or about 101 kPa).

[0018] The terms "weight percent" and "wt. %," which may be used interchangeably, refer to the percent by weight of a given component, based on the total weight of the composition, unless otherwise specified. That is, all weight percent values ​​are based on the total weight of the composition, unless otherwise specified. It is understood that the sum of the weight percent values ​​of all components in a disclosed composition or formulation equals 100.

[0019] Bulk catalysts and bulk catalyst precursors A quaternary metallic bulk catalyst precursor composition is provided that includes oxides of Ni, Mo, W, and Ti. Prior to use in hydroprocessing, the catalyst precursor may be sulfided, which converts the metals to metal sulfides. After sulfiding, the composition corresponds to / is defined as a "catalyst" for purposes of the appended claims.

[0020] The bulk catalyst and / or the corresponding bulk catalyst precursor may contain nickel (Ni), molybdenum (Mo), tungsten (W), and titanium (Ti) metals. The bulk catalyst and / or the corresponding bulk catalyst precursor may contain 1 to 60 wt. % Ni, e.g., 5 to 40 wt. % or 20 to 60 wt. % Ni, calculated as metal oxide; 1 to 40 wt. % Mo, e.g., 1 to 25 wt. % or 3 to 20 wt. % W, calculated as metal oxide; and 2 to 45 wt. % Ti, e.g., 5 to 40 wt. %, 10 to 35 wt. %, or 20 to 30 wt. % Ti, calculated as metal oxide. Thus, the bulk catalyst disclosed herein may have the designation Ni-Mo-W-Ti, where each metal is present in the amount specified above.

[0021] In some embodiments, the bulk catalyst and / or corresponding bulk catalyst precursor can be defined by a region of a quaternary phase diagram, such as that shown in FIG. 1 , where the region is defined by ten points A, B, C, D, E, F, G, H, I, and J, where the ten points are, in weight percent metal oxide equivalents: A (Ni=0.39, Mo=0.00, W=0.41, Ti=0.2), B (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), C (Ni=0.09, Mo=0.17, W=0.54, Ti=0.2), D (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), E (Ni=0.09, Mo=0.17, W=0.54, Ti=0.2), F (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), G (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), H (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), I (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), J (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), J (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), K ... J (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), K (Ni=0.08, Mo=0.00, W=0.72 0.31, Mo=0.25, W=0.24, Ti=0.2), E(Ni=0.40, Mo=0.14, W=0.26, Ti=0.2), F(Ni=0.34, Mo=0.00, W=0.36, Ti=0.3), G(Ni=0.07, Mo=0.00, W=0 .63, Ti=0.3), H (Ni=0.08, Mo=0.15, W=0.48, Ti=0.3), I (Ni=0.27, Mo=0.22, W=0.21, Ti=0.3), and J (Ni=0.35, Mo=0.12, W=0.23, Ti=0.3).

[0022] In some embodiments, the bulk catalyst and / or corresponding bulk catalyst precursor can be defined by a region of a quaternary phase diagram defined by eight points A, B, C, D, E, F, G, H, and H, as shown in FIG. 2, where the eight points are, in terms of metal oxides (wt %): A (Ni=52.5, Mo=3.5, W=14, Ti=30), B (Ni=38.5, Mo=17.5, W=14, Ti=30), C (Ni=38.5, Mo=17.5, W=14, Ti=30), D (Ni=38.5, Mo=17.5, W=14, Ti=30), E (Ni=38.5, Mo=17.5, W=14, Ti=30), F (Ni=38.5, Mo=17.5, W=14, Ti=30), G (Ni=38.5, Mo=17.5, W=14, Ti=30), H (Ni=38.5, Mo=17.5, W=14, Ti=30), J ... =30), C(Ni=21, Mo=17.5, W=31.5, Ti=30), D(Ni=35, Mo=3.5, W=31.5, Ti=30), E(Ni=60, Mo=4, W=16, Ti= 20), F (Ni=44, Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4, W=36, Ti=20).

[0023] The molar ratio of metals in the bulk catalyst and / or the corresponding bulk catalyst precursor can in principle vary within a wide range. The molar ratio of Ti / (Ni+Mo+W) in the bulk catalyst and / or the corresponding bulk catalyst precursor can be in the range of 10:1 to 1:10 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 bulk catalyst precursor can be in the range of 100:1 to 1:100.

[0024] The bulk catalyst precursor is a hydroxide and has the following chemical formula: A v [Ni(OH) x (L) p y ] z [Mo m W 1-m O4][Ti(OH) n O 2-n / 2 ] w (where (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 ≦ y ≦ 2 / p, 0 ≦ x < 2, 0 ≦ v < 2, 0 < z, 0 < m < 1, 0 < n < 4, 0.1 < w / (z + 1) < 10), and may be characterized by having the following.)

[0025] The bulk catalyst precursor may be composed of at least 60 wt% (at least 70 wt%, at least 80 wt%, or at least 90 wt%) of oxides of Ni, Mo, W, and Ti before being sulfided to form the bulk catalyst. In any embodiment, the bulk catalyst and / or the corresponding bulk catalyst precursor may contain 40 wt% or less of a binder. A binder can be added to improve the physical and / or thermal properties of the catalyst.

[0026] The bulk catalyst and / or the corresponding bulk catalyst precursor may further contain an organic compound-based component, and the organic compound-based component 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. When the 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.

[0027] The BET specific surface area of the bulk catalyst and / or the corresponding bulk catalyst precursor is at least 20 m 2 / g, at least 50 m 2 / g, at least 75 m 2 / g, at least 100 m 2 / g. In any embodiment, the BET specific surface area of the self-supported catalyst and / or the corresponding self-supported catalyst precursor is 250 m 2 / g or less, 200 m 2 / g or less, 175 m 2 / g or less, 150 m 2 / g or less, 125 m 2 / g or less. Each of the above lower limits for BET specific surface area is expressly contemplated in combination with each of the above upper limits. The term "BET specific surface area" refers to the specific surface area measured from nitrogen adsorption data according to the method of S. Brunauer, P.H. Emmett and E. Teller (J. Am. Chem. Soc. 1938, 60, 309-331).

[0028] The pore volume of the bulk catalyst and / or the corresponding bulk catalyst precursor is at least 0.02 cm 3 / g, at least 0.03 cm 3 / g, at least 0.04 cm 3 / g, at least 0.05 cm 3 / g, at least 0.06 cm 3 / g, at least 0.08 cm 3 / g, at least 0.09 cm 3 / g, at least 0.10 cm 3 / g, at least 0.11 cm 3 / g, at least 0.12 cm 3 / g, at least 0.13 cm 3 / g, at least 0.14 cm 3 / g, at least 0.15 cm 3 In any embodiment, the pore volume of the self-supported catalyst and / or the corresponding self-supported catalyst precursor may be 0.80 cm 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, 0.30cm 3 / g or less. Each of the above lower pore volume limits is expressly contemplated in combination with each of the above upper limits. Pore volume is measured from nitrogen adsorption data according to the procedure described by EP Barrett, LG Joyner and PP Halenda (J. Am. Chem. Soc. 1951, 73, 373-380).

