A silicon-aluminum material comprising a layered structure, its manufacturing method and applications

Abstract

This invention relates to a silicon-aluminum material, its manufacturing method, and its applications. The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 0.8-1.5, comprises a lamellar structure with an average length of 0.5-2 μm and an average thickness of 30-80 nm, and its calcination form exhibits a specific XRD pattern. The silicon-aluminum material of this invention possesses macropore volume, a two-level gradient of mesopore and macropore channels, and the characteristics of high Brønsted acid content characteristic of molecular sieves, exhibiting the crystal properties of molecular sieves. It has low impurity content and is suitable for use as a catalyst support, especially as a support for heavy oil hydrogenation catalysts.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, and relates to a silicon-aluminum material, its manufacturing method and application. Prior Technology

[0002] Molecular sieves are introduced into hydrocracking catalyst supports to improve the catalyst's cracking performance. However, due to the characteristics of large molecules and high nitrogen content in residue feedstocks, rapid deactivation is prone to occur when using molecular sieve catalysts, limiting their application in residue hydrocracking processes. Macroporous silica-alumina materials possess suitable pore structure and acidity, good hydrothermal stability, and strong cracking performance, making them particularly suitable for residue hydrocracking processes.

[0003] Manufacturing methods for aluminum silicate (ASi) materials generally include the sol-gel method, kneading method, and impregnation method. Macroporous ASi materials are typically manufactured using the sol-gel method, which generally uses water glass or silica sol as the silica source. The difficulty in manufacturing macroporous ASi materials lies in the fact that as the silica content increases, the pore volume of the ASi material gradually decreases, while the sodium content increases significantly. Sodium, as an impurity in ASi materials, needs to be removed; generally, the sodium content needs to be less than 0.5%. Industrially, expensive silica sol is often used as the silica source to reduce the number of subsequent washing steps for sodium removal, or ion exchange is used for sodium removal. However, these methods significantly increase the manufacturing cost of ASi materials, resulting in poor economic efficiency and limiting their large-scale industrial application.

[0004] CN201710382457.7 discloses a highly active silicon-aluminum material and its manufacturing method. This active silicon-aluminum material contains 15-45% silicon and 55-85% aluminum by weight of oxides, with a total BET specific surface area of ​​300-500 m² / g, and the proportion of microporous specific surface area to the total BET specific surface area is [not specified in the original text]. 8%, average pore size 5-18nm; c represents the Al / Si atomic ratio on the material surface measured by XPS method, and when d represents the Al / Si atomic ratio in the bulk phase of the material measured by XRF method, c / d=1.2-1.9.

[0005] CN201710630418.4 discloses a mesoporous and macroporous silicon-aluminum material and its manufacturing method. The aforementioned mesoporous and macroporous silicon-aluminum material, based on oxide weight, has the following anhydrous chemical formula: (0-0.3)Na₂O:(2-18)Al₂O₃:(82-98)SiO₂; its pore volume is 0.8-2 mL / g, its specific surface area is 150-350 m² / g, its most probable pore size is 30-100 nm, and its B / L acid ratio is 0.8-2.0. The silicon-aluminum material of this invention features high pore volume, large pore size, and a high B / L acid ratio. Furthermore, the manufacturing method of this invention uses an inexpensive silicon-aluminum source, requires no organic template agent, and is characterized by low cost and simple operation. The ammonium salt exchange method provided in this invention involves exchanging the filtered solid precipitate 1-3 times at room temperature to 100°C according to a weight ratio of precipitate (dry basis): ammonium salt: H2O = 1:(0.1-1):(5-10), each exchange lasting 0.3-1 hour, until the sodium content in the solid precipitate is less than 0.3 wt%. The ammonium salt used for exchange is selected from one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate, and ammonium bicarbonate.

[0006] CN201710102634.1 discloses a silicon-aluminum material, its manufacturing method, and its application. The silicon-aluminum material, with a chemical composition determined by XRF method based on oxide weight as: (0-0.3)Na₂O·(50-80)SiO₂·(20-50)Al₂O₃, is characterized by a diffuse diffraction peak appearing only at 25°-27° in its XRD spectrum, a pore size between 20-50 nm, and x / y = 0.55-0.75, where x represents the Si / Al atomic ratio measured by XPS method, and y represents the Si / Al atomic ratio measured by XRF method. Summary of the Invention

[0007] The inventors of this invention discovered that the difficulty in preparing macroporous aluminum silica (AHS) materials lies in the fact that as the silica content increases, the pore volume of AHS materials gradually decreases, while the sodium content increases significantly. Effectively reducing the sodium content while maintaining a large pore volume is crucial. However, in prior art AHS material manufacturing methods, ammonium salt ion exchange is used to reduce the impurity content, especially sodium, which is a cumbersome process and increases the manufacturing cost of AHS materials. The inventors of this invention also found that industrially, expensive silica sol is typically used as a silica source to reduce the number of subsequent washing and sodium removal steps, or ion exchange is used for sodium removal. However, these methods significantly increase the preparation cost of AHS materials, resulting in poor economic efficiency and limiting their large-scale industrial application. Therefore, the inventors of this invention believe that preparing macroporous AHS materials while simultaneously reducing the cost of sodium removal is an effective way to prepare high-performance and inexpensive AHS materials. To this end, through diligent research, the inventors of this invention discovered a novel AHS material. This invention is based on this discovery.

[0008] Specifically, the present invention relates to the following state.

[0009] 1. A silicon-aluminum material having a SiO₂ / Al₂O₃ molar ratio of 0.8-1.5 (preferably 1.0-1.4), comprising a layered structure with an average length of 0.5-2 μm (preferably 0.5-1.5 μm) and an average thickness of 30-80 nm (preferably 30-75 nm), and having an XRD pattern substantially as shown in Table I or Table II below in its calcined form, preferably having an XRD pattern substantially as shown in Figure 2. Table I [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 14.0 0.12-0.13 VS 24.3 0.18-0.19 VS 34.3 0.07-0.08 S 42.6 0.11-0.13 M 51.9 0.10-0.13 M 66.4 0.06-0.08 M Table II [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 13.9 0.12-0.13 VS 24.2 0.17-0.18 VS 31 0.36-0.38 M 34.4 0.08-0.10 S 39.9 0.08-0.10 M 42.5 0.11-0.12 M 51.6 0.12-0.13 W 57.8 0.14-0.16 W 66.4 0.07-0.09 W If the intensity value of the strongest diffraction peak in the aforementioned XRD pattern is 100, then W = weak, i.e., relative intensity >0 to ≤20; M = moderate, i.e., relative intensity >20 to ≤40; S = strong, i.e., relative intensity >40 to ≤60; and VS = extremely strong, i.e., relative intensity >60 to ≤100.

[0010] 2. The silicon-aluminum material as described above, having a pore volume of not less than 1.1 mL / g (preferably greater than 1.15 mL / g, more preferably 1.15-1.5 mL / g), and / or having a specific surface area of ​​260-340 m² / g (preferably 260-310 m² / g). 2 / g), and / or, the pore distribution is as follows: pore volume of pores with a diameter <10nm accounts for ≤5% of the total pore volume (preferably pore volume of pores with a diameter <10nm accounts for ≤3% of the total pore volume), pore volume of pores with a diameter of 10-50nm accounts for 65%-85% of the total pore volume (preferably pore volume of pores with a diameter of 10-50nm accounts for 70%-85% of the total pore volume), pore volume of pores with a diameter >50nm accounts for 10%-30% of the total pore volume (preferably pore volume of pores with a diameter >50nm accounts for 12%-25% of the total pore volume), and / or, the average pore diameter is 14-23nm (preferably 16-21nm).

[0011] 3. The silicon-aluminum material as described above has a Brønsted acid content greater than 0.08 mmol / g (preferably 0.1-0.2 mmol / g or 0.1-0.15 mmol / g), and / or a Brønsted acid to Lewis acid ratio of 0.2-0.8 (preferably 0.3-0.7), and / or a Na₂O content less than 0.3 wt% (preferably less than 0.2 wt%), and / or an absorption peak at a chemical shift of -87 ppm to -89 ppm in its silicon nuclear magnetic resonance spectrum, and an absorption peak near a chemical shift of 57 ppm in its aluminum nuclear magnetic resonance spectrum, and / or no diffraction peak in its calcined form on a small-angle XRD pattern.

[0012] 4. Any of the aforementioned silicon-aluminum materials also includes non-lamellar structures, wherein, based on the total volume of the aforementioned silicon-aluminum materials, the proportion of the aforementioned lamellar structures is 3% or more (preferably 5% or more, more preferably 10-80% or 10-60%).

[0013] 5. A method for manufacturing a silicon-aluminum material, comprising the following steps in sequence: (1) A mixture A is obtained by adding an acidic aluminum source to a silicon source. (2) The aforementioned mixture A was contacted with an alkaline aluminum source in the presence of water to obtain slurry B, and (3) The aforementioned slurry B is subjected to hydrothermal treatment to obtain the aforementioned silicon-aluminum material.

