Method for preparing a hydrocracking catalyst

Abstract

The present invention provides a method for preparing a supported catalyst, preferably a hydrocracking catalyst, comprising at least the steps of: a) providing a zeolite Y having a bulk silica-to-alumina ratio (SAR) of at least 10; b) mixing the zeolite Y provided in step a) with a base, water, and a surfactant, thereby obtaining a slurry of zeolite Y; and c) reducing the water content of the slurry obtained in step b), thereby obtaining a solid having a reduced water content, wherein the reduction in water content in step c) is d) shaping the solid having reduced water content obtained in step c) to obtain a shaped catalyst support; e) calcining the shaped catalyst support obtained in step d) at a temperature above 300°C in the presence of the surfactant of step b) to obtain a calcined catalyst support; and f) impregnating the catalyst support calcined in step e) with a hydrogenation component to obtain a supported catalyst, wherein no heat treatment at a temperature above 500°C is performed between the mixing in step b) and the shaping in step d).

Description

[Technical Field]

[0001] The present invention relates to a method for preparing a supported catalyst, preferably a hydrocracking catalyst.

[0002] Various methods for preparing supported catalysts are known in the field of technology.

[0003] As an example, CN103769197A discloses a method for preparing a sulfurized hydrocracking catalyst.

[0004] As a further example, US20130292300A1 discloses mesostructured zeolites, methods for preparing catalyst compositions from such mesostructured zeolites, and the use of such catalyst compositions in a hydrocracking process. According to Examples 7 and 8 of US20130292300A1 (describes a small-scale experiment), the zeolite material was mixed with deionized water and CTAB (alkylammonium halide surfactant), followed by the addition of concentrated ammonium hydroxide (NH4OH). After stirring at room temperature for 24 hours, the solid was separated by vacuum filtration and washed three times with hot deionized water. The solid was then dried and subsequently calcined in two stages, first at 550°C (under nitrogen) and then at 600°C (under air). Next, this calcined material (see Example 8 of US20130292300A1) was combined with a binder material and impregnated with nickel oxide (NiO) and molybdenum trioxide (MoO3) to form several different hydrocracking catalysts.

[0005] The problem with the catalyst preparation method described in US20130292300A1, where surfactants are present in the zeolite material during combustion in air, is that when scaling up the catalyst preparation process to a commercial scale, considering the presence of surfactants, for example, due to their carbon content, combustion in air may pose an explosive risk. Furthermore, combustion under an inert gas such as nitrogen on a commercial scale is costly in terms of equipment investment. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Chinese Patent Application Publication No. 103769197 Specification [Patent Document 2] U.S. Patent Application Publication No. 2013 / 0292300 Specification [Overview of the Initiative]

[0007] The object of the present invention is to overcome or minimize one or more of the above or other problems.

[0008] A further object of the present invention is to provide an alternative method for preparing supported catalysts, particularly for use as hydrocracking catalysts.

[0009] One or more of the above or other objectives can be achieved by providing a method for preparing a supported catalyst, preferably a hydrocracking catalyst, which provides at least, a) A step of providing a zeolite Y having a bulk silica-to-alumina ratio (SAR) of at least 10, b) A step of mixing the zeolite Y provided in step a) with a base, water, and a surfactant to obtain a slurry of zeolite Y. c) A step of reducing the water content of the slurry obtained in step b), thereby obtaining a solid having the reduced water content, wherein the reduction in water content in step c) is accompanied by the addition of a binder. d) A step of molding the solid obtained in step c) having a reduced water content, thereby obtaining a molded catalyst support, e) The molded catalyst support obtained in step d) is calcined at a temperature exceeding 300°C in the presence of the surfactant from step b), thereby obtaining a calcined catalyst support. f) The process includes impregnating the catalyst support calcined in step e) with a hydrogenation component to obtain a supported catalyst, No heat treatment at temperatures exceeding 500°C is performed between the mixing in step b) and the molding in step d).

[0010] Surprisingly, according to the present invention (see, for example, Table 3), the explosion risk during air calcination is significantly reduced or completely eliminated, thereby improving the ease of manufacture (since the use of inert gases such as nitrogen during calcination is removed). Further, the calcination can be carried out in one step, resulting in a simplified process.

[0011] Another advantage of the present invention is that the supported catalyst prepared by the method according to the present invention provides a higher middle distillate (MD) selectivity (150 °C to 370 °C) when used in the hydroconversion of hydrocarbon feeds.

Brief Description of the Drawings

[0012] [Figure 1-1] It is a diagram showing the m / z = 44 signal indicating CO2 formation as a function of temperature (°C) and the m / z = 18 signal indicating H2O formation as a function of temperature (°C) in TGA MS measurement. [Figure 1-2] It is a diagram showing the mass change as a function of temperature (°C) and the first-order time derivative (δm / δt) of the mass change as a function of temperature (°C) in TGA MS measurement.

Mode for Carrying Out the Invention

[0013] In step a) of the method according to the present invention, zeolite Y having at least 10 bulk (molar) silica to alumina ratio (SAR) (determined by XRF (X-ray fluorescence)) is provided.

[0014] Those skilled in the art will readily understand that this zeolite Y (having a faujasite structure) can vary widely. It will also be possible to combine zeolite Y with different zeolites (for example, zeolite beta). However, the amount of zeolite Y used according to the present invention preferably constitutes at least 70% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, or even at least 95% by weight, and even at least 98% by weight of the total amount of zeolites.