[0029] The particle density of the bulk catalyst and / or the corresponding bulk catalyst precursor is at least 1.00 g / cm 3 (e.g., at least 1.10 g / cm 3 , at least 1.20 g / cm 3 , at least 1.30 g / cm 3 , at least 1.40 g / cm 3 , at least 1.50 g / cm 3 , or at least 1.60 g / cm 3 In any embodiment, the particle density of the self-supported catalyst and / or the corresponding self-supported catalyst precursor may be 3.00 g / cm 3 or less (e.g., 2.90 g / cm 3 Below 2.80g / cm 3 Below 2.70g / cm 3 Below, 2.60g / cm 3 Below 2.50g / cm 3 or less, or 2.40 g / cm 3 Below 2.30g / cm 3 or less than 2.20 g / cm 3 Each of the above particle density lower limits is expressly contemplated in combination with each of the above upper limits. Particle density (D) is obtained by applying the formula D=M / V, where M is the weight and V is the volume of the catalyst sample. Volume is measured by measuring the volume displacement by immersing the sample in mercury under a vacuum of 28 mmHg.

[0030] The bulk catalysts and / or corresponding bulk catalyst precursors can be characterized by powder X-ray diffraction as poorly crystalline materials having broad diffraction peaks of low intensity, where broad diffraction peaks refer herein to peaks with a full width at half maximum (FWHM) greater than 1° (on the 2θ scale).

[0031] Preparation of the bulk catalyst and catalyst precursor The bulk catalyst precursor is a hydroxide, and the step prior to sulfiding to form the bulk catalyst is carried out at a temperature of 200°C or less, and the catalyst precursor is prepared by a method that maintains the hydroxide prior to sulfiding to form the bulk catalyst.

[0032] In one embodiment, the first step in the preparation of the bulk catalyst precursor is a precipitation or cogelation step, which involves reacting a Ni-containing precursor compound in solution with molybdenum and tungsten precursor compounds in solution in a reaction mixture to obtain a precipitate or cogel. The precipitation or cogelation is carried out at a temperature and pH at which the nickel precursor and the molybdenum and tungsten precursors form a precipitate or cogel.

[0033] Titanium can be introduced either in situ or ex situ. In the in situ route, a Ti-containing precursor compound may be added to the reaction mixture to precipitate titanium during the co-precipitation or cogelation of Ni-Mo-W oxide. In the ex situ route, one or more titanium precursor compounds may be composited with the Ni-Mo-W oxide precipitate or cogel.

[0034] In one embodiment, the in situ addition of titanium comprises (a) combining in a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) a Ti-containing precursor, (v) an optional organic component, and (vi) a protic liquid, and (b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor. The reaction mixture can be obtained by (1) preparing a first mixture containing the Ni-containing precursor, a protic liquid, and an optional organic component, (2) preparing a second mixture containing the Mo-containing precursor, the W-containing precursor, and a protic liquid, (3) adding the Ti-containing precursor to the first mixture, the second mixture, or a combination thereof, (4) heating both the first mixture and the second mixture to a temperature between 60°C and 150°C, and (5) combining the first mixture and the second mixture together. After the reaction step, if desired, the resulting bulk catalyst precursor may be separated from the liquid, for example, by filtration or spray drying.

[0035] In either embodiment, the ex situ addition of titanium can include a) combining in a reaction mixture (i) a Ni-containing precursor, (ii) a Mo-containing precursor, (iii) a W-containing precursor, (iv) an optional organic compound-based component, and (vi) a protic liquid; (b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor; and (c) composite the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor. The reaction mixture can be obtained by (1) preparing a first mixture containing the Ni-containing precursor, a protic liquid, and an optional organic compound-based component; (2) preparing a second mixture containing the Mo-containing precursor, the 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) combining the first and second mixtures together. After the reaction step, if desired, the resulting intermediate bulk catalyst may be separated from the liquid, for example by filtration or spray drying.

[0036] The temperature at which the catalyst precursor is formed may range from 60°C to 150°C. When the temperature is lower than the boiling point of the protic liquid (e.g., 100°C for water), the process is generally carried out at atmospheric pressure. The reaction can also be carried out under hydrothermal conditions where the reaction temperature is higher than the boiling point of the protic liquid. Such conditions usually result in pressures above atmospheric pressure, so the reaction is preferably carried out in an autoclave, preferably under autogenous pressure, i.e., without the application of additional pressure. An autoclave is a pressure-resistant device designed to heat a liquid above its boiling point. In either embodiment, the bulk catalyst precursor formation process is carried out at one or more temperatures: (a) in the range of 50°C to 100°C at atmospheric pressure, or (b) above 100°C under autogenous pressure.

[0037] The reaction time is selected to be sufficiently long to drive the reaction to substantial completion under both atmospheric and hydrothermal reaction conditions. The reaction time may be very short (e.g., less than 1 hour for highly reactive reactants). Clearly, less reactive materials may require longer reaction times, perhaps as long as 24 hours. In some circumstances, the reaction time may vary inversely with temperature.

[0038] Generally, the reaction mixture is maintained at its natural pH during the reaction step. The pH may be maintained in the range of 0 to 12 (e.g., 3 to 9, or 5 to 8). Depending on the desired properties of the product, the pH may be altered to increase or decrease the rate of precipitation or cogelation.

[0039] The metal precursors may be added to the reaction mixture as a solution, a suspension, or a combination thereof. If soluble salts are added neat, they dissolve in the reaction mixture and then precipitate or cogel.

[0040] Representative examples of Mo-containing precursor compounds include molybdenum (di- and tri-)oxides, molybdic acid, alkali metal molybdates (e.g., sodium molybdate, potassium molybdate), ammonium molybdates (e.g., ammonium molybdate, ammonium dimolybdate, ammonium heptamolybdate), and heteropolymolybdates (e.g., silicomolybdic acid, phosphomolybdic acid).

[0041] Representative examples of W-containing precursor compounds include tungsten (di- and tri-)oxide, 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., tungstic silicate, tungstic phosphonate).

[0042] Representative examples of Ni-containing precursor compounds include nickel acetate, nickel acetylacetonate, nickel bromide, nickel carbonate, nickel hydroxycarbonate, nickel bicarbonate, nickel chloride, nickel nitrate, nickel phosphate, and nickel sulfate.