[0014] 6. A method for manufacturing any of the aforementioned samples, wherein in step (1), the aforementioned silicon source is a water-soluble or water-dispersible alkaline silicon-containing compound (preferably a water-soluble or water-dispersible alkaline inorganic silicon-containing compound, more preferably selected from one or more of water-soluble silicates, water glass, and silica sol, preferably water glass), and / or, the aforementioned silicon source is used in the form of an aqueous solution, and the concentration of the aforementioned silicon source (based on SiO2) is 5-30 wt% (preferably 15-30 wt%) based on the total weight of the aforementioned aqueous solution, and / or, the aforementioned acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, especially a water-soluble inorganic strong acid aluminum salt, more preferably selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate), and / or, the aforementioned acidic aluminum source is used in the form of an aqueous solution, and the concentration of the aforementioned acidic aluminum source (based on Al2O2) is 5-30 wt% (preferably 15-30 wt%) based on the total weight of the aforementioned aqueous solution. The concentration of the silicon source (as SiO2) is 30-100 g / L (preferably 30-80 g / L), and / or the weight ratio of the aforementioned silicon source (as SiO2) to the aforementioned acidic aluminum source (as Al2O3) is 1:1-9:1 (preferably 1:1-7:1).

[0015] 7. A method for manufacturing any of the aforementioned samples, wherein in step (1), an acid is also added (preferably the aforementioned acidic aluminum source is added to the aforementioned silicon source, and then the aforementioned acid is added to obtain the aforementioned mixture A), and / or, the aforementioned acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably selected from one or more of sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid), and / or, the aforementioned acid is used in the form of an aqueous solution, and the concentration of the aforementioned acid is 2-6 wt% (preferably 2-5 wt%) based on the total weight of the aforementioned aqueous solution, and / or, the amount of the aforementioned acid added makes the pH value of the aforementioned mixture A 2-4 (preferably 3-4).

[0016] 8. A method for manufacturing any of the aforementioned samples, wherein in step (2), the aforementioned alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, especially an alkali metal aluminate, more preferably selected from one or more of sodium aluminate and potassium aluminate, preferably sodium aluminate), and / or, the aforementioned alkaline aluminum source is used in the form of an aqueous solution, and based on the total weight of the aforementioned aqueous solution, the aforementioned alkaline aluminum source (in Al₂O₃) is... The concentration of (3) is 130-350 g / L (preferably 150-250 g / L), and / or, based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water, the amount of the aforementioned mixture A is 40-80 vol% (preferably 45-75 vol%), and / or, based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water, the amount of the aforementioned alkaline aluminum source is 10-30 vol% (preferably 12-25 vol%), and / or, based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water, the amount of the aforementioned water is 10-30 vol%. 0 vol% (preferably 10-25 vol%), and / or, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water sequentially or simultaneously (preferably the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water in a co-current manner), and / or, the addition flow rate of the aforementioned mixture A is 15-50 mL / min (preferably 20-40 mL / min), and / or, the addition flow rate of the aforementioned alkaline aluminum source is controlled so that the pH value of the aforementioned slurry B is maintained at 7.5-10.5 (preferably 8.0-10.5, more preferably 8.5-10.5).

[0017] 9. A method for manufacturing any of the aforementioned samples, wherein in step (2), a water-soluble carbonate is also added (preferably, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water, and then the aforementioned water-soluble carbonate is added to obtain the aforementioned slurry B), and / or, the aforementioned water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate, preferably sodium carbonate), and / or, the aforementioned water-soluble carbonate is used in solid form, and / or, the amount of the aforementioned water-soluble carbonate added is such that the pH value of the aforementioned slurry B is 10.5-12 (preferably 11-12).

[0018] 10. A method for manufacturing any of the aforementioned samples, wherein in step (3), the aforementioned silicon-aluminum material is separated from the aforementioned hydrothermal treatment reaction system (e.g., by filtration or centrifugation), washed to neutral, and subsequently dried, and / or the aforementioned drying conditions include: a drying temperature of 100-150°C and a drying time of 6-10 hours.

[0019] 11. A method for manufacturing any of the aforementioned samples, wherein in step (1), the temperature is 25-50℃ (preferably 25-40℃) and the pressure is atmospheric pressure, and / or, in step (2), the temperature is 50-90℃ (preferably 50-80℃) and the pressure is atmospheric pressure, and / or, in step (3), the temperature is 180-300℃ (preferably 180-280℃, more preferably 180-250℃) and the pressure is 0.1-0.5MPa (preferably 0.1-0.3MPa), and / or, in step (3), let the initial time of the aforementioned hydrothermal treatment be t0, and the time when the reaction system of the aforementioned hydrothermal treatment reaches the maximum viscosity be tmax, Δt=tmax-t If 0, then the time of the aforementioned hydrothermal treatment (in hours) is from Δt+1 to Δt+20 (preferably from Δt+2 to Δt+12, especially from Δt+4 to Δt+8), and / or, in step (3), the time of the aforementioned hydrothermal treatment is 6-20 hours (preferably 8-12 hours).

[0020] 12. The manufacturing method of any of the foregoing states, wherein an additive (preferably selected from one or more of phosphorus, boron and titanium) is also added, and / or the weight content of the aforementioned additive, calculated as oxide, is 1-8 wt% (preferably 2-6 wt%) relative to 100 wt% of the total weight of the aforementioned silicon-aluminum material.

[0021] 13. A catalytic material comprising an active metal component and a silicon-aluminum material of any of the aforementioned states, or a silicon-aluminum material manufactured according to the manufacturing method of any of the aforementioned states.

[0022] 14. The catalytic material in any of the aforementioned states, wherein the aforementioned active metal component is a metal component with hydrogenation activity (preferably selected from at least one of Group VIB and Group VIII metals of the periodic table, especially at least one of Mo, W, Ni and Co), and / or, based on the total weight of the aforementioned catalytic material, the weight percentage content of the aforementioned active metal component (based on oxides) is 5-30 wt% (preferably 5-25 wt%).

[0023] 15. A hydrogenation method comprising the step of subjecting a hydrocarbon-containing material to a hydrogenation reaction in the presence of a catalytic material in any of the aforementioned states.

[0024] 16. The hydrogenation method for any of the aforementioned samples, wherein the aforementioned hydrocarbon-containing material is selected from at least one of diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry, and / or the reaction conditions for the aforementioned hydrogenation reaction include: a reaction pressure of 5-20 MPaG, a reaction temperature of 300-450°C, a liquid hourly space velocity of 0.1-1.5 h⁻¹, and a hydrogen-to-oil volume ratio of 100-1000.

[0025] [Technical Effects] [] (1) The silicon-aluminum material provided by the present invention has the characteristics of macroporous volume, mesoporous-macroporous two-level gradient channels, and high Brønsted acid content of molecular sieve. Moreover, the appearance of the aforementioned layered structure causes the aforementioned silicon-aluminum material to begin to show the crystal characteristics of molecular sieve. It has low impurity content (especially low sodium content) and is suitable for use as a catalyst material carrier, especially suitable for use as a carrier of heavy oil hydrogenation catalyst.

[0026] (2) In the method for manufacturing silicon-aluminum materials provided by the present invention, the silicon source is in contact with an acidic aluminum source, and preferably further in contact with an acid, so that the cations (such as sodium ions) encapsulated in the silica polymer within the ring or cage in the silicon source are released. The acidified silica micelles are adsorbed onto the aluminum hydroxide colloid, so that the sodium ions are effectively separated from the silica micelles. The addition of the acidic aluminum source plays a role in isolating the free cations, making the subsequent removal of cations (sodium ions) easier, greatly reducing the difficulty of subsequent washing to remove sodium and reducing the amount of washing water. More importantly, it can effectively remove cations (sodium ions), restore the acidic sites occupied by Na, and make the silicon-aluminum material have higher acidity.

[0027] (3) In the method for manufacturing silicon-aluminum materials provided by the present invention, the acidified silicon colloids are adsorbed on aluminum hydroxide colloids, providing crystal nuclei for subsequent reactions, promoting the growth of silicon-aluminum material grains, and facilitating the formation of silicon-aluminum materials with large pore volume and large pore size.

[0028] (4) In the method for manufacturing silicon-aluminum materials provided by the present invention, in a preferred case, the pH value of slurry B is adjusted by adding water-soluble carbonate. Then, during the treatment process at a certain temperature and pressure, the slurry system will change from a fluid state to a thixotropic state similar to a gel. The viscosity of the reaction system gradually increases and reaches a peak. After a period of treatment, it will change back to a fluid state. The viscosity of the reaction system will gradually decrease. During the process of changing to a thixotropic state similar to a gel, silicon-aluminum materials and water form a variable silicon-aluminum-oxygen network structure, which is beneficial to manufacturing silicon-aluminum materials with large pore volume.

[0029] (5) Under adjusted SiO2 / Al2O3 ratio and hydrothermal high-temperature conditions, the added carbonate promotes the directional growth of silicon-aluminum grain lamellar structure. As the processing time increases, the lamellar structure content increases. The formation of lamellar structure changes the bonding mode between Si and Al, promoting the increase of Brønsted acid content. Simple Explanation of the Diagram

[0030] Figure 1 is a SEM image of the silicon-aluminum material produced in Example 1 of this invention. Figure 2 is the XRD pattern of the silicon-aluminum material produced in Example 1 of the present invention (as hydrothermal treatment time, h1=8 hours, h2=16 hours). Figure 3 shows the nuclear magnetic resonance silicon spectrum of the silicon-aluminum material produced in Example 1 of this invention (as hydrothermal treatment time, h1=8 hours, h2=16 hours). Figure 4 shows the nuclear magnetic resonance aluminum spectrum of the silicon-aluminum material produced in Example 1 of this invention (as hydrothermal treatment time, h1=8 hours, h2=16 hours). Figure 5 is a small-angle XRD pattern of the silicon-aluminum material obtained in Example 1 of the present invention. Implementation

[0031] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited by these specific embodiments, but is determined by the scope of the patent application in the appendix.