[0015] Typically, the zeolite Y used in step a) according to the present invention has a unit cell size in the range of 24.20 - 24.50 Å. This unit cell size of the faujasite zeolite is a general characteristic and can be evaluated with an accuracy of ±0.01 Å by various standard techniques. The most common measurement technique is by X-ray diffraction (XRD) according to the method of ASTM D3942 - 80.

[0016] Furthermore, zeolite Y typically has a surface area of at least 700 m 2 / g, preferably at least 750 m 2 / g, typically less than 1050 m 2 / g, measured by the well-known BET adsorption method of ASTM D4365 - 95 (using argon instead of nitrogen and involving argon adsorption at a p / p0 value of 0.03).

[0017] Also, zeolite Y typically has a crystallinity of at least 50% (determined according to X-ray diffraction (XRD) using ASTM D3906 - 97, adopting commercially available zeolite Y of the same unit cell size as a standard).

[0018] Furthermore, zeolite Y typically has an alkali level of at most 0.5% by weight, preferably at most 0.2% by weight, more preferably at most 0.1% by weight (determined according to XRF).

[0019] Furthermore, zeolite Y typically has a total pore volume of at least 0.4 ml / g (measured by a point argon desorption assay at P / P0 = 0.99).

[0020] As described above, the zeolite Y provided in step a) has a bulk (molar) silica-to-alumina ratio (SAR) of at least 10 (determined, for example, by XRF), and typically, the zeolite Y has an SAR of less than 200. Preferably, the zeolite Y provided in step a) has a bulk silica-to-alumina ratio (SAR) of 20 to 100. More preferably, the zeolite Y provided in step a) has an SAR of more than 40, and even more preferably, more than 60.

[0021] In step b) of the method according to the present invention, the zeolite Y provided in step a) is mixed with a base, water, and a surfactant to obtain a slurry of zeolite Y.

[0022] Step b) is intended to increase the mesoporosity of zeolite Y in step a). According to IUPAC nomenclature, a mesoporous material is a material containing pores with a diameter of 2 to 50 nm, but the increase in mesoporosity of zeolite Y occurs particularly in pores of 2 to 8 nm, so the present invention also focuses particularly on this pore range. Those skilled in the art are familiar with increasing the mesoporosity of zeolites, so this will not be discussed in detail here, and a general explanation of increasing mesoporosity is discussed, for example, in US20070227351A1 and the aforementioned US20130292300A1. Those skilled in the art will also understand that the order of addition of water, base, surfactant, and zeolite Y may be changed when obtaining the slurry of zeolite Y in step b). As a mere example, zeolite Y may be added to a pre-prepared basic aqueous solution of a surfactant, or zeolite Y may be added to the aqueous solution of the surfactant first, and then the base may be added.

[0023] Those skilled in the art will readily understand that the base used in step b) can vary widely. Suitable bases used are, for example, alkali hydroxides, alkaline earth hydroxides, NH4OH, and tetraalkylammonium hydroxides.

[0024] Furthermore, those skilled in the art will also readily understand that the surfactant can vary widely and can include cationic, ionic, or neutral surfactants. Preferably, the surfactant is a cationic surfactant. Furthermore, it is preferred that the surfactant contains a quaternary ammonium salt. Particularly suitable surfactants are quaternary ammonium salts having 8 to 25 carbon atoms.

[0025] In a preferred embodiment of the method according to the invention, the surfactant used in step b) contains an alkylammonium halide. Preferably, the alkylammonium halide contains at least 8 carbon atoms and typically less than 25 carbon atoms. Preferably, the surfactant is selected from CTAC (cetyltrimethylammonium chloride) and CTAB (cetyltrimethylammonium bromide), preferably CTAC.

[0026] If necessary, the aqueous solution may also contain a "swelling agent", that is, a compound capable of swelling micelles. Such swelling agents can vary widely and preferably include i) aromatic hydrocarbons and amines having 5 to 20 carbon atoms, and their halogen-substituted and C 1-14 alkyl-substituted derivatives (a preferred example is mesitylene), ii) cycloaliphatic hydrocarbons having 5 to 20 carbon atoms, and their halogen-substituted and C 1-14 alkyl-substituted derivatives, iii) polycyclic aliphatic hydrocarbons having 6 to 20 carbon atoms, and their halogen-substituted and C 1-14 alkyl-substituted derivatives, iv) straight-chain and branched aliphatic hydrocarbons having 3 to 16 carbon atoms, and their halogen-substituted and C 1-14 alkyl-substituted derivatives, v) alcohols and their derivatives, preferably C8~C 20 alcohol, more preferably C 10 ~C18 Alcohols and their derivatives, and vi) combinations thereof, can be selected from the group. According to a particularly preferred embodiment of the present invention, in step b), zeolite Y is C8-C 20 Alcohol, preferably C 10 ~C 18 It is mixed with alcohol.

[0027] Those skilled in the art will understand that the mixing conditions and duration in step b) are not particularly limited and can vary widely. Typically, mixing is carried out at a temperature of room temperature to 200°C and a pressure of 0.5 to 5.0 bara, preferably atmospheric pressure. The duration of mixing is typically in the range of 30 minutes to 10 hours. The pH of the resulting slurry is typically in the range of 9.0 to 12.0, preferably greater than 10.0 and preferably less than 11.0.

[0028] According to a particularly preferred embodiment of the method according to the present invention, the zeolite Y in the slurry obtained in step b) has a total mesopore volume in pores having a volume of 2 to 8 nm, determined by a desorption method by argon-NLDFT adsorption, at least 0.2 ml / g, preferably in the range of 0.30 to 0.65 ml / g. Furthermore, the zeolite Y in the slurry obtained in step b) has a ratio of total mesopore volume in pores having a volume of 2 to 8 nm (determined by point argon desorption at P / P0 = 0.99) of typically 0.55 to 0.85 (55 to 85%), preferably less than 0.70 (70%).