[0043] Any titanium-containing compound suitable for preparing bulk catalysts of the type described herein can be used as the Ti-containing precursor compound. The Ti-containing precursor can be tetravalent titanium (Ti 4+ )-containing compounds, trivalent titanium (Ti 3+ )-containing compounds, or combinations thereof.

[0044] Representative Ti-containing precursor compounds include TiO2 nanoparticles, colloidal TiO2, fumed TiO2, titanium hydroxide, organotitanium compounds, titanium halides, and water-soluble titanium salts.

[0045] The titanium dioxide nanoparticles may be any type of titanium dioxide. The titanium dioxide may have a high content of anatase and / or rutile. For example, the titanium dioxide may contain at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98 weight percent anatase and / or rutile, or even at least 99 weight percent anatase and / or rutile. In some embodiments, the titanium dioxide consists essentially of anatase and / or rutile. The titanium dioxide particles preferably have a median particle size (D50) of less than 100 nm (e.g., 3-50 nm). The titanium dioxide nanoparticles may be introduced into the composition as a sol prepared by dispersion in a dispersant, as a paste containing water or a solvent, or as a powder. Dispersants used in preparing the sol include water, alcohols (eg, methanol, ethanol, isopropanol, n-butanol, isobutanol), and ketones (eg, methyl ethyl ketone, methyl isobutyl ketone).

[0046] Representative organotitanium compounds include titanium alkoxides and titanium acyl compounds of the general structure Ti(OR)4, where each R is independently C1-C4 alkyl. Representative titanium alkoxides include titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, 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 organotitanium compounds characterized by the general formula Ti(OR')2(acac)2, where each R is independently C1-C4 alkyl and "acac" is acetylacetonate.

[0047] Titanium halides represented by the formula TiX4 or TiX3 (wherein X is chloro, bromo, iodo, or fluoro), or mixtures thereof, can be used as the titanium precursor. In one embodiment, the titanium halide is titanium tetrachloride, titanium tetrabromide, or a combination thereof.

[0048] The present disclosure also contemplates the use of organotitanium halides, such as chlorotitanium triisopropoxide [Ti(Oi-Pr)3Cl], as Ti-containing precursor compounds.

[0049] Representative water-soluble titanium salts include titanium nitrate and titanium sulfate.

[0050] The organic compound-based component may be an organic compound suitable for forming a metal-ligand complex in solution, and may be selected from an organic acid or a salt thereof, a sugar, a sugar alcohol, or a combination thereof.

[0051] Representative organic acids include 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, and ethylenediaminetetraacetic acid.

[0052] Representative sugars include fructose, glucose, galactose, mannose, sucrose, lactose, maltose, etc., and derivatives thereof.

[0053] Representative sugar alcohols include erythritol, xylitol, mannitol, sorbitol, and the like, and derivatives thereof.

[0054] The protic liquid may 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 an alcohol.

[0055] Further processing Before being used in a hydrotreating process, the bulk catalyst precursor may be subjected to one or more of the following process steps: (i) composite with a material selected from the group consisting of a binder, a conventional hydrotreating catalyst, a cracking compound, or a mixture thereof; (ii) spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing, or a combination thereof; (iii) shaping; (iv) drying and / or heat treating; and (v) sulfiding. The listing of these process steps (i) through (v) is for convenience only and does not imply that the processes are constrained to be performed in this order. These process steps are described in further detail below.

[0056] Further processing step (i) - Combining with further materials If necessary, additional materials selected from the group consisting of binders, conventional hydrotreating catalysts, cracking compounds, or mixtures thereof may be added to the bulk catalyst precursor during or after the preparation of the bulk catalyst precursor. The materials are preferably added after the preparation of the bulk catalyst precursor and before spray drying or an alternative technique, or before shaping if spray drying or an alternative technique is not used. Optionally, the bulk metal precursor prepared as described above may be subjected to solid-liquid separation before being composited with the material. A washing step may be optionally included after the solid-liquid separation. Furthermore, the bulk catalyst particles may be heat-treated after the optional solid-liquid separation and drying step and before being composited with the material.

[0057] In all the above process alternatives, the expression "composite the bulk catalyst precursor with a material" means that the material is added to bulk metal particles, or vice versa, and the resulting composition is mixed. Mixing is preferably carried out in the presence of a liquid ("wet mixing"), which improves the mechanical strength of the final bulk catalyst composition.

[0058] Composites of the bulk catalyst precursor with the additional materials and / or incorporation of the materials during preparation of the catalyst precursor result in particularly high mechanical strength for the bulk catalyst, 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) but not more than 5000 μm (e.g., not more than 1000 μm, not more than 500 μm, not more than 150 μm). The median particle size of the catalyst precursor can be in the range of 1 to 150 μm (e.g., 2 to 150 μm).

[0059] The composite of the bulk metal particles with the material results in the bulk metal particles being embedded in the material, or vice versa, and typically the morphology of the bulk metal particles is essentially maintained in the resulting bulk catalyst composition.

[0060] The binder used may be any material conventionally used as a binder in hydrotreating 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 may be used as is or after peptization.

[0061] When alumina is used as a binder, the surface area of ​​the alumina is 50 to 600 m as measured by the BET method. 2 / g (e.g., 100 to 450 m 2 The pore volume of the alumina may be in the range of 0.1 to 1.5 cm3 as measured by nitrogen adsorption. 3 / g.

[0062] Typically, the added binder has less catalytic activity than the bulk metal particles, or no catalytic activity at all. Depending on the intended catalytic application, binder amounts of 0 to 40 wt. % of the total composition may be suitable. However, to take advantage of the resulting high activity of the bulk metal particles of the present disclosure, the amount of added binder generally ranges from 0.1 to 30 wt. % (e.g., 1 to 20 wt. %, 3 to 20 wt. %, or 4 to 12 wt. %) of the total composition.

[0063] Further process steps (ii) - spray drying, (flash) drying, grinding, kneading, slurry mixing, dry or wet mixing The bulk catalyst precursor, optionally comprising any of the above (additional) materials, may be subjected to spray drying, (flash) drying, grinding, kneading, slurry mixing, dry or wet mixing, or a combination thereof, preferably to a combination of wet mixing and kneading or slurry mixing and spray drying.

[0064] These techniques can be utilized before or after any of the above (additional) materials are added (if added), after solid-liquid separation, before or after heat treatment, and after rewetting.