[0032] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification shall have the meaning conventionally understood by one skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0033] When this specification uses the prefixes "familiar to those skilled in the art," "prior art," or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those not currently commonly used, but which will become generally recognized in the art as suitable for similar purposes.

[0034] In the context of this specification, unless otherwise explicitly stated otherwise, both the silicon-aluminum material and the catalyst undergo calcination treatment prior to measurement, sometimes referred to as "calcination process". Here, the aforementioned calcination conditions include: calcination at 600°C in an air atmosphere for a calcination time of 3 hours or more.

[0035] In the context of this specification, the pore volume, specific surface area, average pore size, and pore distribution of silicon-aluminum materials and catalysts are measured using a low-temperature nitrogen adsorption method.

[0036] In the context of this specification, the total acid, Brønsted acid, and Lewis acid of the silicon-aluminum materials and catalysts are measured using pyridine infrared adsorption.

[0037] In the context of this specification, the contents of sodium oxide, aluminum oxide and silicon dioxide in silicon-aluminum materials are measured by fluorescence analysis.

[0038] In the context of this specification, the active metal content of the catalyst is measured using spectrophotometry.

[0039] In the context of this specification, the wear index is measured using the air jet method.

[0040] In the context of this specification, X-ray diffraction (XRD) characterization was performed using a RIGAKU D / max2500 X-ray diffraction analyzer manufactured in Japan, with an operating voltage of 40 kV, an operating current of 40 mA, a scanning area of ​​10 (°) to 70 (°), a step size of 0.06 (°), and a scanning rate of 0.21 (°)·min⁻¹.

[0041] In the context of this specification, small-angle XRD characterization was performed using a RIGAKU D / max2500 X-ray diffraction analyzer manufactured in Japan, with an operating voltage of 40 kV, an operating current of 40 mA, a scanning area of ​​1.5 (°) to 8 (°), a step size of 0.01 (°), and a scanning rate of 0.02 (°)·min⁻¹.

[0042] In the context of this specification, sample morphology characterization (SEM) was performed using a JXM-7500F field emission scanning electron microscope manufactured by Nippon Egis Corporation, with an operating voltage of 6.5 eV, an accelerating voltage of 5.0 kV, and a magnification of 30,000x.

[0043] In the context of this specification, solid-state MAS NMR experiments of 27Al were performed on a Bruker-Avance III-400 solid-state NMR spectrometer, on which the resonance frequencies of 1H and 27Al nuclei are 399.33 MHz and 104.05 MHz, respectively. 27Al MAS NMR was performed on a 4 mm dual-resonance probe using a single-pulse plate rotation technique (<π / 12, 0.21 μs) with a pulse delay of 1 s. The chemical shifts of the 27Al spectra were calibrated using 1 M Al(NO₃)₃.

[0044] In the context of this specification, solid-state 29Si MAS NMR experiments were performed on a Varian Infinity plus-600 solid-state NMR spectrometer. On this spectrometer, the resonance frequencies of 1H and 29Si nuclei were 599.51 MHz and 120.35 MHz, respectively. 29Si MAS NMR was acquired using a single-pulse high-power decoupling technique on a 7.5 mm dual-resonance probe with a π / 2 pulse width of 6.1 μs, a pulse delay of 80 s, and a rotation speed of 5 kHz. The chemical shift of the 29Si spectrum was calibrated using kaolin (-91.5 ppm).

[0045] In the context of this specification, the average particle size of the silicon aluminum material was obtained by averaging 20 different images using SEM magnification up to 30,000 times.

[0046] In the context of this specification, the average particle size of the primary silicon-aluminum material was obtained by averaging 20 different images using SEM magnification up to 30,000 times.

[0047] In the context of this specification, the average length and average thickness of the sheet structure were obtained by averaging 20 different images using SEM magnification up to 30,000 times.

[0048] In the context of this specification, the viscosity of the reaction system can be measured by any method, as long as it can be effectively compared with the extension of reaction time, and there are no particular limitations.

[0049] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0050] In the context of this specification, any two or more embodiments of the present invention may be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0051] According to one embodiment of the present invention, the present invention relates to a silicon-aluminum material having a SiO2 / Al2O3 molar ratio of 0.8-1.5 (preferably 1.0-1.4).

[0052] According to one embodiment of the present invention, the aforementioned silicon-aluminum material comprises a sheet structure with an average length of 0.5-2 μm (preferably 0.5-1.5 μm) and an average thickness of 30-80 nm (preferably 30-75 nm). This can be confirmed by SEM images.

[0053] According to one embodiment of the present invention, the calcination form of the aforementioned silicon-aluminum material has an XRD pattern that is substantially as shown in Table I below. Table I [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 14.0 0.12-0.13 VS 24.3 0.18-0.19 VS 34.3 0.07-0.08 S 42.6 0.11-0.13 M 51.9 0.10-0.13 M 66.4 0.06-0.08 M Table I (Preferred) [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 14.0 0.117 VS 24.3 0.190 VS 34.3 0.078 S 42.6 0.121 M 51.9 0.106 M 66.4 0.079 M

[0054] According to one embodiment of the present invention, the aforementioned silicon-aluminum material preferably has an XRD pattern as shown in Table II below after calcination. Table II [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 13.9 0.12-0.13 VS 24.2 0.17-0.18 VS 31 0.36-0.38 M 34.4 0.08-0.10 S 39.9 0.08-0.10 M 42.5 0.11-0.12 M 51.6 0.12-0.13 W 57.8 0.14-0.16 W 66.4 0.07-0.09 W Table II (Preferred) [2θ] [d-] [spacing] [(nm)] [Relative Intensity] 13.9 0.125 VS 24.2 0.171 VS 31 0.373 M 34.4 0.077 S 39.9 0.086 M 42.5 0.114 M 51.6 0.124 W 57.8 0.142 W 66.4 0.079 W

[0055] According to the present invention, if the intensity value of the strongest diffraction peak in the aforementioned XRD pattern is 100, then W = weak, that is, relative intensity >0 to ≤20, M = moderate, that is, relative intensity >20 to ≤40, S = strong, that is, relative intensity >40 to ≤60, and VS = extremely strong, that is, relative intensity >60 to ≤100.

[0056] According to one embodiment of the present invention, the calcination form of the aforementioned silicon-aluminum material has an XRD pattern that is substantially as shown in FIG2.

[0057] According to one embodiment of the present invention, the pore volume of the aforementioned silicon-aluminum material is not less than 1.1 mL / g (preferably greater than 1.15 mL / g, more preferably 1.15-1.5 mL / g).

[0058] According to one embodiment of the present invention, the specific surface area of ​​the aforementioned silicon-aluminum material is 260-340 m² / g (preferably 260-310 m² / g).

[0059] According to one embodiment of the present invention, the pore distribution of the aforementioned silicon-aluminum material is as follows: the pore volume of pores with a diameter <10nm accounts for ≤5% of the total pore volume (preferably, the pore volume of pores with a diameter <10nm accounts for ≤3% of the total pore volume), the pore volume of pores with a diameter of 10-50nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of pores with a diameter of 10-50nm accounts for 70%-85% of the total pore volume), and the pore volume of pores with a diameter >50nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of pores with a diameter >50nm accounts for 12%-25% of the total pore volume).

[0060] According to one embodiment of the present invention, the average pore size of the aforementioned silicon-aluminum material is 14-23 nm (preferably 16-21 nm).

[0061] According to one embodiment of the present invention, the Brønsted acid content of the aforementioned silicon-aluminum material is greater than 0.08 mmol / g (preferably 0.1-0.2 mmol / g or 0.1-0.15 mmol / g).

[0062] According to one embodiment of the present invention, the ratio of Brønsted acid to Lewis acid in the aforementioned silicon-aluminum material is 0.2-0.8 (preferably 0.3-0.7).

[0063] According to one embodiment of the present invention, the Na₂O content of the aforementioned silicon-aluminum material is less than 0.3 wt% (preferably less than 0.2 wt%).

[0064] According to one embodiment of the present invention, the average particle size of the aforementioned silicon-aluminum material is 30-100 nm (preferably 30-80 nm).

[0065] According to one embodiment of the present invention, the aforementioned silicon-aluminum material has an absorption peak in its nuclear magnetic resonance silicon spectrum at a chemical shift of -87ppm to -89ppm, indicating that the silicon-oxygen tetrahedron is directly connected to three aluminum-oxygen tetrahedrons.

[0066] According to one embodiment of the present invention, the aforementioned silicon-aluminum material has an absorption peak near a chemical shift of 57 ppm in its nuclear magnetic resonance aluminum spectrum, indicating the presence of four-coordinated framework aluminum in the material.

[0067] According to one embodiment of the present invention, the calcination form of the aforementioned silicon-aluminum material has no diffraction peaks in the small-angle XRD pattern, indicating the absence of molecular sieve characteristic peaks.