[0029] In step c) of the method according to the present invention, the water content of the slurry obtained in step b) is reduced, thereby obtaining a solid having a reduced water content. The reduction in water content in step c) is preferably accompanied by the addition of a binder in an amount of 70 to 95% by weight, preferably 75 to 95% by weight, on a dry weight basis and based on the combined weight of the binder and the zeolite.

[0030] Those skilled in the art will readily understand that the water reduction step in step c) is not particularly limited, provided that the reduction in water content in step c) is accompanied by the addition of a binder. In addition to the addition of a binder, the water reduction step may also include drying and filtration or a combination thereof.

[0031] Surprisingly, according to the present invention, it has been found that by adding a binder at the water reduction stage, the resulting solid has lower viscosity, is therefore easier to transport and handle, and results in a more uniform dispersion of the binder material.

[0032] The binder is not particularly limited, but preferably comprises (and preferably even comprises) one or more non-zeolite inorganic oxides. Preferably, the non-zeolite inorganic oxide constitutes more than 90% by weight, more preferably more than 95% by weight, and even more preferably more than 98% by weight of the binder. Examples of non-zeolite inorganic oxides are alumina, silica, silica-alumina, zirconia, clay, aluminum phosphate, magnesia, titania, silica-zirconia, and silica-boria. Preferably, the binder comprises a component selected from the group consisting of silica-alumina and amorphous silica-alumina.

[0033] Preferably, the binder has an acidity of less than 100 micromoles / gram as measured by IR (H / D exchange at 323K via C6D6 as described in Chem.Commun.,2010,46,3466-3468).

[0034] According to the present invention, the binder is preferably added in an amount of 70 to 95% by weight, more preferably 75 to 95% by weight, on a dry weight basis and based on the combined weight of the (non-zeolite) binder and the zeolite.

[0035] If necessary, for example, a (optional) washing step may be included between the mixing in step b) and the reduction of water content in step c) to remove halides and / or alkali ions.

[0036] Typically, the solid with reduced water content obtained in step c) has an LOI (loss on ignition) of 35–70%, preferably less than 50%, more preferably less than 40%, as measured using an Arizona Computrac Max 5000XL moisture analyzer at 485°C. If a (non-zeolite) binder is used in step c), the LOI will typically be in the range of 20–35%, preferably less than 30%, more preferably less than 25%, as a flowable powder is obtained (again, in this case, also measured using an Arizona Computrac Max 5000XL moisture analyzer at 485°C).

[0037] In step d) of the method according to the present invention, the solid having a reduced water content obtained in step c) is molded to obtain a molded catalyst support.

[0038] Those skilled in the art are familiar with the molding of catalyst supports, and therefore will not discuss this in detail here. Typically, molding is carried out by extrusion using an extruder, thereby obtaining the desired shape (e.g., cylindrical or trefoil).

[0039] Preferably, the surfactant content during molding in step d) (expressed as the carbon content of the modified zeolite and determined according to ASTM D5291) is at least 20% by weight, preferably at least 25% by weight, based on dry zeolite.

[0040] In step e) of the method according to the present invention, the molded catalyst support obtained in step d) is calcined at a temperature exceeding 300°C in the presence of the surfactant of step b), thereby obtaining a calcined catalyst support. Preferably, the surfactant content during calcination in step e) (in this case also expressed as the carbon content of the modified zeolite and determined according to ASTM D5291) is at least 20% by weight on a dry zeolite basis.

[0041] Those skilled in the art are familiar with the calcination conditions for molded catalyst supports, and therefore will not discuss them in detail here. Preferably, the calcination in step e) is carried out at a temperature above 500°C, more preferably above 600°C, typically below 1000°C, preferably below 900°C, and more preferably below 850°C. The typical calcination time is 30 minutes to 10 hours. The typical calcination pressure is 0.5 to 5.0 bara, preferably atmospheric pressure.

[0042] Furthermore, since the risk of explosion during calcination is minimized, step e) may be carried out in the presence of oxygen (or more typically air). This eliminates the need for nitrogen blankets, etc., thus increasing the ease of processing. It is also preferable that the calcination be carried out in a single step.

[0043] In step f) of the method according to the present invention, the catalyst support calcined in step e) is impregnated with a hydrogenation component (usually a metal salt such as a metal oxide or metal sulfide) to obtain a supported catalyst.

[0044] In this case as well, those skilled in the art are familiar with impregnating the catalyst support with hydrogenation components (typically including a calcination process), so this will not be discussed in detail here.

[0045] Preferably, the hydrogenation component includes a metal selected from the group consisting of Group VIB and Group VIII metals. In this regard, see CRC Handbook of Chemistry and Physics ("The Rubber Handbook"), 66. thRefer to the periodic table of elements printed on the inside of the cover of this edition, which uses CAS version notation. Examples of Group VIB metals are molybdenum and tungsten, and examples of Group VIII metals are cobalt, nickel, iridium, platinum, and palladium. According to a particularly preferred embodiment of the present invention, the metal is selected from Ni, W, and Mo, preferably Ni and W. Preferably, the final supported catalyst contains at least two hydrogenation components, e.g., molybdenum and / or tungsten components combined with a cobalt and / or nickel component. Particularly preferred combinations are nickel / tungsten and nickel / molybdenum.