[0065] Preferably, the catalyst precursor is composited with any of the above materials and subjected to any of the above techniques. It is believed that the use of any of the above techniques, including spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing, or a combination thereof, improves the degree of mixing between the catalyst precursor particles and any of the above materials. This is applicable when the materials are added before as well as after any of the above methods. However, it is generally preferred that the materials are added before step (ii). When the materials are added after step (ii), the resulting composition can be thoroughly mixed by any conventional technique before any further process steps, such as forming. An advantage of spray drying is that no wastewater stream is generated when this technique is used.

[0066] Spray drying can be carried out at an outlet temperature in the range of 100°C to 200°C (eg, 120°C to 180°C).

[0067] Dry mixing refers to mixing the catalyst precursor particles in a dry state with any of the above materials in a dry state, while wet mixing generally involves mixing a wet filter cake containing the catalyst precursor particles with any of the above materials, optionally as a powder or wet filter cake, to form a homogeneous paste thereof.

[0068] Further process steps (iii) - molding If necessary, the bulk catalyst precursor containing any of the above (additional) materials may be optionally shaped after step (ii). Shaping methods include extrusion, pelletizing, beading, and / or spray drying. It should be noted that spray drying or beading is typically used when the bulk catalyst composition is to be used in a slurry reactor, a fluidized bed, a moving bed, or an expanded bed. For fixed-bed or ebullated-bed applications, the bulk catalyst composition is typically extruded, pelletized, and / or beaded. In the latter case, any additives conventionally used to facilitate shaping may be added at any stage before or during the shaping step. 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 shaping step to peptize the alumina and increase the mechanical strength of the extrudate.

[0069] When forming involves extrusion, beading, and / or spray drying, the forming step is preferably carried out in the presence of a liquid such as water. For extrusion and / or beading, the amount of liquid in the forming mixture, expressed as loss on ignition, may range from 20% to 80%.

[0070] Further process steps (iv) - drying and / or heat treatment After an optional drying step, preferably above 100°C, the resulting shaped bulk catalyst composition may be heat-treated if desired, although heat treatment is not required for the process of the present disclosure. "Heat treatment" in the context of the present disclosure refers to treatment carried out in an inert gas, such as nitrogen, or in an oxygen-containing gas, such as air or pure oxygen, at a temperature of 100°C to 200°C for a time period varying from 0.5 to 48 hours. The heat treatment may be carried out in the presence of water vapor.

[0071] In all the above process steps, the amount of liquid needs to be controlled. If the amount of liquid is too low before the bulk catalyst composition is subjected to spray drying, additional liquid needs to be added. Conversely, if the amount of liquid is too high before the bulk catalyst composition is extruded, the amount of liquid needs to be reduced using solid-liquid separation techniques such as filtration, decantation, or evaporation, and the resulting material should be dried, if necessary, and then re-wetted to some extent. It is within the skill of the art to appropriately control the amount of liquid in all the above process steps.

[0072] Further process step (v) - sulfurization The above-mentioned quaternary metallic bulk catalysts are generally used in their sulfided form. The sulfidation of the catalyst can be carried out by any method effective to convert the catalyst to the sulfided form, including conventional sulfidation methods. The 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 the preparation of the precursor or after any one of the further process steps (i) to (iv). The sulfidation step can be carried out in the liquid phase and the gas phase.

[0073] The sulfiding can generally be carried out in situ and / or ex situ, and is preferably carried out in situ (i.e., the sulfiding is carried out in a hydrotreating reactor after the bulk catalyst precursor composition has been loaded into the hydrotreating unit).

[0074] Use in hydroprocessing The bulk catalyst precursors of the present disclosure are particularly useful for hydroprocessing hydrocarbon feedstocks, including processes such as hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrogenolysis, hydrotreating, hydroisomerization, and hydrocracking.

[0075] A wide range of petroleum and chemical hydrocarbon feedstocks can be hydroprocessed according to the present disclosure. Hydrocarbon feedstocks include those obtained or derived from crude oil, tar sands, coal liquids, and shale oil, including atmospheric resids, hydrocracked oils, raffinates, hydrotreated oils, atmospheric and vacuum gas oils, coker gas oils, atmospheric and vacuum resids, deasphalted oils, dewaxed oils, slack wax, Fischer-Tropsch wax, biorenewable feedstocks, and mixtures thereof. Suitable feedstocks range from relatively light distillate fractions, such as diesel, lubricating oil, and residual oils, to heavier feedstocks. Examples of light distillate feedstocks include naphtha (typical boiling range: about 25°C to about 210°C), diesel (typical boiling range: about 150°C to about 400°C), kerosene, or jet fuel (typical boiling range: about 150°C to about 250°C), and the like. Examples of heavy feedstocks include vacuum (or heavy) gas oils (typical boiling range of about 315°C to about 610°C), raffinates, lube 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).

[0076] The hydrotreating conditions are: temperature of 200°C to 450°C or 315°C to 425°C, pressure of 250 to 5000 psig (1.7 to 34.6 MPa) or 300 to 3000 psig (2.1 to 20.7 MPa), and time of 0.1 to 10 hours. -1 , or 0.5 to 5 hours -1 Liquid hourly space velocity (LHSV) and 100-15,000 SCF / B (17.8-2672 m 3 / m 3 ), or 500-10,000 SCF / B (89-1781 m 3 / m 3 ) hydrogen gas velocity can be mentioned.

[0077] Hydroprocessing according to the present 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. The fixed-bed reactor may contain one or more vessels, single or multiple beds of catalyst in each vessel, and various combinations of hydroprocessing catalysts in the one or more vessels.

[0078] example The following illustrative examples are intended to be non-limiting.

[0079] Example 1 (Comparative Example) Bulk Catalyst Precursors [Ni(2)-Mo(1)-W(1)] Synthesis of Preparation of Solution A: In a 4 L flask, 70.6 g of ammonium heptamolybdate and 102.0 g of ammonium metatungstate hydrate were added to 2000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0080] Preparation of Solution B: In a separate 500 mL beaker, 232.6 g of nickel nitrate and 13.9 g of maleic acid were dissolved in 100 g of deionized water.

[0081] Solution B was added to solution A at a rate of 10 mL / min. The pH was monitored during the addition. A green precipitate formed immediately upon addition of solution B. The final pH after addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours.

[0082] The slurry was filtered to recover the wet cake, which was washed with 300 g of deionized water to remove the ammonium nitrate by-product, and then dried in an oven at 130° C. to remove all moisture.

[0083] Example 2 (Comparative Example) Bulk Catalyst Precursors [Ni-Mo-W-Co] Synthesis of Preparation of Solution A: In a 4 L flask, 45.0 g of ammonium heptamolybdate and 58.0 g of ammonium metatungstate were added to 2500 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0084] Solution B preparation: In a separate 500 mL beaker, 140.0 g of nickel nitrate, 140.0 g of cobalt nitrate, and 16.0 g of maleic acid were dissolved in 125 g of deionized water.