[0068] According to one embodiment of the present invention, the aforementioned aluminum silicon material also includes a non-lamellar structure. This can also be confirmed by SEM images. Here, the aforementioned non-lamellar structure is an aggregate of multiple primary aluminum silicon particles, exhibiting the characteristics of amorphous aluminum silicon. In addition, the average particle size of the aforementioned primary aluminum silicon particles is generally 5-25 nm (preferably 10-25 nm).

[0069] According to one embodiment of the present invention, the proportion of the aforementioned layered structure is 3% or more (preferably 5% or more, more preferably 10-80% or 10-60%) based on the total volume of the aforementioned silicon-aluminum material.

[0070] According to one embodiment of the present invention, which is also related to a method for manufacturing a silicon-aluminum material, the aforementioned manufacturing method can be used to manufacture the silicon-aluminum material as described above in this specification.

[0071] According to one embodiment of the present invention, the aforementioned manufacturing method sequentially includes the following steps: (1) A mixture A is obtained by adding an acidic aluminum source to a silicon source. (2) The aforementioned mixture A was contacted with an alkaline aluminum source in the presence of water to obtain slurry B, and (3) The aforementioned slurry B is subjected to hydrothermal treatment to obtain the aforementioned silicon-aluminum material.

[0072] According to the present invention, in step (1), the acidic aluminum source is added to the silicon source, instead of the silicon source being added to the acidic aluminum source, otherwise a large amount of precipitation will be generated.

[0073] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (1), the aforementioned silicon source is a water-soluble or water-dispersible alkaline silicon-containing compound (preferably a water-soluble or water-dispersible alkaline inorganic silicon-containing compound, more preferably selected from one or more of water-soluble silicates, water glass, and silica sol, preferably water glass).

[0074] According to one embodiment of the present invention, in the aforementioned manufacturing method, the silicon source is used in the form of an aqueous solution. The concentration of the silicon source (as SiO₂) is 5-30 wt% (preferably 15-30 wt%) based on the total weight of the aqueous solution, and its modulus is generally 2.5-3.2.

[0075] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, especially a water-soluble inorganic strong acid aluminum salt, more preferably selected from one or more of aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate).

[0076] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned acidic aluminum source is used in the form of an aqueous solution, and the concentration of the aforementioned acidic aluminum source (calculated as Al₂O₃) is 30-100 g / L (preferably 30-80 g / L) based on the total weight of the aforementioned aqueous solution.

[0077] According to one embodiment of the present invention, in the aforementioned manufacturing method, the weight ratio of the aforementioned silicon source (calculated as SiO2) to the aforementioned acidic aluminum source (calculated as Al2O3) is 1:1-9:1 (preferably 1:1-7:1).

[0078] According to one embodiment of the present invention, in order to achieve better technical effects of the present invention in the aforementioned manufacturing method, especially to obtain silicon-aluminum material with larger pore volume and lower impurity content, acid is also added in step (1) (preferably, the aforementioned acidic aluminum source is added to the aforementioned silicon source, and then the aforementioned acid is added to obtain the aforementioned mixture A).

[0079] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably selected from one or more of sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid).

[0080] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned acid is used in the form of an aqueous solution. The concentration of the aforementioned acid is 2-6 wt% (preferably 2-5 wt%) based on the total weight of the aforementioned aqueous solution.

[0081] According to one embodiment of the present invention, in the aforementioned manufacturing method, the amount of acid added is such that the pH value of the aforementioned mixture A is 2-4 (preferably 3-4).

[0082] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (1), generally speaking, the aluminum content of the aforementioned mixture A, calculated as Al 2O 3, is 5-20g Al 2O 3 / L, and the silicon content, calculated as SiO 2, is 5-40g SiO 2 / L.

[0083] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (2), the aforementioned alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, especially an alkali metal aluminate, more preferably selected from one or more of sodium aluminate and potassium aluminate, preferably sodium aluminate).

[0084] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned alkaline aluminum source is used in the form of an aqueous solution. The concentration of the aforementioned alkaline aluminum source (calculated as Al₂O₃) is 130-350 g / L (preferably 150-250 g / L) based on the total weight of the aforementioned aqueous solution, and its caustic ratio is generally 1.15-1.35, preferably 1.15-1.30.

[0085] According to one embodiment of the present invention, in the aforementioned manufacturing method, the amount of the aforementioned mixture A is 40-80 vol% (preferably 45-75 vol%) based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water.

[0086] According to one embodiment of the present invention, in the aforementioned manufacturing method, the amount of the aforementioned alkaline aluminum source is 10-30 vol% (preferably 12-25 vol%) based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water.

[0087] According to one embodiment of the present invention, in the aforementioned manufacturing method, the amount of water used is 10-30 vol% (preferably 10-25 vol%) based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water.

[0088] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water sequentially or simultaneously (preferably, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water in a parallel flow manner).

[0089] According to one embodiment of the present invention, in the aforementioned manufacturing method, the flow rate of adding the aforementioned mixture A is 15-50 mL / min (preferably 20-40 mL / min).

[0090] According to one embodiment of the present invention, in the aforementioned manufacturing method, the addition flow rate of the aforementioned alkaline aluminum source is controlled so that the pH value of the aforementioned slurry B is maintained at 7.5-10.5 (preferably 8.0-10.5, more preferably 8.5-10.5).

[0091] According to one embodiment of the present invention, in order to achieve better technical effects of the present invention in the aforementioned manufacturing method, especially to obtain silicon-aluminum material with larger pore volume, water-soluble carbonate is also added in step (2) (preferably, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water, and then the aforementioned water-soluble carbonate is added to obtain the aforementioned slurry B).

[0092] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate, preferably sodium carbonate).

[0093] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned water-soluble carbonate is used in solid form.

[0094] According to one embodiment of the present invention, in the aforementioned manufacturing method, the amount of water-soluble carbonate added is such that the pH value of the aforementioned slurry B is 10.5-12 (preferably 11-12).

[0095] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (3), the aforementioned silicon-aluminum material is separated from the aforementioned hydrothermal treatment reaction system, washed until neutral, and then dried. Here, the aforementioned washing can be performed using washing methods commonly used in the art, preferably using deionized water, and more preferably at 50°C-90°C. In addition, the aforementioned separation can be performed using any means in the art that can achieve the separation of liquid and solid two-phase materials, such as filtration, centrifugation, etc. Specifically, in the present invention, filtration separation can be used for separation, and after separation, a solid phase material and a liquid phase material are obtained. The solid phase material is washed and dried to obtain the aforementioned silicon-aluminum material.

[0096] According to one embodiment of the present invention, in the aforementioned manufacturing method, the aforementioned drying conditions include: a drying temperature of 100-150°C and a drying time of 6-10 hours.

[0097] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (1), the temperature is 25-50°C (preferably 25-40°C) and the pressure is atmospheric pressure.

[0098] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (2), the temperature is 50-90°C (preferably 50-80°C) and the pressure is atmospheric pressure.

[0099] According to one embodiment of the present invention, in the aforementioned manufacturing method, in step (3), the temperature is 180-300°C (preferably 180-280°C, more preferably 180-250°C), and the pressure is 0.1-0.5 MPa (preferably 0.1-0.3 MPa).

[0100] According to one embodiment of the present invention, in order to achieve better technical effects of the present invention in the aforementioned manufacturing method, especially to obtain a higher proportion of layered structures, in step (3), let the initial time of the aforementioned hydrothermal treatment be t0, and the time when the reaction system of the aforementioned hydrothermal treatment reaches the maximum viscosity be tmax, Δt=tmax-t0, then the time of the aforementioned hydrothermal treatment (in hours) is from Δt+1 to Δt+20 (preferably from Δt+2 to Δt+12, especially from Δt+4 to Δt+8). Alternatively, from the perspective of simplifying the control of the manufacturing method, in step (3), the time of the aforementioned hydrothermal treatment can be 6-20 hours (preferably 8-12 hours).

[0101] According to one embodiment of the present invention, in the aforementioned manufacturing method, additives, such as one or more of P₂O₅, B₂O₃, or TiO₂, may be added as needed. For this purpose, these precursors may be added in the form of water-soluble inorganic salts during the reaction in step (1). Examples of such inorganic salts include borates, sulfates, or nitrates. Furthermore, the amount of these additives added can be adjusted arbitrarily according to the requirements of subsequent catalysts, etc. Generally, the weight content of these additives, calculated as oxides, is typically 1-8 wt%, preferably 2-6 wt%, relative to 100 wt% of the total weight of the aforementioned silicon-aluminum material.

[0102] According to one embodiment of the present invention, which also relates to a catalytic material, the material comprises an active metal component and a silicon-aluminum material as described above in this specification or a silicon-aluminum material manufactured according to the manufacturing method described above in this specification.

[0103] According to one embodiment of the present invention, the aforementioned active metal component is a metal component with hydrogenation activity (preferably selected from at least one of Group VIB and Group VIII metals of the periodic table, especially at least one of Mo, W, Ni and Co).

[0104] According to one embodiment of the present invention, the weight percentage content of the aforementioned active metal component (based on oxide) is 5-30 wt% (preferably 5-25 wt%) based on the total weight of the aforementioned catalytic material.

[0105] According to one embodiment of the present invention, which also relates to a hydrogenation method, the step of hydrogenating a hydrocarbon-containing material in the presence of a catalyst as described above in this specification is included.