[0046] The resulting supported catalyst may contain up to 50 parts by weight of hydrogenation components, calculated as metal oxides per 100 parts by weight (dry weight) of the total catalyst composition.

[0047] An important feature of the present invention is that no heat treatment at a temperature exceeding 500°C is performed between the mixing in step b) and the molding in step d). As a result, the surfactant is not removed in the same way that it would be removed if caulking were performed between the mixing in step b) and the molding in step d).

[0048] Preferably, no heat treatment at a temperature above 300°C is performed between the mixing in step b) and the molding in step d), preferably no heat treatment at a temperature above 250°C is performed between the mixing in step b) and the molding in step d), and even more preferably no heat treatment at a temperature above 200°C is performed between the mixing in step b) and the molding in step d).

[0049] In a further embodiment, the present invention provides a supported catalyst obtained by the method described in any one of the prior claims.

[0050] In a further embodiment, the present invention provides a process for converting hydrocarbon raw materials into lower boiling point substances, the process comprising contacting the raw materials with hydrogen at high temperature and pressure in the presence of a catalyst obtained by the method according to the present invention.

[0051] Those skilled in the art are familiar with processes for converting hydrocarbon raw materials into lower boiling point substances, and therefore will not discuss these in detail here. Examples of such processes include single-stage hydrocracking, double-stage hydrocracking, and series-flow hydrocracking, as defined on pages 602 and 603 of Chapter 15 (titled "Hydrocarbon processing with zeolites") of "Introduction to zeolite science and practice" (edited by Van Bekkum, Flanigen, and Jansen and published by Elsevier in 1991).

[0052] Typically, contact occurs at (high) temperatures of 250-450°C and 3 × 10⁻⁶ 6 ~3×10 7 The process is carried out under a pressure of Pa. The raw material is 0.1 to 10 kg (kg·l) per liter of catalyst per hour. -1 ·h -1 A space velocity within the range of ) is conveniently used. The ratio of hydrogen gas to the raw materials used (total gas velocity) is typically in the range of 100 to 5000 Nl / kg.

[0053] The hydrocarbon feedstocks useful in this process can vary over a wide boiling point range and include atmospheric diesel, coker diesel, vacuum diesel, deasphaltized oil, waxes obtained from the Fischer-Tropsch synthesis process, long and short residues, catalytic cracking cycle oils, pyrolytic or catalytic cracking diesel, synthetic crude oil, and combinations thereof. The feedstocks will generally contain hydrocarbons with a boiling point of at least 330°C.

[0054] The present invention can be further illustrated by the following non-limiting examples. [Examples]

[0055] Zeolite modification The following commercially available zeolite Y materials were obtained from Zeolyst International BV (Delfzijl, The Netherlands): CBV-720, CBV-760, and CBV-780. The properties of these zeolite Y materials are shown in Table 1 below. [Table 1]

[0056] Modified zeolite 1 (according to the present invention) A basic aqueous solution (187.5 ml) was prepared using 2.82 g of NaOH (commercially available from VWR Chemicals (Leuven, Belgium)) and 60 g of CTAC (25% aqueous solution, commercially available from Sigma-Aldrich (Darmstadt, Germany)). 30 g of CBV-720 zeolite (by dry weight) was added to this solution, and the resulting slurry was magnetically stirred for 5 minutes.

[0057] Next, the slurry was heated to 80°C and stirred for 6 hours. After that, the slurry was quenched with cold (approximately 20°C) demineralized water, followed by filtration and thorough washing with demineralized water.

[0058] The resulting mesoporous zeolite will be referred to as "MZ1" or "720mp".

[0059] Modified zeolite 2 (according to the present invention) An aqueous solution was prepared by mixing 72 g of CTAC (25% solution, Sigma-Aldrich (Darmstadt, Germany)) with 232 g of water. 30 g of CBV-760 zeolite (by dry weight) was added to this solution, and the resulting slurry was heated to 80°C under magnetic stirring. After 1 hour at 80°C, 4.8 g of NaOH (50% solution in demineralized water, prepared from NaOH pellets from VWR Chemicals (Leuven, Belgium)) was added, and the slurry was stirred at 80°C for 5 hours. The slurry was then quenched with cold (approximately 20°C) demineralized water, followed by filtration and thorough washing with demineralized water. The filtrate was resuspended in 300 g of demineralized water and heated to 70°C under magnetic stirring. After reaching 70°C, 4.6 g of 65% HNO3 (commercially available from Merck KGaA (Darmstad, Germany)) was added. After 1 hour at 70°C, the slurry was filtered and thoroughly washed with demineralized water. Hereafter, the obtained mesoporous zeolite Y will be called "MZ2" or "760mp".

[0060] Modified Zeolite 3 (Comparison) Half of the 760mp was dried at 120°C, calcined in an N2 atmosphere at 760°C for 1 hour, and then calcined in air at 550°C for 2 hours. This calcined sample was designated "MZ3" or "760mp-C" and served as a comparative material (prepared using a two-step calcination procedure similar to Example 7 of US2013 / 0292300A1).