[0085] Solution B was added to solution A at a rate of 10 mL / min. The pH was monitored during the addition. A green precipitate formed immediately upon addition of solution B. The final pH after addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours.

[0086] The slurry was filtered to recover the wet cake, which was washed with 300 g of deionized water to remove the ammonium nitrate by-product, and then dried in an oven at 130° C. to remove all moisture.

[0087] Example 3 Ex-situ addition of Ti Bulk Catalyst Precursors [Ni-Mo-W-Ti] Synthesis of Preparation of Solution A: In a 4 L flask, 10.4 g of ammonium heptamolybdate and 44.8 g of ammonium metatungstate were added to 1000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0088] Preparation of Solution B: In a separate 500 mL beaker, 128.5 g of nickel nitrate and 7.1 g of maleic acid were dissolved in 100 g of deionized water.

[0089] Solution B was added to solution A at a rate of 10 mL / min. The pH was monitored during the addition. A green precipitate formed immediately upon addition of solution B. The final pH after addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours.

[0090] The slurry was filtered to recover the wet cake. The wet cake was washed with 300 g of deionized water to remove the ammonium nitrate by-product. The wet cake was transferred to a beaker and heated at 60°C with stirring. Next, 100 g of hydrophilic fumed TiO2 (AEROXIDE® TiO2 P25, Evonik) was mixed into the wet cake until the mixture was uniform. The wet cake was dried at 130°C to remove all moisture.

[0091] Example 4 In-situ addition of Ti Bulk Catalyst Precursors [Ni-Mo-W-Ti] Synthesis of Preparation of Solution A: In a 4 L flask, 10.4 g of ammonium heptamolybdate and 44.8 g of ammonium metatungstate were added to 1000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia. The solution was then heated to 80°C.

[0092] Preparation of Gel C: In a 500 mL beaker, 128.3 g of nickel nitrate was dissolved in 210 g of ethylene glycol. In a separate 1 L beaker, 116.1 g of titanium tetra-n-butoxide [Ti(OBu)4] was mixed with 1200 g of ethylene glycol. This Ti(OBu)4 / ethylene glycol solution was added to the nickel nitrate / ethylene glycol solution at a rate of 5 mL / min. Gel C was aged at 80 °C for 2 hours.

[0093] Gel C was then added to Solution A at a rate of 10 mL / min. The pH was monitored during the addition. A green precipitate formed immediately after the addition of Gel C. The final pH after the addition was 6.0-7.0. The slurry was aged at 80°C for 4 hours.

[0094] The slurry was filtered to recover the wet cake, which was washed with 300 g of deionized water to remove the ammonium nitrate by-product and ethylene glycol, and dried at 130° C. to remove all moisture.

[0095] Figure 3 shows the isotherm plot of N2 physisorption performed on the catalyst precursor at 77 K. Figure 3 shows that the material has B-type slit-shaped pores.

[0096] Figure 4 shows the HAADF-STEM image obtained for this catalyst precursor, which shows that all four metal oxides are uniformly distributed; no TiO2 islands are observed.

[0097] Example 5 In-situ addition of Ti Bulk Catalyst Precursors [Ni-Mo-W-Ti] Synthesis of Example 4 was repeated except that 766.1 g of titanium tetra-n-butoxide was used.

[0098] Figure 5 shows the isotherm plot of N2 physisorption performed on the above catalyst precursor at 77 K. Figure 5 shows that the material has B-type slit-shaped pores.

[0099] Example 6 Manufacturing of extruded products Prior to catalytic evaluation, the catalyst precursor was formed into extrudates: the dried catalyst precursor was ground to a fine powder (<100 mesh) and mixed with an appropriate amount of binder and water to form an extrudable mixture, which was then extruded in a Carver press.

[0100] Example 7 Characterization of bulk catalyst precursors The particle density (D), BET surface area (SA), and pore volume (PV) were measured for the bulk catalyst precursors of Examples 1 to 5. The results are shown in Table 1 below. Table 1 shows that the addition of TiO2 can increase the pore volume and reduce the particle density. [Table 1]

[0101] Example 8 Catalyst evaluation - hydrogenolysis of tetralin The tetralin hydrogenolysis activity of the catalyst precursor extrudates from Examples 1 and 3-4 was tested in a fixed-bed reactor. All catalyst precursors were presulfided using tetralin spiked with 300 wppm sulfur in the form of dimethyl disulfide. The catalyst precursors were sulfided using the spiked tetralin feed at 450°F and 800 psig H pressure for 24 hours, then ramped to 650°F at 25°F / hour and held at 650°F / 800 psig for 10 hours.

[0102] The catalyst was subjected to a total reactor pressure of 2300 psig, a hydrogen feed rate of 8000 SCF / B, and 1 h -1 The tetralin feedstock contained 300 wppm sulfur.

[0103] Table 2 shows the hydrocracking performance of each catalyst. [Table 2]

[0104] The above results show that the activity of the bulk catalyst of Example 3 is comparable to that of the conventional bulk catalyst of Example 1, but the amount of active metals (i.e., Ni, Mo, and W) in the bulk catalyst of Example 3 is lower. The activity of the bulk catalyst of Example 4 is significantly higher than that of the bulk catalysts of Examples 1 and 3 at higher temperatures. Without being bound by any theory, it is believed that the in situ route of introducing TiO2 results in a higher dispersion of the metals, significantly increasing the acidity of the catalyst. The TiO2 control catalyst itself does not have sufficient activity to cause ring-opening in any substantial amount.

[0105] Example 9 (Comparative Example) Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)] Synthesis of 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, and the solution was heated to 80°C.

[0106] Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0107] Solution B was added to solution A within 15 minutes. A green precipitate formed during the addition of solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration, washed with deionized water, and dried at 130°C.

[0108] Example 10 (Comparative Example) Bulk Catalyst Precursors [Ni(7.5)-Mo(1)-W(3)] Synthesis of Example 9 was repeated, except that the following reagents were used in the amounts shown in parentheses: ammonium heptamolybdate (10.4 g), ammonium metatungstate (44.8 g), maleic acid (5.8 g), and nickel nitrate (128.3 g).

[0109] Example 11 (Comparative Example) Bulk Catalyst Precursors [Ni(3.8)-Mo(1)-W(1.1)] Synthesis of Example 9 was repeated, except that the following reagents were used in the amounts shown in parentheses: ammonium molybdate (17.6 g), ammonium heptamolybdate (27.8 g), maleic acid (5.8 g), and nickel nitrate (110.3 g).