[0106] According to one embodiment of the present invention, the aforementioned hydrocarbon-containing material is selected from at least one of diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry.

[0107] According to one embodiment of the present invention, the reaction conditions for the aforementioned hydrogenation reaction include: a reaction pressure of 5-20 MPaG, a reaction temperature of 300-450°C, a liquid hourly space velocity of 0.1-1.5 h⁻¹, and a hydrogen-to-oil volume ratio of 100-1000.

[0108] [Example] [] The present invention will be further illustrated in detail below with examples, but the present invention is not limited to these examples.

[0109] In the following examples and comparisons, all the pharmaceuticals and raw materials are either commercially available or manufactured based on existing knowledge.

[0110] [Example] [1] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0111] 1.44 L of a silica sol solution with a concentration of 50 g SiO₂ / L was measured and added to a container. Under stirring, 1 L of an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L was slowly added. During this process, aluminum hydroxide colloids were formed, but the solution remained in liquid form. Then, a 1 mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification treatment and obtaining mixture A.

[0112] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, mixture A was added to the reactor at a rate of 28 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, while maintaining a constant slurry temperature and pH within the reactor. After the reaction was complete, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain the dried sample PO-1. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material P-1, the properties of which are shown in Table 1.

[0113] According to the SEM images (Figure 1), the aforementioned aluminum silicon material contains both lamellar and non-lamellar structures, with an average particle size of 50 nm. The average length of the lamellar structure is 1.0 μm, the average thickness is 50 nm, and it accounts for 35% of the total volume of the aluminum silicon material. Measurements show that the SiO₂ / Al₂O₃ molar ratio of the aforementioned aluminum silicon material is 1.21. Furthermore, the XRD pattern of the calcined form of the aforementioned aluminum silicon material is shown in Figure 2, revealing a crystalline structure. With increasing hydrothermal treatment time (h₁ = 8 hours above, h₂ = 16 hours below), all diffraction peaks gradually intensify, indicating that the proportion of the lamellar structure in the aforementioned aluminum silicon material gradually increases. In the nuclear magnetic resonance silicon spectrum of the aforementioned aluminum silicon material (Figure 3), there is an absorption peak near a chemical shift of -87 ppm, and this absorption peak gradually intensifies with increasing hydrothermal treatment time (h₁ = 8 hours, h₂ = 16 hours). In the NMR aluminum spectrum of the aforementioned silicon-aluminum material (Figure 4), there is an absorption peak near the chemical shift of 57 ppm, and this absorption peak gradually becomes stronger with the extension of hydrothermal treatment time (h1=8 hours, h2=16 hours). The calcination form of the aforementioned silicon-aluminum material shows no diffraction peaks in the small-angle XRD pattern (Figure 5).

[0114] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PO-1 silicon-aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z1 with a particle size of 0.3-0.8mm.

[0115] Weigh 28.57 g of phosphoric acid and add 800 mL of distilled water. Then add 77.58 g of molybdenum oxide and 35.56 g of basic nickel carbonate in sequence. Heat and stir until completely dissolved, then dilute the solution to 1000 mL with distilled water to obtain solution L1. Saturate the support Z1 with solution L1, dry it at 110 °C for 2 h, and calcine it at 450 °C for 3 h to obtain catalyst C1. The specific properties are shown in Table 2.

[0116] [Example] [2] Other conditions are the same as in Example 1, except that: the silica sol is replaced with water glass solution, the concentration is adjusted to 58 g SiO 2 / L, the flow rate of the mixture A is 15 mL / min, and the deionized water in the reactor is heated to 80℃ to obtain a dried silica-alumina material sample PO-2. After calcination at 600℃ for 5 h, silica-alumina material P-2 is obtained, and its properties are shown in Table 1.

[0117] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.44 and comprises a sheet structure with an average length of 1.5 μm and an average thickness of 61 nm. This sheet structure accounts for 54% of the total volume of the aforementioned silicon-aluminum material.

[0118] Take 500g of the prepared PO-2 silicon aluminum dry sample, add 21.4g of acetic acid (85wt%) and 410g of water, mix evenly and then form into spheres. The spheres are then calcined at 600℃ for 5h to obtain carrier Z2 with a particle size of 0.3-0.8mm.

[0119] The support Z2 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 580℃ for 3 h to obtain catalyst C2. The specific properties are shown in Table 2.

[0120] [Example] [3] Other conditions are the same as in Example 1, except that: the pH of the reaction is controlled to be 9.0 by adjusting the flow rate of sodium aluminate; 53g of sodium carbonate is added to the reactor under stirring to adjust the pH to 11.0; the treatment temperature is 280℃; and the treatment pressure is 0.4MPa. A dry silicon-aluminum sample PO-3 is obtained. After calcination at 600℃ for 5h, silicon-aluminum material P-3 is obtained. Its properties are shown in Table 1.

[0121] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.19 and comprises a sheet structure with an average length of 1.4 μm and an average thickness of 56 nm. This sheet structure accounts for 40% of the total volume of the aforementioned silicon-aluminum material.

[0122] Take 500g of the prepared PO-3 silicon aluminum dry sample, add 10.0g of methylcellulose and 450g of water, mix evenly and form into spheres. Then, calcine the spheres at 600℃ for 5h to obtain carrier Z3 with a particle size of 0.3-0.8mm.

[0123] The support Z3 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 480℃ for 4 h to obtain catalyst C3. The specific properties are shown in Table 2.

[0124] [Example] [4] Other conditions are the same as in Example 1, except that: no 1 mol / L dilute sulfuric acid solution is added for acidification treatment, and a dry silicon-aluminum sample PO-4 is prepared. The sample is then calcined at 600℃ for 5 h to obtain silicon-aluminum material P-4, the properties of which are shown in Table 1.

[0125] Take 500g of the prepared PO-4 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z4 with a particle size of 0.3-0.8mm.

[0126] The support Z4 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst C4. The specific properties are shown in Table 2.

[0127] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.19 and comprises a sheet structure with an average length of 1.5 μm and an average thickness of 32 nm. This sheet structure accounts for 15% of the total volume of the aforementioned silicon-aluminum material.

[0128] [Example] [5] Other conditions are the same as in Example 1, except that the sodium aluminate caustic ratio is adjusted to 1.20 and the pH value of the gel is adjusted to 6.0 to prepare the silicon-aluminum dry sample PFO-5. The silicon-aluminum material P-5 is obtained by calcination at 600℃ for 5h, and its properties are shown in Table 1.

[0129] Take 500g of the prepared PO-5 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z5 with a particle size of 0.3-0.8mm.

[0130] The support Z5 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst C5. The specific properties are shown in Table 2.

[0131] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.19 and comprises a sheet structure with an average length of 1.0 μm and an average thickness of 20 nm. This sheet structure accounts for 10% of the total volume of the aforementioned silicon-aluminum material.

[0132] [Example] [6] Other conditions are the same as in Example 1, except that the water-soluble carbonate is replaced with sodium hydroxide to prepare a dry silicon-aluminum sample PFO-6. The sample is then calcined at 600℃ for 5 hours to obtain silicon-aluminum material P-6, the properties of which are shown in Table 1.

[0133] Take 500g of the prepared PO-6 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z6 with a particle size of 0.3-0.8mm.

[0134] The support Z6 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst C6. The specific properties are shown in Table 2.

[0135] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.19 and comprises a sheet structure with an average length of 0.8 μm and an average thickness of 15 nm. This sheet structure accounts for 5% of the total volume of the aforementioned silicon-aluminum material.

[0136] [Example] [7] Other conditions are the same as in Example 1, except that no water-soluble carbonate is added to adjust the pH value. The dried silicon aluminum sample PFO-7 is prepared and calcined at 600℃ for 5h to obtain silicon aluminum material P-7. Its properties are shown in Table 1.

[0137] Take 500g of the prepared PO-7 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z7 with a particle size of 0.3-0.8mm.

[0138] The support Z7 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst C7. The specific properties are shown in Table 2.

[0139] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.19, which prevents it from forming a layered structure.

[0140] [Example] [8] Other conditions are the same as in Example 1, except that: ammonium carbonate was added to adjust the pH value to 9.5, and a dry silicon-aluminum sample PFO-8 was prepared. After calcination at 600℃ for 5 h, silicon-aluminum material P-7 was obtained, and its properties are shown in Table 1.

[0141] Take 500g of the prepared PO-8 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z8 with a particle size of 0.3-0.8mm.

[0142] The support Z8 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst C8. The specific properties are shown in Table 2.

[0143] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.20 and comprises a sheet structure with an average length of 0.6 μm and an average thickness of 20 nm. This sheet structure accounts for 3% of the total volume of the aforementioned silicon-aluminum material.

[0144] [Example] [9] [(1)] [Silicon-aluminum material manufacturing] []

[0145] Prepare an aluminum sulfate solution with a concentration of 60 g Al₂O₃ / L and a water glass solution with a concentration of 75 g SiO₂ / L and a modulus of 3.0 for later use. Prepare a dilute nitric acid solution with a concentration of 2 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.30 and a concentration of 130 g Al₂O₃ / L for later use.