[0061] Modified zeolite 4 (according to the present invention) An aqueous solution was prepared by mixing 72 g of CTAC (25% aqueous solution, Sigma-Aldrich) with 232 g of water. Cetyl alcohol ("CA", a commercially available synthetic grade from Sigma Aldrich (Zwijndrecht, The Netherlands)) was added as a swelling agent in a CA / CTAC molar ratio of 0.4. 30 g of CBV-760 zeolite (by dry weight) was added to this solution, and the slurry was heated to 80°C while magnetically stirring. After 1 hour at 80°C, 4.8 g of NaOH (50% solution in demineralized water, prepared with NaOH pellets (VWR Chemicals)) was added, and the slurry was stirred at 80°C for 5 hours. The hot slurry was then quenched with cold (approximately 20°C) demineralized water, filtered, and thoroughly washed with demineralized water. The filtrate was resuspended in 300 g of demineralized water and heated to 70°C while magnetically stirring. After reaching 70°C, 0.1 grams of HNO3 (commercially available as a 65% solution from Merck KGaA (Darmstad, Germany)) was added per gram of zeolite (totaling 4.6 g of 65% HNO3). After 1 hour at 70°C, the slurry was filtered and thoroughly washed with desalinated water. The resulting modified zeolite Y is called "MZ4" or "760mpSA" (i.e., treated with a swelling agent).

[0062] Modified Zeolite 5 (Comparison) Half of "MZ4" (760mpSA) was dried at 120°C, then calcined at 760°C for 1 hour in an N2 atmosphere, and then calcined in air at 550°C for 2 hours. This calcined sample was called "MZ5" or "760mpSA-C" and served as a comparative material (prepared using a two-step calcination procedure similar to Example 7 of US2013 / 0292300A1).

[0063] Modified zeolite 6 (according to the present invention) An aqueous solution was prepared using 24 g of CTAC (25% aqueous solution, Sigma-Aldrich) and 77.3 g of demineralized water. To this solution, 10 g of CBV-780 zeolite (based on dry weight) was added, and the resulting slurry was heated to 80°C while magnetically stirring. After 1 hour at 80°C, 4.8 g of NaOH (50% solution in the demineralized water, prepared from NaOH pellets (VWR Chemicals)) was added, and the slurry was stirred at 80°C for 4 hours. The hot slurry was then quenched with cold (approximately 20°C) demineralized water, filtered, and thoroughly washed with demineralized water. The filtrate was resuspended in 300 g of demineralized water and heated to 70°C while magnetically stirring. After reaching 70°C, 0.1 g of HNO3 (commercially available as a 65% aqueous solution from Merck KGaA) was added per gram of zeolite (totaling 1.54 g of 65% HNO3). After 1 hour at 70°C, the slurry was filtered and thoroughly washed with desalinated water. The resulting zeolite is called "MZ6" or "780mp".

[0064] Modified Zeolite 7 (Comparison) A portion of "MZ6" (760mp) was dried at 120°C, then calcined at 760°C for 1 hour in an N2 atmosphere, and then calcined in air at 550°C for 2 hours. This calcined sample was designated "MZ7" or "780mp-C" and served as a comparative material (prepared using a two-step calcination procedure similar to Example 7 of US2013 / 0292300A1).

[0065] Powder analysis of (modified) zeolite Y Prior to powder analysis, all samples were dried at 120°C, then calcined at 760°C for 1 hour under an N2 atmosphere, followed by calcination at 550°C for 2 hours under air, using a two-step calcination procedure similar to Example 7 of US20130292300A1. This was done to remove surfactants and ensure accessibility for adsorption experiments.

[0066] The following tests / equipment were used for the analysis.

[0067] - Pore volume: The total pore volume ("total PV") and mesopore volume ("mesoPV") were determined by argon physicoadsorption.

[0068] For this purpose, sorbation experiments were performed using a Micromeritics 3FLEX version 4.03 instrument with argon (-186°C). Prior to the adsorption experiment, the samples were degassed under vacuum at 350°C for at least 12 hours.

[0069] To determine the "total PV," point argon desorption data with P / P0 = 0.99 was used.

[0070] To determine the "meso-PV" (in the range of 2-8 nm), argon adsorption data was used with the HS-2D-NLDFT, Cylindrical oxide, Ar, 87 model from Micromeritics. From this data, the average pore size in the 2-8 nm pore range was also calculated.

[0071] -Argon surface area: The surface area was determined by argon adsorption according to the conventional BET (Brunauer-Emmett-Teller) method adsorption technique described in the literature by S. Brunauer, P. Emmett, and E. Teller, J. Am. Chm. Soc., 60, 309 (1938), and ASTM Method D4365-95. The surface area was measured at P / P0 = 0.03.

[0072] -Unit cell parameter A0: For example, unit cell constants were determined using XRD analysis according to ASTM D3942-80.

[0073] The samples were measured using an X'Pert diffractometer at Malvern Panalytical. The samples were measured in a powdered and homogenized form.

[0074] The sample and reference sample (i.e., the untreated parent zeolite) were held for at least 16 hours in the closed radiation cabinet of the diffractometer to ensure equilibrium equivalent to the ambient conditions of the cabinet.

[0075] - Crystallinity: The degree of crystallinity was determined using XRD analysis.

[0076] Crystallinity was determined by comparing the total diffraction intensity of the sample's diffraction pattern with that of a reference sample (corresponding parent zeolite). The intensity ratio was reported as a percentage of the reference intensity.

[0077] - Bulk (molar) silica to alumina ratio (SAR): The bulk (molar) silica-to-alumina ratio (SAR) can be measured using various methods such as ICP, AAS, and XRF, yielding similar results. Here, XRF analysis was applied using a 4kW WD-XRF analyzer.

[0078] The results are shown in Table 2 below. [Table 2]

[0079] Explosives test The following four samples were prepared (or obtained) for explosiveness testing and TGA-MS experiments.

[0080] 1. A portion of the sample MZ2 (760 mp) obtained above was subjected to an explosive test (described later).