[0110] Example 12 In-situ addition of Ti Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] Synthesis of Preparation of Slurry A: In a 4 L flask, 45 g of ammonium heptamolybdate, 72 g of ammonium metatungstate, and 56 g of TiO (Venator Hombikat 8602) were added to 2000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80 °C.

[0111] Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0112] Solution B was added to Slurry A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration, washed with deionized water, and dried at 130°C.

[0113] Example 13 Ex-situ addition of Ti Bulk Catalyst Precursors Synthesis of [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] 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, and the solution was heated to 80°C.

[0114] Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0115] Solution B was added to solution A within 15 minutes. A green precipitate formed during the addition of solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration. The filter cake and 56 g of TiO2 (Venator Hombikat 8602) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was recovered by filtration, washed with deionized water, and dried at 130°C.

[0116] Example 14 Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] Synthesis of Example 12 was repeated except that Venator Hombikat ADW-1 TiO2 was used as the TiO2 source.

[0117] Example 15 Ex-situ addition of Ti Bulk Catalyst Precursors [Ni(6.6)-Mo(1)-W(3)-Ti(9.8)] Synthesis of Preparation of Solution A: In a 4 L flask, 32 g of ammonium heptamolybdate and 139.4 g of ammonium metatungstate were added to 2000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0118] Preparation of Solution B: 354.7 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0119] Solution B was added to Solution A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration. The filter cake and 56 g of TiO2 (Evonik AEROXIDE® E0167) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was recovered by filtration, washed with deionized water, and dried at 130°C.

[0120] Example 16 Bulk Catalyst Precursors Synthesis of [Ni(6.6)-Mo(1)-W(3)-Ti(5)] Example 14 was repeated except that 93.1 g of TiO2 (Evonik AEROXIDE® E0167) was used.

[0121] Example 17 Bulk Catalyst Precursors [Ni(6.6)-Mo(1)-W(3)-Ti(2.5)] Synthesis of Example 14 was repeated except that 46.6 g of TiO2 (Evonik AEROXIDE® E0167) was used.

[0122] Example 18 In-situ addition of Ti compounds Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(3)] Synthesis of 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, and the solution was heated to 80°C.

[0123] Preparation of Gel C: 184.3 g of nickel nitrate was dissolved in 210 g of ethylene glycol. In a separate 1 L beaker, 321.6 g of Ti(OBu)4 was mixed in 1200 g of ethylene glycol. This Ti(OBu)4 mixture was then added to the nickel nitrate mixture at a rate of 5 mL / min with vigorous mixing. The resulting gel was aged at 80°C for 2 hours.

[0124] Gel C was added to Solution A within 15 minutes. A green precipitate formed during the addition of Gel C. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration, washed with deionized water, and dried at 130°C.

[0125] Example 19 Bulk Catalyst Precursors [Ni(7.5)-Mo(1)-W(3)-Ti(3.8)] Synthesis of Example 16 was repeated except that 128.3 g of nickel nitrate was dissolved in 210 g of ethylene glycol and 76.1 g of Ti(OBu)4 was mixed with 230 g of ethylene glycol.

[0126] Example 20 Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] Synthesis of Example 12 was repeated, except that anatase nanopowder (99.5% 5 nm) from US Research Nanomaterials, Inc. was used as the TiO2 source.

[0127] Example 21 Ex-situ addition of Ti Bulk Catalyst Precursors [Ni(7.5)-Mo(1)-W(3)-Ti(21.2)] Synthesis of Preparation of Solution A: In a 4 L flask, 10.4 g of ammonium heptamolybdate and 44.8 g of ammonium metatungstate were added to 1000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0128] Preparation of Solution B: 128.5 g of nickel nitrate and 7.1 g of maleic acid were dissolved in 100 g of deionized water.

[0129] Solution B was added to Solution A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration. The filter cake and 100 g of hydrophilic fumed TiO2 (Evonik AEROXIDE® P25) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was collected by filtration, washed with deionized water, and dried at 130°C.

[0130] Example 22 Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] Synthesis of Example 12 was repeated except that Venator Hombikat S141 was used as the TiO2 source.

[0131] Example 23 Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(6.2)] Synthesis of Example 12 was repeated except that Venator S141 was used as the TiO2 source in an amount of 128 g.

[0132] Example 24 In-situ addition of Ti Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Ti(2.7)] Synthesis of Preparation of Slurry A: In a 4 L flask, 56 g of ammonium heptamolybdate, 90 g of ammonium metatungstate, and 467 g of colloidal TiO (15 wt% TiO solids, Cerion Nanomaterials) were added to 2000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80 °C.

[0133] Preparation of Solution B: 230 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0134] Solution B was added to Slurry A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration, washed with deionized water, and dried at 130°C.

[0135] Example 25 (Comparative Example) Ex-situ addition of silicon Bulk Catalyst Precursors [Ni(7.5)-Mo(1)-W(3)-Si(2)] Synthesis of Preparation of Solution A: In a 4 L flask, 10.4 g of ammonium heptamolybdate and 44.8 g of ammonium tungstate were added to 1000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0136] Preparation of Solution B: 128.5 g of nickel nitrate and 7.1 g of maleic acid were dissolved in 100 g of deionized water.

[0137] Solution B was added to Solution A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration. The filter cake and 8.9 g of tetraethyl orthosilicate (TEOS) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was collected by filtration, washed with deionized water, and dried at 130°C.

[0138] Example 26 (Comparative Example) Ex-situ addition of silicon Bulk Catalyst Precursors [Ni(6.6)-Mo(1)-W(3)-Si(6.6)] Preparation of Solution A: In a 4 L flask, 32.4 g of ammonium heptamolybdate and 139.4 g of ammonium tungstate were added to 2000 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0139] Preparation of Solution B: 354.7 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0140] Solution B was added to Solution A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration. The filter cake and 91 g of silica gel (Davisil Grade 636) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was recovered by filtration, washed with deionized water, and dried at 130°C.

[0141] Example 27 (Comparative Example) Bulk Catalyst Precursors [Ni(6.6)-Mo(1)-W(3)-Si(2.9)] Synthesis of Example 27 was repeated except that 39 g of the above silica gel was used.

[0142] Example 28 (Comparative Example) Ex-situ addition of zirconium Bulk Catalyst Precursors [Ni(2.5)-Mo(1)-W(1.1)-Zr(1.8)] Synthesis of Preparation of Solution A: 45 g of ammonium heptamolybdate and 72 g of ammonium tungstate were added to 2000 g of deionized water in a 4 L flask. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0143] Preparation of Solution B: 184.5 g of nickel nitrate and 10.1 g of maleic acid were dissolved in 100 g of deionized water.