[0146] 1.4 L of a silica sol solution with a concentration of 80 g SiO₂ / L was added to a container. While stirring, 1 L of an aluminum sulfate solution with a concentration of 60 g Al₂O₃ / L was slowly added. During this process, aluminum hydroxide colloid was formed, but the solution remained in liquid form. Then, 2 mol / L dilute nitric acid solution was added to adjust the pH to 4.0, completing the acidification treatment and yielding mixture A.

[0147] 1000 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 60 °C, mixture A was added to the reactor at a rate of 20 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 9.5 by adjusting the sodium aluminate flow rate, while maintaining a constant temperature and pH of the slurry within the reactor. After the reaction was complete, 620 mL of sodium aluminate was added, and 84 g of ammonium bicarbonate was added to the reactor under stirring to adjust the pH to 11.0. The slurry was then placed in the reactor and treated at 230 °C and 0.5 MPa for 10 h under stirring. The treated slurry was washed with 90 °C hot water until neutral, and dried at 150 °C for 4 h to obtain dried sample PFO-9. This dried sample was then calcined at 600 °C for 5 h to obtain silicon-aluminum material P-9, the properties of which are shown in Table 1.

[0148] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.35 and comprises a sheet structure with an average length of 1.44 μm and an average thickness of 59 nm. This sheet structure accounts for 48% of the total volume of the aforementioned silicon-aluminum material.

[0149] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-9 silicon-aluminum dry sample, add 7g of guar gum powder, 31.3g of nitric acid (65wt%), and 410g of water, mix evenly and then form into spheres. The spheres are then calcined at 550℃ for 5h to obtain carrier Z9 with a particle size of 0.3-0.8mm.

[0150] Weigh 78.88 g of phosphoric acid and add 800 mL of distilled water. Then, add 185.68 g of molybdenum oxide and 50.81 g of basic cobalt carbonate sequentially. Heat and stir until completely dissolved, then dilute the solution to 2000 mL with distilled water to obtain solution L2. Saturate the support Z9 with solution L2, dry at 110 °C for 4 h, and calcine at 500 °C for 3 h to obtain catalyst C9. The specific properties are shown in Table 2.

[0151] [Example]

[10] Other conditions were the same as in Example 4, except that 600 mL of water was added to the reactor, the gelation temperature was adjusted to 80℃, the pH value was adjusted to 10.0, 20 g of sodium carbonate was added to the slurry after gelation to adjust the pH value to 10.5, the treatment temperature was 280℃, and the treatment pressure was 0.4 MPa, resulting in a dried silicon-aluminum sample PFO-10. After calcination at 600℃ for 5 h, silicon-aluminum material PF-10 was obtained, and its properties are shown in Table 1.

[0152] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.34 and comprises a sheet structure with an average length of 1.41 μm and an average thickness of 58 nm. This sheet structure accounts for 44% of the total volume of the aforementioned silicon-aluminum material.

[0153] Take 500g of the prepared PFO-10 silicon-aluminum dry sample, add 15g of guar gum powder and 470g of water, mix evenly and form into spheres, and calcine the spheres at 750℃ for 3h to obtain carrier Z10 with a particle size of 0.3-0.8mm.

[0154] The support Z10 was saturated with solution L2, dried at 110℃ for 2 h, and calcined at 550℃ for 3 h to obtain catalyst C10. The specific properties are shown in Table 2.

[0155] [Comparative Example] [1] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0156] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, aluminum sulfate and silica sol were added to the reactor at a rate of 25 mL / min and 28 mL / min, respectively. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the flow rate of sodium aluminate, while maintaining a constant temperature and pH of the slurry within the reactor. After the reaction was complete, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain the dried sample PFO-1. This dried sample was then calcined at 600 °C for 5 hours to obtain the silicon-aluminum material PF-1, the properties of which are shown in Table 1.

[0157] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20, and no lamellar structure can be seen in the SEM images; all of them are non-lamellar structures.

[0158] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-1 silicon-aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly, and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier ZF1 with a particle size of 0.3-0.8mm.

[0159] The support ZF1 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst CF1. The specific properties are shown in Table 2.

[0160] [Comparative Example] [2] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0161] Measure 1L of aluminum sulfate solution with a concentration of 50g Al₂O₃ / L into a container. Under stirring, slowly add 1.44L of silica sol solution with a concentration of 50g SiO₂ / L. A large amount of aluminum hydroxide gel is generated during the process, which has poor fluidity. Then, add 1mol / L dilute sulfuric acid solution to adjust the pH to 3.5 to complete the acidification treatment and obtain mixture A.

[0162] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, mixture A was added to the reactor at a rate of 28 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, while maintaining a constant slurry temperature and pH within the reactor. After the reaction was complete, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain the dried sample PFO-2. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material PF-2, the properties of which are shown in Table 1.

[0163] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-2 silicon-aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly, and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier ZF2 with a particle size of 0.3-0.8mm.

[0164] The support ZF2 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain the catalyst CF2. The specific properties are shown in Table 2.

[0165] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.19, and no lamellar structure can be seen in the SEM images; all of them are non-lamellar structures.

[0166] [Comparative Example] [3] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0167] 1.44 L of a silica sol solution with a concentration of 50 g SiO₂ / L was measured and added to a container. Under stirring, 1 L of an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L was slowly added. During this process, aluminum hydroxide colloids were formed, but the solution remained in liquid form. Then, a 1 mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification treatment and obtaining mixture A.

[0168] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, mixture A was added to the reactor at a rate of 28 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, while maintaining a constant temperature and pH in the reactor slurry. After the reaction was complete, 325 mL of sodium aluminate was added to the reactor, and 75 g of ammonium carbonate was added under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and washed with 90 °C hot water until neutral. It was then dried at 120 °C for 6 h to obtain the dried sample PFO-1. Calcination at 600 °C for 5 h yielded the silicon-aluminum material PF-3, the properties of which are shown in Table 1.

[0169] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20, and no lamellar structure can be seen in the SEM images; all of them are non-lamellar structures.

[0170] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-3 silicon-aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly, and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier ZF3 with a particle size of 0.3-0.8mm.

[0171] The support ZF3 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain the catalyst CF3. The specific properties are shown in Table 2.

[0172] [Comparative Example] [4] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0173] 1.44 L of a silica sol solution with a concentration of 50 g SiO 2 / L was added to a container. Under stirring, 325 mL of sodium aluminate solution was slowly added, followed by 1 mol / L dilute sulfuric acid solution to adjust the pH to 3.5. During the process, a large amount of aluminum hydroxide gel was generated, which had poor fluidity and formed suspension A.

[0174] 1 L of aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L was added. During this process, aluminum hydroxide colloid was formed, but the solution remained in liquid form. Then, 1 mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification treatment and yielding mixture A.

[0175] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, suspension A was added to the reactor at a rate of 28 mL / min. Simultaneously, 1 L of a 50 g Al₂O₃ / L aluminum sulfate solution was added concurrently. The pH of the reaction was controlled to 8.3 by adjusting the flow rate of sodium aluminate, while maintaining a constant temperature and pH in the reactor. After the reaction was complete, 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain dried sample PFO-4. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material PF-4, the properties of which are shown in Table 1.

[0176] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20, and no lamellar structure can be seen in the SEM images; all of them are non-lamellar structures.

[0177] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-4 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier ZF4 with a particle size of 0.3-0.8mm.

[0178] Weigh 28.57 g of phosphoric acid and add 800 mL of distilled water. Then add 77.58 g of molybdenum oxide and 35.56 g of basic nickel carbonate in sequence. Heat and stir until completely dissolved, then dilute the solution to 1000 mL with distilled water to obtain solution L1. Saturate the support ZF4 with solution L1, dry at 110 °C for 2 h, and calcine at 450 °C for 3 h to obtain catalyst CF4. The specific properties are shown in Table 2.

[0179] [Comparative Example] [5] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0180] 1.44 L of a silica sol solution with a concentration of 50 g SiO₂ / L was measured and added to a container. Under stirring, 1 L of an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L was slowly added. During this process, aluminum hydroxide colloids were formed, but the solution remained in liquid form. Then, a 1 mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification treatment and obtaining mixture A.

[0181] Mixture A was added to a 5000 mL reactor at a rate of 28 mL / min, while a prepared sodium aluminate solution was added concurrently. The pH of the reaction was controlled to be 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature and pH were kept constant in the reactor by water bath heating. After the reaction was completed, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with hot water at 90 °C until neutral, and dried at 120 °C for 6 hours to obtain the dried sample PFO-5. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material PF-5, the properties of which are shown in Table 1.

[0182] The SiO2 / Al2O3 molar ratio of the aforementioned silicon-aluminum material is 1.20.

[0183] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-5 silicon-aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly, and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier ZF5 with a particle size of 0.3-0.8mm.

[0184] Weigh 28.57 g of phosphoric acid and add 800 mL of distilled water. Then add 77.58 g of molybdenum oxide and 35.56 g of basic nickel carbonate in sequence. Heat and stir until completely dissolved, then dilute the solution to 1000 mL with distilled water to obtain solution L1. Saturate the support ZF5 with solution L1, dry at 110 °C for 2 h, and calcine at 450 °C for 3 h to obtain catalyst CF5. The specific properties are shown in Table 2.