[0081] 2. A portion of the sample MZ2 (760 mp) obtained above was re-slurried in desalinated water (10 ml / g dry material) with amorphous silica-alumina in a mass ratio (based on dry weight) of 70% ASA and 30% zeolite. Approximately 500 ml of ASA was used. 2It had a surface area of ​​1.03 ml / g, a pore volume of 1.03 ml / g, and an apparent bulk density of 0.24 g / ml, and contained 45% silica and 55% alumina. After stirring for at least 60 minutes, the slurry was filtered and dried at 80°C for 2 hours. The resulting material is called "MZ2-ASA 30% blend" (or "760mp-30 blend").

[0082] 3. A portion of the sample MZ2 (760 mp) obtained above was re-slurried in desalinated water (10 ml / g dry material) with amorphous silica-alumina in a mass ratio (based on dry weight) of 75% ASA and 25% zeolite. Approximately 500 ml of ASA was used. 2 It had a surface area of ​​1.03 ml / g, a pore volume of 1.03 ml / g, and an apparent bulk density of 0.24 g / ml, and contained 45% silica and 55% alumina. After stirring for at least 60 minutes, the slurry was filtered and dried at 80°C for 2 hours. The resulting material is called "MZ2-ASA 25% blend" (or "760mp-25 blend").

[0083] 4. Using a portion of the sample MZ2 (760 mp) obtained above, the carrier material described in Example 5 under "Preparation of Carrier and Hydrocracking Catalyst" was prepared. MZ2 and ASA were mixed to achieve a zeolite content of 15% (dry basis) in the carrier. An extrusion aid was added, followed by mixing and extrusion, and the resulting extruded material was dried at 80°C for 2 hours. The resulting extruded material is referred to as Example 5 (or "MZ2-15% carrier").

[0084] Explosiveness tests were conducted at Dekra (DEKRA Process Safety, Princeton, USA). Dust explosiveness classification tests were performed using a vertical tube apparatus described by Bartknecht (1989) in accordance with ASTM E1226 (Standard Test Method for Explosiveness of Dust Clouds) and ASTM E1515 (Standard Test Method for Minimum Explosive Concentration).

[0085] A summary of the explosiveness test results is shown in Table 3 below. "Non-explosive" indicates that the powder will not explode in a 5 kJ chemical ignition source, while "Explosive" indicates the possibility of explosiveness. [Table 3]

[0086] Table 3 shows that the obtained powder (MZ2) and the blend of ASA and 30% modified zeolite are potentially explosive.

[0087] The "non-explosive" results for blends with a lower MZ2 content (25%), and for carriers with 15% MZ2, indicate that this material does not exhibit explosive behavior. This means it can be safely heat-treated on a commercial scale. In this regard, it should be noted that this does not rule out the possibility of combustion of the material, as a certain amount of organic matter is still present.

[0088] The TGA-MS experiment was performed in dynamic mode on a Netzsch STA 449 F3 Jupiter® (NETZSCH-Geratebbau GmbH (Selb), Germany) at a heating rate of 2°C / min up to 800°C. Argon (5 bar utility) was used as a protective gas at 20 ml / min, and 20% oxygen in argon was used as a purge gas at 65 ml / min. The gases generated during heating were monitored online using a mass spectrometer (QMS 403D Aeolos, NETZSCH-Geratebbau GmbH). The test was performed using an 85 μl aluminum oxide crucible, with the reference crucible kept empty.

[0089] A zeolite sample (approximately 30-40 mg of powder) was weighed and placed in a container, then placed on a DSC support.

[0090] The samples were heated to 800°C at a rate of 2°C / min. Both MZ2 (760mp) and MZ2-ASA blend (760mp-25% blend) samples, as well as a hydrocracking catalyst support containing 15% by weight of MZ2 (760mp) (i.e., Example 1, Table 4 below), were analyzed for comparison.

[0091] The results of these TGA MS measurements are shown in Figure 1. -The left column shows a comparison between MZ2 (thick line) and MZ2-ASA blend (dotted line), and -In the right column, a comparison is made between MZ2 (again, a thick line) and the hydrocracking catalyst support according to Example 5 (gray line). From top to bottom, - Mass spectrometer data: m / z=44 signal showing CO2 formation as a function of temperature (°C), - Mass spectrometer data: m / z=18 signal showing H2O formation as a function of temperature (°C), - Thermogravimetric analysis data: Mass change as a function of temperature (°C), and - We will show the first time derivative (δm / δt) of the mass change as a function of temperature (°C).

[0092] Mass spectrometer data clearly allows monitoring of the H2O removal and surfactant decomposition processes as a function of temperature. Surfactant decomposition manifests as the formation of CO2 and CO (data not included).

[0093] These steps are also consistent with the mass changes observed for both the MZ2 powder, the MZ2-ASA blend, and the catalyst support according to Example 5.

[0094] From the mass change as a function of temperature, it can be seen that the decomposition of surfactants in the MZ2-ASA blend and catalyst support proceeds at a slower rate than in the parent MZ2 sample. This lower decomposition rate (for the MZ2-ASA blend and catalyst support) is also reflected in the lower negative values ​​in the δm / δt plot.

[0095] Therefore, the data in Figure 1 is consistent with the explosiveness tests described above, indicating that the addition of a binder slows down the exothermic decomposition of the surfactant in air, thereby eliminating the risk of dust explosions during incineration.