[0144] Solution B was added to solution A within 15 minutes. A green precipitate formed during the addition of solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was recovered by filtration. The filter cake and 56 g of calcined ZrO2 (Aldrich) were mixed until homogeneous and stirred at 80°C for 2 hours. The mixture was recovered by filtration, washed with deionized water, and dried at 130°C.

[0145] Example 29 (Comparative Example) Ex-situ addition of carbon Bulk Catalyst Precursors [Ni(6.6)-Mo(1)-W(3)-C(14.5)] Example 27 was repeated except that 39 g of activated carbon (DARCO® G-60) was used instead of the silica gel.

[0146] Example 30 Catalyst Evaluation - Vacuum Gas Oil Hydroconversion Bulk catalyst precursor extrudates from Examples 9-11, 15-17, and 25-29 were sulfided and their catalytic activity was evaluated using VGO feed in a three-phase fixed bed reactor.

[0147] The catalyst precursor was sulfided at 482°F / 800 psig (250°C / 5.5 MPa) for 5 hours, then ramped at 30°F / hour to 572°F (300°C) for a 5 hour soak, then ramped at 30°F / hour to 650°F / 800 psig (343°C / 5.5 MPa) for a 6 hour soak.

[0148] Hydrotreating conditions included a pressure of 2300 psig and 2 hours -1 The LHSV included 4000 SCF / B and an H2 treat gas rate of 4880 SCF / B.

[0149] The catalytic activity was measured at a particle density of 2.5 g / cm 3 The results are summarized in Table 3. [Table 3]

[0150] The results in Table 3 show that the addition of various amounts of TiO2 reduces particle density without sacrificing activity, while the temperature required to achieve the HDN target remains the same as for the Ni-Mo-W catalyst. In comparison, the addition of SiO2, ZrO2, and C also reduces particle density but at the expense of activity.

[0151] Example 31 Catalyst evaluation - hydrogenolysis of tetralin The tetralin hydrogenolysis activity of the Ni-Mo-W bulk catalyst precursors of Examples 10-11 and the Ni-Mo-W-Ti bulk catalyst precursors of Examples 14, 18, and 20-24 was tested in a three-phase fixed-bed reactor as described in Example 9.

[0152] The catalyst evaluation conditions were a reactor pressure of 2300 psig, a hydrogen feed rate of 3500 SCF / B, and 1 h -1 The tetralin feedstock contained 300 wppm sulfur.

[0153] Table 4 summarizes the ring-opening activity of the above catalysts. [Table 4]

[0154] The results in Table 4 show that TiO2 alone without Ni-Mo-W is inactive for ring-opening of tetralin. The Ni-Mo-W-Ti system has varying levels of activity depending on the type and preparation of TiO2. Selection of TiO2 type and preparation may offer advantages in both low particle density and improved ring-opening activity.

[0155] Example 32 Catalyst Testing - Hydroconversion of Straight-Run Gas Oil / Tetralin Feedstock The catalytic activities of the Ni-Mo-W bulk catalyst precursors of Examples 9-11 and the Ni-Mo-W-Ti bulk catalyst precursors of Examples 14, 18, and 22-23 were tested in a fixed-bed reactor using a 30% by volume straight-run gas oil / 70% by volume tetralin blend feedstock. The catalytic activities were compared based on the conversion of polynuclear aromatic compounds (PNAs).

[0156] The catalyst precursor was sulfided as described in Example 8.

[0157] Hydrotreating conditions were 1200 psig pressure, 1 hour -1 and H2 gas rate of 3500 SCF / B.

[0158] Table 5 summarizes the ring-opening activity of the above catalysts. [Table 5]

[0159] The results in Table 5 show that the activity of the Ni-Mo-W-Ti system for hydroconversion of straight-run gas oil / tetralin feedstock is equivalent to that of the Ni-Mo-W system.

[0160] Example 33 (Comparative Example) Trimetallic bulk catalyst precursors [Ni(1.25)-Mo(1)-Ti(1.12)] Synthesis of Preparation of Slurry A: In a 4 L flask, 112 g of ammonium heptamolybdate and 57 g of TiO (Venator S141) were added to 3200 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0161] Preparation of Solution B: 230 g of nickel nitrate and 12.6 g of maleic acid were dissolved in 100 g of deionized water.

[0162] Solution B was added to Slurry A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration, washed with deionized water, and dried at 130°C.

[0163] Example 34 (Comparative Example) Trimetallic bulk catalyst precursors [Ni(1.1)-W(1)-Ti(1.37)] Synthesis of Preparation of Slurry A: In a 4 L flask, 182.7 g of ammonium metatungstate and 79 g of TiO (Venator S141) were added to 3200 g of deionized water. The pH was adjusted to 9.8 with aqueous ammonia, and the solution was heated to 80°C.

[0164] Preparation of Solution B: 230 g of nickel nitrate and 12.6 g of maleic acid were dissolved in 100 g of deionized water.

[0165] Solution B was added to Slurry A within 15 minutes. A green precipitate formed during the addition of Solution B. The final pH was 6.0-7.0. The slurry was aged at 80°C for 4 hours with stirring. After aging, the product was collected by filtration, washed with deionized water, and dried at 130°C.

Claims

1. (a) 1 to 60 wt % Ni in terms of metal oxide; (b) 1 to 40 wt % of Mo in terms of metal oxide; (c) 5 to 80 wt % W in terms of metal oxide; (d) 2 to 45 wt % of Ti in terms of metal oxide; A bulk catalyst precursor comprising:

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

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

4. 3. The bulk catalyst precursor of claim 2, wherein the organic compound-based component 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. 3. The bulk catalyst precursor of 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. 2. The bulk catalyst precursor of claim 1, wherein the molar ratio of Ti / (Ni+Mo+W) ranges from 10:1 to 1:

10.

7. 2. The bulk catalyst precursor of claim 1, wherein the molar ratio of Ni / W ranges from 10:1 to 1:

10.

8. 2. The bulk catalyst precursor of claim 1, wherein the molar ratio of W / Mo ranges from 100:1 to 1:

100.

9. formula: A ｖ [N](PH) ｘ (L) ｐ ｙ ] ｚ [M / ｍ W １－ｍ Oh ４ ][Ti(OH) ｎ Oh 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) 0≦y≦2 / p, 0≦x<2, 0≦v<2, 0<z, 0<m<1, 0<n<4, 0.1<w / (z+1)<10.