[0185] [Comparative Example] [6] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0186] Weigh 72g of silica and add it to a container. Slowly add 1L of aluminum sulfate solution with a concentration of 50g Al₂O₃ / L and stir to form a suspension. Then add 1mol / L dilute sulfuric acid solution to adjust the pH to 3.5 to complete the acidification treatment, obtaining suspension A.

[0187] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, mixture A was added to the reactor at a rate of 28 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, while maintaining a constant slurry temperature and pH within the reactor. After the reaction was complete, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 8 hours (equivalent to Δt + 6 hours) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain the dried sample PFO-6. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material PF-6, the properties of which are shown in Table 1.

[0188] The aforementioned silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20, and no lamellar structure can be seen in the SEM images.

[0189] [Comparative Example] [7] [(1)] [Silicon-aluminum material manufacturing] [] Prepare an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L and a silica sol solution with a concentration of 50 g SiO₂ / L and a modulus of 2.8 for later use. Prepare a dilute sulfuric acid solution with a concentration of 1 mol / L for later use. Prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160 g Al₂O₃ / L for later use.

[0190] 1.44 L of a silica sol solution with a concentration of 50 g SiO₂ / L was measured and added to a container. Under stirring, 1 L of an aluminum sulfate solution with a concentration of 50 g Al₂O₃ / L was slowly added. During this process, aluminum hydroxide colloids were formed, but the solution remained in liquid form. Then, a 1 mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification treatment and obtaining mixture A.

[0191] 700 mL of deionized water was added to a 5000 mL reactor as bottom water. Stirring and heating were started. After the deionized water was heated to 80 °C, mixture A was added to the reactor at a rate of 28 mL / min. Simultaneously, a prepared sodium aluminate solution was added in a co-current flow. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, while maintaining a constant slurry temperature and pH within the reactor. After the reaction was complete, 325 mL of sodium aluminate was added, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was then placed in the reactor and treated at 210 °C and 0.4 MPa for 3 hours (equivalent to Δt + 1 hour) under stirring. The treated slurry was washed with 90 °C hot water until neutral and dried at 120 °C for 6 hours to obtain the dried sample PFO-7. This dried sample was then calcined at 600 °C for 5 hours to obtain silicon-aluminum material PF-7, the properties of which are shown in Table 1.

[0192] The aforementioned silicon-aluminum material has a SiO₂ / Al₂O₃ molar ratio of 1.20 and comprises a sheet structure with an average length of 0.85 μm and an average thickness of 25 nm. This sheet structure accounts for 2% of the total volume of the aforementioned silicon-aluminum material.

[0193] [] [(2)] [Hydrogenation Catalyst Manufacturing] [] Take 500g of the prepared PFO-7 silicon aluminum dry sample, add 10g of guar gum powder, 12.15g of citric acid, and 420g of water, mix evenly and then form into spheres. The spheres are then calcined at 650℃ for 4h to obtain carrier Z7 with a particle size of 0.3-0.8mm.

[0194] The support Z7 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ for 3 h to obtain catalyst CF7. The specific properties are shown in Table 2. [surface] [1] [Properties of silicon-aluminum materials] [(] [Example] [)] serial number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Pore ​​volume, mL / g 1.28 1.34 1.30 0.95 0.88 1.00 0.91 0.98 1.36 1.21 Specific surface area, m² / g 284 269 276 274 296 301 316 311 274 288 Average pore size / nm 18.01 19.90 18.84 13.86 11.89 13.26 11.50 12.58 19.83 16.80 Pore ​​distribution, % <10nm 2.98 2.18 2.36 5.06 18.41 6.87 10.14 7.23 2.08 3.42 10-50nm 79.57 77.51 79.15 84.62 71.36 77.79 80.92 79.23 78.60 79.57 >50nm 17.45 20.31 18.49 10.32 10.23 15.34 8.94 13.54 19.32 17.01 Na₂O,wt% 0.02 0.03 0.02 0.10 0.06 0.04 0.03 0.03 0.02 0.03 SiO₂ / Al₂O₃ Mohrbi 1.21 1.44 1.19 1.19 1.19 1.20 1.20 1.19 1.35 1.34 Brønsted acid, mmol / g 0.164 0.189 0.170 0.08 0.07 0.146 0.110 0.132 0.169 0.149 B / L 0.639 0.687 0.671 0.364 0.313 0.531 0.412 0.508 0.651 0.639 [surface] [1] [Properties of silicon-aluminum materials] [(] [Comparative example] [)] Number Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Pore ​​volume, mL / g 0.86 0.23 0.70 0.35 0.90 0.48 1.15 Specific surface area, m² / g 271 84 218 143 241 210 296 Average pore size / nm 12.69 10.91 12.82 9.79 14.93 9.13 15.54 Pore ​​distribution, % <10nm 13.81 78.11 28.31 59.23 4.23 69.43 2.31 10-50nm 77.28 21.48 44.55 28.61 72.34 16.19 81.46 >50nm 8.91 0.41 27.14 12.16 23.43 14.38 16.23 Na₂O,wt% 3.24 0.28 0.17 3.86 0.08 0.12 0.03 SiO₂ / Al₂O₃ Mohrbi 1.19 1.30 1.19 0.91 1.20 1.20 1.20 Brønsted acid, mmol / g 0.04 0.01 0.06 0.02 0.151 0.02 0.101 B / L 0.398 0.09 0.449 0.312 0.548 0.402 0.458 [surface] [2] [Properties of Catalysts] [(] [Example] [)] serial number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Specific surface area, m² / g 201 192 194 171 182 188 192 187 194 153 Pore ​​volume, mL / g 0.74 0.78 0.76 0.66 0.59 0.68 0.63 0.66 0.67 0.59 Total acid, mmol / g 0.512 0.556 0.531 0.342 0.302 0.412 0.398 0.402 0.564 0.423 Catalyst composition, wt% 14.7 15.9 15.6 15.4 12.9 14.4 13.1 14.0 13.8 15.4 MoO 3 5.89 5.93 5.90 5.93 5.84 5.86 5.84 5.87 12.89 12.83 NiO / CoO 1.39 1.43 1.38 1.41 1.36 1.39 1.40 1.42 2.10 2.21 P 0.50 0.58 0.52 0.53 0.51 0.54 0.56 0.53 1.38 1.40 Wear index, % 0.48 0.51 0.50 0.56 0.53 0.51 0.49 0.47 0.45 0.48 [surface] [2] [Properties of Catalysts] [(] [Comparative Example] [)] serial number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Specific surface area, m² / g 186 17 102 28 143 79 205 Pore ​​volume, mL / g 0.51 0.08 0.35 0.12 0.52 0.15 0.70 Total acid, mmol / g 0.161 0.02 0.188 0.101 0.338 0.113 0.426 Catalyst composition, wt% MoO 3 5.82 5.89 5.91 5.86 5.88 5.92 5.90 NiO / CoO 1.41 1.43 1.39 1.41 1.38 1.39 1.40 P 0.52 0.56 0.52 0.51 0.50 0.53 0.55 Wear index, % 3.87 2.17 1.89 4.65 0.60 0.64 0.53

[0195] The above catalysts were evaluated for activity in a high-pressure reactor. The evaluation of feedstock properties and evaluation conditions are shown in Table 3. The activity of Comparative Example 1 was set as 100, and the evaluation results of the other catalysts compared with the activity of Comparative Example 1 are shown in Table 4. [, , ] [] [surface] [3] [Properties and Evaluation Conditions of Feedstock Oil] [] project numerical values properties of crude oil sulfur,% 5.76 Carbon residue,% 24.86 Nickel + Vanadium / µg·g⁻¹ 214.38 >500℃ Residue oil yield, % 93.2 Process conditions Reaction temperature / ℃ 420 Reaction pressure / MPa 15 Oil volume ratio 13:1 Reaction time / h 1 [surface] [4] [Catalyst Evaluation Results] [(] [Example] [)] serial number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Relative hydrogenation activity HDS 162 173 168 136 132 138 136 138 206 196 HDCCR 140 144 141 119 116 121 120 122 179 174 HD(Ni+V) 182 196 193 128 118 123 121 126 151 159 Relative conversion rate of residue oil at >500℃ 143 148 145 121 119 122 120 122 158 151 [surface] [5] [Catalyst Evaluation Results] [(] [Comparative Example] [)] serial number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Relative hydrogenation activity HDS 100 52 101 61 123 68 136 HDCCR 100 37 105 44 114 45 124 HD(Ni+V) 100 78 108 84 125 88 129 Relative conversion rate of residue oil at 500℃ 100 90 104 93 113 94 136

[0196] As can be seen from the data in the tables, the silicon-aluminum material manufactured using this invention has a large pore volume, a small proportion of pores <10nm, low sodium oxide content, and high Brønsted acid content. The hydrogenation catalyst manufactured using this silicon-aluminum material, compared to the catalyst manufactured in the comparative example, increases the impurity removal rate and residue oil conversion rate, making it particularly suitable for use as a heavy oil or residue oil hydrogenation catalyst.

Claims

1. A silicon-aluminum material having a SiO2 / Al2O3 molar ratio of 0.8-1.5, comprising a sheet structure with an average length of 0.5-2 μm and an average thickness of 30-80 nm, and having an XRD pattern in its calcination state as shown in Table I below. Table I Wherein, if the intensity value of the strongest diffraction peak in the aforementioned XRD pattern is 100, then W = weak, i.e., relative intensity > 0 to ≤ 20, M = moderate, i.e., relative intensity > 20 to ≤ 40, S = strong, i.e., relative intensity > 40 to ≤ 60, VS = very strong, i.e., relative intensity > 60 to ≤ 100.