[0096] Preparation of support and hydrocracking catalyst Several hydrocracking catalysts were prepared. First, catalyst supports (i.e., extruded and calcined extruded materials containing zeolite and ASA as a binder) were prepared using either commercially available zeolite or one of the modified zeolites prepared above, in the amounts of zeolite and ASA shown in Table 4 below. Approximately 15 g of catalyst support was prepared. 500 ml of ASA was used. 2 It had a surface area of ​​1.03 ml / g, a pore volume of 1.03 ml / g, and an apparent bulk density of 0.24 g / ml, and contained 45% silica and 55% alumina.

[0097] Reference supports for producing catalysts containing parent zeolites were prepared using 1% by weight acetic acid (Merck KGaA), 1% by weight nitric acid (Merck KGaA), 0.5% by weight PVA (5% aq Mowiol® 18-88), and 1% by weight methylcellulose (K15M, available from Dow Chemical Company) as degellating agents and extrusion aids (see Reference Examples 1, 2, 3, 5, and 6 in Table 4).

[0098] For all carriers and catalysts containing modified zeolite, 2.24% nitric acid (Merck KgaA), 0.5% by weight PVA (5% aq Mowiol® 18-88), and 1% by weight methylcellulose (K15M) were used, both for comparison and in accordance with the present invention.

[0099] After mixing zeolite with ASA, a molded catalyst support was obtained by extruding it into a 1.6 mm diameter tri-lobed extruded product. The obtained molded catalyst support was calcined at 650°C for 1 hour.

[0100] Next, hydrogenation components were added to the calcined catalyst support by initial aqueous wetting impregnation with nickel carbonate (commercially available from Umicore (Belgium)), ammonium metatungstate (commercially available from Sigma-Aldrich), and citric acid (VWR Chemicals). Citric acid and Ni were added in a 1:1 molar ratio, aiming for a filling of 4% by weight Ni and 19% by weight W. After drying at 120°C, the catalyst was calcined at 450°C for 2 hours.

[0101] In Table 4 below, catalysts prepared from parent (i.e., unmodified) zeolite are shown as "Reference Examples," catalysts prepared from zeolite according to the present invention are shown as "Examples," and catalysts prepared from zeolite following the two-step calcination procedure of US20130292300A1 are shown as "Comparative Examples." [Table 4]

[0102] Catalyst testing The hydrocracking performance of the catalyst of the present invention was evaluated using two types of tests.

[0103] - Test 1 In Test 1, a second-stage serial flow simulation was performed to evaluate the catalyst of the present invention and the comparative catalyst against a reference catalyst. The test was conducted in a once-through nanoflow apparatus loaded with a top catalyst bed containing 0.6 ml of C-424 catalyst (commercially available from Shell Catalysts & Technologies (Ghent, Belgium)) diluted with 0.6 ml of Zirblast (B120, commercially available from Saint-Gobain ZirPro (France)) and a bottom catalyst bed containing 0.6 ml of test catalyst diluted with 0.6 ml of Zirblast (B120). Both catalyst beds were pre-sulfurized in situ by gas-phase sulfurization prior to testing. Pre-sulfurization was performed in the gas phase (5 wt% H2S in hydrogen) at 15 barg, increasing the temperature from room temperature (20°C) to 135°C on a 20°C / h ramp, holding for 12 hours, then increasing to 280°C, holding for another 12 hours, and then increasing the temperature again at a rate of 20°C / h to 355°C.

[0104] Each test is conducted under the following process conditions, namely: - 1.5 kg (kg.l) of heavy diesel fuel per liter of catalyst per hour -1 .h -1 ) spatial velocity, -1440 Nl / kg hydrogen gas / heavy diesel fuel ratio, -5.6 × 10 5 The partial pressure of hydrogen sulfide at Pa (5.6 bar), and -14×10 6 The once-through operation at a total pressure of Pa (140 bar) involved sequentially bringing the hydrocarbon feedstock (heavy diesel fuel) into contact with the top catalyst bed, and then with the bottom catalyst bed.

[0105] The heavy diesel fuel used had the following characteristics: -Carbon content: 86.82% by weight - Hydrogen content: 13.18% by weight - Nitrogen (N) content: 28 ppmw - Added n-decylamine: 12.3 g / kg (equivalent to 1100 ppmw N) -Total nitrogen (N) content: 1110 ppmw -Density (70℃): 0.8586g / ml -Mono-Aromatic rings: 4.57% by weight -Aromatic ring: 1.83% by weight -Initial boiling point: 316℃ -50% wt boiling point: 425℃ -Final boiling point: 600℃ - Fractions with a boiling point below 370°C: 8.75% by weight -Fractions with a boiling point above 540°C: 4.18% by weight

[0106] Hydrocracking performance was evaluated by the conversion level of the net conversion rate of 40–90 wt% of the feed component boiling above 370°C. Experiments were conducted at different temperatures, and in all experiments, the net conversion rate of 65 wt% of the feed component boiling above 370°C was obtained by interpolation. Table 4 shows the results obtained for the catalysts listed in Table 3.

[0107] - Test 2 In Test 2, the second stage of a two-stage simulation was performed to evaluate the catalyst of the present invention and the comparative catalyst against a reference catalyst. The test was conducted in a once-through nanoflow apparatus packed with 0.6 ml of the test catalyst diluted with 0.6 ml of Zirblast (B120). The catalyst was pre-sulfurized as described in Test 1 above.

[0108] Each test is conducted under the following process conditions, namely: - 1.5 kg (kg.l) of heavy diesel fuel per liter of catalyst per hour -1 .h -1 ) spatial velocity, -1500 Nl / kg hydrogen gas / heavy diesel fuel ratio, - 50 ppmV H2S obtained by spiking the raw material with Sulfrzol S54 (obtained from Lubrizol), and -14×10 6 The once-through operation at a total pressure of Pa (140 bar) involved contacting the hydrocarbon feedstock (heavy diesel fuel) with the catalyst bed.