2. The bulk catalyst precursor of claim 1, wherein the bulk catalyst precursor is

10. It is defined by the region of the quaternary phase diagram, However, the region is defined by ten points ABCDEFGHIJ, However, the 10 points are expressed as follows in terms of metal oxide (wt%): A (Ni=0.39, Mo=0.00, W=0.41, Ti=0.2), B (Ni=0.08, Mo=0.00, W=0.72, Ti=0.2), C (Ni=0.09, Mo=0.17, W=0.54, Ti=0.2), D (Ni=0.31, Mo=0.25, W=0.24, Ti=0.2), E (Ni=0.40, Mo=0.14, W=0.26, Ti=0.2), F (Ni=0.34, Mo=0.00, W=0.36, Ti=0.3), G (Ni=0.07, Mo=0.00, W=0.63, Ti=0.3), H (Ni=0.08, Mo=0.15, W=0.48, Ti=0.3), I (Ni = 0.27, Mo = 0.22, W = 0.21, Ti = 0.3), and J (Ni=0.35, Mo=0.12, W=0.23, Ti=0.3) 2. The bulk catalyst precursor of claim 1, wherein:

11. The phase diagram is defined by a region of a quaternary phase diagram defined by eight points ABCDEFGH, where the eight points are, in terms of metal oxide (wt%): A (Ni=52.5, Mo=3.5, W=14, Ti=30), B (Ni=38.5, Mo=17.5, W=14, Ti=30), C (Ni=21, Mo=17.5, W=31.5, Ti=30), D (Ni=35, Mo=3.5, W=31.5, Ti=30), E (Ni=60, Mo=4, W=16, Ti=20), F (Ni=44, Mo=20, W=16, Ti=20), G (Ni=24, Mo=20, W=36, Ti=20), and H (Ni=40, Mo=4, W=36, Ti=20) 2. The bulk catalyst precursor of claim 1, wherein:

12. 10. The bulk catalyst precursor of claim 1, further comprising 1 to 15 wt. % of a binder.

13. The following properties: 50 to 250 m ２ / g BET specific surface area, 0.02~0.80cm ３ / g pore volume, 1.00~3.00cm ３ / g particle density, 10. The bulk catalyst precursor of claim 1, having one or more of:

14. A sulfided bulk catalyst, characterized in that it is the sulfided bulk catalyst precursor of claim 1.

15. 10. A method for preparing the bulk catalyst precursor of claim 1, comprising: (a) in the reaction mixture: (i) a Ni-containing precursor; (ii) Mo-containing precursors; (iii) a W-containing precursor; (iv) a Ti-containing precursor; (v) optionally, an organic compound-based component, and (vi) protic liquid and (b) reacting the mixture under conditions sufficient to cause precipitation of the bulk catalyst precursor; Including, The method of preparing the bulk catalyst precursor, wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200° C. or less.

16. Preparing a first mixture comprising a Ni-containing precursor, a protic liquid, and optionally an organic compound-based component; preparing a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid; adding a Ti-containing precursor to the first mixture, the second mixture, or a combination thereof; heating both the first mixture and the second mixture to a temperature of from 60°C to 150°C; blending the first mixture and the second mixture together; 16. The method of claim 15, wherein the reaction mixture is prepared by:

17. The Ti-containing precursor is TiO ２ Nanoparticles, colloidal TiO ２ , fumed TiO ２ 17. The method of claim 16, wherein the titanium compound is selected from titanium hydroxide, an organotitanium compound, a titanium halide, an organotitanium halide, a water-soluble titanium salt, or a combination thereof.

18. 10. A method for preparing the bulk catalyst precursor of claim 1, comprising: (a) in the reaction mixture: (i) a Ni-containing precursor; (ii) Mo-containing precursors; (iii) a W-containing precursor; (iv) optionally, an organic compound-based component, and (v) protic liquid and (b) reacting the mixture under conditions sufficient to cause precipitation of an intermediate bulk catalyst precursor; (c) composite the intermediate bulk catalyst precursor with a Ti-containing precursor to form the bulk catalyst precursor; Including, The method of preparing the bulk catalyst precursor, wherein the step of preparing the bulk catalyst precursor is carried out at a temperature of 200° C. or less.

19. the reaction mixture Preparing a first mixture comprising a Ni-containing precursor, a protic liquid, and optionally an organic compound-based component; preparing a second mixture comprising a Mo-containing precursor, a W-containing precursor, and a protic liquid; heating both the first mixture and the second mixture to a temperature of from 60°C to 150°C; blending the first mixture and the second mixture together; 20. The method of claim 18, wherein the reaction mixture is prepared by:

20. The Ti-containing precursor is TiO ２ Nanoparticles, fumed TiO ２ 19. The method of claim 18, wherein the compound is selected from the group consisting of:

21. The method of claim 18, wherein the intermediate bulk catalyst precursor is a Ni—Mo—W bulk catalyst precursor.

22. The reacting (a) in the range of 60°C to 100°C at atmospheric pressure, or (b) above 100°C under autogenous pressure 19. The method of claim 15 or claim 18, wherein the method is carried out at one or more temperatures of any one of

23. 19. The method of claim 15 or claim 18, wherein the organic compound-based component is selected from an organic acid or a salt thereof, a sugar, a sugar alcohol, or a combination thereof.

24. 24. The method of claim 23, wherein the organic compound-based component is selected from 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 a combination thereof.

25. The following steps: composite the bulk catalyst precursor with 0 to 40 wt. % of a material selected from the group of a binder, a conventional hydroprocessing catalyst, a cracking compound, or a mixture thereof; spray drying, (flash) drying, milling, kneading, slurry mixing, dry or wet mixing, or combinations thereof; a molding step; drying and / or heat treating at a temperature of not more than 200°C; or Sulfurization step 19. The method of claim 15 or claim 18, further comprising one or more of:

26. 1. A method for hydrotreating a hydrocarbon feedstock, comprising contacting said hydrocarbon feedstock with hydrogen in the presence of a bulk catalyst under hydrotreating conditions to obtain at least one product; The bulk catalyst is (a) 1 to 60 wt % Ni in terms of metal oxide; (b) 1 to 40 wt % of Mo in terms of metal oxide; (c) 5 to 80 wt % W in terms of metal oxide; (d) 2 to 45 wt % of Ti in terms of metal oxide; The process is derived or derivable from a bulk catalyst precursor comprising:

27. 27. The method of claim 26, wherein the hydrotreating is selected from the group consisting of hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization, hydrodearomatization, hydrogenation, hydrogenolysis, hydrofinishing, hydroisomerization, and hydrocracking.

28. The hydrotreating conditions are a temperature of 200°C to 450°C; a pressure of 250 to 5000 psig (1.7 to 34.6 MPa); 0.1 to 10 hours －１ and the liquid hourly space velocity of 100~15,000SCF / B (17.8~2672m ３ / m ３ ) hydrogen gas velocity and 27. The method of claim 26, comprising:

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