[0109] The heavy diesel fuel used had the following characteristics: -Carbon content: 85.86% by weight - Hydrogen content: 14.14% by weight -Nitrogen (N) content: 0.3ppmw - Sulfrzol (0.186 g / kg of sulfrzol 54) was added to achieve 50 ppmV H2S in the gas phase. -Density (70℃): 0.812g / ml -Mono-Aromatic ring: 0.75% by weight -Aromatic ring: 0.68% by weight -Initial boiling point: 297℃ -50% wt boiling point: 429°C -Final boiling point: 580℃ - Fractions with a boiling point below 370°C: 11.6% by weight -Fractions with a boiling point above 540°C: 3.83% by weight

[0110] Hydrocracking performance was evaluated by the conversion level of the net conversion rate of 30–70 wt% of the feed component boiling above 370°C. Experiments were conducted at different temperatures, and in all experiments, a net conversion rate of 55 wt% of the feed component boiling above 370°C was obtained by interpolation. Table 5 below shows the results obtained for the catalysts listed in Table 4. [Table 5]

[0111] The results in Table 5 are as follows: -As can be seen from the delta-MD values, catalysts having mesoporous zeolite (Examples 1-4 and Comparative Examples 1 and 2) give higher middle distillate (MD) selectivity (150-370°C) than the corresponding non-mesoporous catalysts (Reference Examples 1-4). - Catalysts containing mesoporous zeolite exhibit a higher diesel / kerosene ratio than non-mesoporous catalysts. - Catalysts prepared with mesoporous zeolites having enlarged mesopore diameters due to the use of a swelling agent (i.e., Examples 2 and Comparative Example 2) exhibit increased MD selectivity compared to catalysts prepared without a swelling agent (Examples 1 and Comparative Example 1), using the same mesoporous zeolite (i.e., MZ2). This is demonstrated by a significant increase in delta-MD. - The MD selectivity of Examples 1-2 of the present invention (including modified CBV-720 or CBV-760) is consistently higher compared to the corresponding examples (Comparative Examples 1-3) in which a two-step calcination process was performed (thus removing at least a portion of the surfactant), as can be seen from the consistently higher delta MD values. Examples 1 and 2 (catalysts prepared from mesoporous zeolite CBV-760) showed improved tri-aromatic saturation compared to Comparative Examples 1 and 2 (which underwent a two-step calcination process).

[0112] Those skilled in the art will readily understand that many modifications can be made without departing from the scope of the present invention.

Claims

1. A method for preparing a supported hydrocracking catalyst, wherein the method is a) A step of providing a zeolite Y having at least 10 bulk silica-to-alumina ratios (SAR), b) A step of mixing the zeolite Y provided in step a) with a base, water, and a surfactant to obtain a slurry of the zeolite Y, c) A step of reducing the water content of the slurry obtained in step b), thereby obtaining a solid having the reduced water content, wherein the reduction in water content in step c) is accompanied by the addition of a binder, the binder being amorphous silica-alumina (ASA) present in an amount of 75% to 95% of the weight of the carrier, d) A step of molding the solid having the reduced water content obtained in step c), thereby obtaining a molded catalyst support, e) A step of calcining the molded catalyst support obtained in step d) at a temperature exceeding 300°C in the presence of the surfactant from step b), thereby obtaining a calcined catalyst support, f) The process includes impregnating the catalyst support calcined in step e) with a hydrogenation component to obtain a supported catalyst, A method wherein no heat treatment at a temperature exceeding 500°C is performed between the mixing in step b) and the molding in step d).

2. The method according to claim 1, wherein the zeolite Y provided in step a) has a bulk silica-to-alumina ratio (SAR) of 20 to 100.

3. The method according to claim 1 or 2, wherein the surfactant used in step b) comprises an alkylammonium halide.

4. In step b), the zeolite Y is C ８ ~C ２０ The method according to any one of claims 1 to 3, which is mixed with alcohol.

5. The method according to any one of claims 1 to 4, wherein the zeolite Y in the slurry obtained in step b) has a total mesopore volume in pores having a volume of 2 to 8 nm, determined by Ar adsorption by NLDFT, at least 0.2 ml / g.

6. The method according to any one of claims 1 to 5, wherein the calcination in step e) is carried out in the presence of oxygen.

7. The method according to any one of claims 1 to 6, wherein the hydrogenation component comprises a metal selected from the group consisting of Group VIB and Group VIII metals.

8. The method according to claim 7, wherein the metal is selected from Ni, W, and Mo.

9. The method according to any one of claims 1 to 8, wherein no heat treatment at a temperature exceeding 300°C is performed between the mixing in step b) and the molding in step d).

10. A supported hydrocracking catalyst comprising a support having a modified zeolite Y having a bulk silica-to-alumina ratio (SAR) of at least 10 and a total mesopore volume in pores having a volume of 2 to 8 nm determined by Ar adsorption by NLDFT, and a binder present in an amount of 75% to 95% of the weight of the support, and a metal supported on the support and selected from the group consisting of group VIB metals and group VIII metals, wherein the binder is amorphous silica-alumina (ASA).

11. A process for converting hydrocarbon raw materials into lower boiling point substances, the process comprising contacting the raw materials with hydrogen at high temperature and pressure in the presence of a catalyst obtained by the method of any one of claims 1 to 10.

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