2. The silicon-aluminum material as claimed in claim 1, having a SiO2 / Al2O3 molar ratio of 1.0-1.4, and comprising a sheet structure with an average length of 0.5-1.5μm and an average thickness of 30-75nm.

3. The silicon-aluminum material as requested in item 1 has a pore volume of not less than 1.1 mL / g, and / or a specific surface area of ​​260-340 m² / g, and / or a pore distribution of ≤5% for pores with a diameter <10 nm, 65%-85% for pores with a diameter of 10-50 nm, 10%-30% for pores with a diameter >50 nm, and / or an average pore diameter of 14-23 nm.

4. The silicon-aluminum material as claimed in Item 1 has a pore volume of 1.15-1.5 mL / g, and / or a specific surface area of ​​260-310 m² / g, and / or a pore distribution of ≤3% for pores with a diameter <10 nm, 70%-85% for pores with a diameter of 10-50 nm, 12%-25% for pores with a diameter >50 nm, and / or an average pore diameter of 16-21 nm.

5. The silicon-aluminum material as requested in item 1, wherein the Brønsted acid content is greater than 0.08 mmol / g, and / or the ratio of Brønsted acid to Lewis acid is 0.2-0.8, and / or the Na₂O content is less than 0.3 wt%, and / or the silicon NMR spectrum has an absorption peak at a chemical shift of -88 ppm to -94 ppm, and the aluminum NMR spectrum has an absorption peak near a chemical shift of 57 ppm, and / or the calcined form has no diffraction peaks in the small-angle XRD pattern.

6. The silicon-aluminum material of claim 1 has a Brønsted acid content of 0.1-0.15 mmol / g, and / or a Brønsted acid to Lewis acid ratio of 0.3-0.7, and / or a Na2O content of less than 0.2 wt%.

7. The silicon-aluminum material of claim 1 also includes a non-lamellar structure, wherein the lamellar structure accounts for 10-80% of the total volume of the aforementioned silicon-aluminum material.

8. A method for manufacturing a silicon-aluminum material as claimed in claim 1, comprising the following steps in sequence: (1) adding an acidic aluminum source to a silicon source to obtain a mixture A; (2) contacting the mixture A with an alkaline aluminum source in the presence of water to obtain a slurry B; and (3) subjecting the slurry B to hydrothermal treatment to obtain the silicon-aluminum material, wherein in step (1), the silicon source is a water-soluble or water-dispersible alkaline silicon-containing compound, the acidic aluminum source is a water-soluble acidic aluminum-containing compound, and the weight ratio of the silicon source (based on SiO2) to the acidic aluminum source (based on Al2O3) is 1:1 to 9:1; in step (1), an acid is also added, the amount of acid added being such that the pH value of the mixture A is 2 to 4. In step (2), the aforementioned alkaline aluminum source is a water-soluble alkaline aluminum-containing compound, and the amount of the aforementioned alkaline aluminum source is 20-40 vol based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source and water.

9. The manufacturing method of claim 8, wherein in step (1), the silicon source is one or more selected from water-soluble silicates, water glass, and silica sol, and / or the silicon source is used in the form of an aqueous solution, and the concentration of the silicon source, calculated as SiO2, is 5-30 wt% based on the total weight of the aqueous solution, and / or the acidic aluminum source is one or more selected from aluminum sulfate, aluminum nitrate, and aluminum chloride, and / or the acidic aluminum source is used in the form of an aqueous solution, and the concentration of the acidic aluminum source, calculated as Al2O3, is 30-100 g / L based on the total weight of the aqueous solution, and / or the weight ratio of the silicon source, calculated as SiO2, to the acidic aluminum source, calculated as Al2O3, is 1:1-7:

1.

10. The manufacturing method of claim 8, wherein in step (1), the silicon source is water glass, and / or the silicon source is used in the form of an aqueous solution, and the concentration of the silicon source, calculated as SiO2, is 15-30 wt% based on the total weight of the aqueous solution, and / or the acidic aluminum source is aluminum sulfate, and / or the concentration of the acidic aluminum source, calculated as Al2O3, is 30-80 g / L based on the total weight of the aqueous solution.

11. The manufacturing method of claim 8, wherein in step (1), the aforementioned acidic aluminum source is added to the aforementioned silicon source, and then the aforementioned acid is added to obtain the aforementioned mixture A, and / or, the aforementioned acid is a water-soluble inorganic acid, and / or, the aforementioned acid is used in the form of an aqueous solution, and the concentration of the aforementioned acid is 2-6 wt% based on the total weight of the aforementioned aqueous solution, and / or, the amount of the aforementioned acid added makes the pH value of the aforementioned mixture A 3-4.

12. The manufacturing method of claim 8, wherein in step (1), the aforementioned acid is one or more selected from sulfuric acid, nitric acid, hydrochloric acid, and / or the aforementioned acid is used in the form of an aqueous solution, and the concentration of the aforementioned acid is 2-5 wt% based on the total weight of the aforementioned aqueous solution.

13. The manufacturing method of claim 8, wherein in step (2), the aforementioned alkaline aluminum source is a water-soluble alkaline inorganic aluminum-containing compound, and / or, the aforementioned alkaline aluminum source is used in the form of an aqueous solution, and the concentration of the aforementioned alkaline aluminum source, calculated as Al2O3, is 130-350 g / L based on the total weight of the aforementioned aqueous solution, and / or, the amount of the aforementioned mixture A is 40-70 vol% based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water, and / or, the amount of the aforementioned water is 10-20 vol% based on the total volume of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water, and / or, the aforementioned mixture A and the aforementioned alkaline aluminum source are added to the water sequentially or simultaneously, and / or, the addition flow rate of the aforementioned mixture A is 15-50 mL / min, and / or, the addition flow rate of the aforementioned alkaline aluminum source is controlled so that the pH value of the aforementioned slurry B is maintained at 7.5-10.

5.

14. The manufacturing method of claim 8, wherein in step (2), the aforementioned alkaline aluminum source is one or more selected from sodium aluminate and potassium aluminate, and / or, the aforementioned alkaline aluminum source is used in the form of an aqueous solution, and the concentration of the aforementioned alkaline aluminum source, calculated as Al2O3, is 150-250 g / L based on the total weight of the aforementioned aqueous solution, and / or, the amount of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water is 40-65 vol%, and / or, the amount of the aforementioned mixture A, the aforementioned alkaline aluminum source, and water is 40-65 vol%. The total volume of the alkaline aluminum source and water is 25-40 vol%, and / or the total volume of the mixture A, the alkaline aluminum source and water is 13-20 vol%, and / or the mixture A and the alkaline aluminum source are added to the water in a co-current manner, and / or the addition flow rate of the mixture A is 20-40 mL / min, and / or the addition flow rate of the alkaline aluminum source is controlled so that the pH value of the slurry B is maintained at 8.5-10.

5.

15. The manufacturing method of claim 8, wherein in step (2), a water-soluble carbonate is also added, and / or the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium, and / or the water-soluble carbonate is used in solid form, and / or the amount of the water-soluble carbonate added is such that the pH value of the slurry B is 10.5-12.

16. The manufacturing method of claim 8, wherein in step (2), the aforementioned mixture A and the aforementioned alkaline aluminum source are added to water, followed by the addition of a water-soluble carbonate to obtain the aforementioned slurry B, and / or the aforementioned water-soluble carbonate is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate, and / or the amount of the aforementioned water-soluble carbonate added makes the pH value of the aforementioned slurry B 11-12.

17. The manufacturing method of claim 8, wherein in step (3), the aforementioned silicon-aluminum material is separated from the aforementioned hydrothermal treatment reaction system, washed to neutral, and subsequently dried, and / or the aforementioned drying conditions include: The drying temperature is 100-150℃, and the drying time is 6-10 hours.

18. The manufacturing method of claim 8, wherein in step (1), the temperature is 25-50°C and the pressure is atmospheric pressure, and / or, in step (2), the temperature is 50-90°C and the pressure is atmospheric pressure, and / or, in step (3), the temperature is 180-300°C and the pressure is 0.1-0.5 MPa, and / or, in step (3), assuming the initial time of the aforementioned hydrothermal treatment is t0 and the time when the reaction system of the aforementioned hydrothermal treatment reaches the maximum viscosity is tmax, Δt=tmax-t0, then the time of the aforementioned hydrothermal treatment, in hours, is from Δt+1 to Δt+20, and / or, in step (3), the time of the aforementioned hydrothermal treatment is 6-20 hours.

19. The manufacturing method of claim 8, wherein in step (1), the temperature is 25-40°C, and / or, in step (2), the temperature is 50-80°C, and / or, in step (3), the temperature is 180-250°C, the pressure is 0.1-0.3 MPa, and / or, in step (3), assuming the initial time of the aforementioned hydrothermal treatment is t0, and the time when the reaction system of the aforementioned hydrothermal treatment reaches the maximum viscosity is tmax, Δt=tmax-t0, then the time of the aforementioned hydrothermal treatment, in hours, is from Δt+4 to Δt+8, and / or, in step (3), the time of the aforementioned hydrothermal treatment is 8-12 hours.

20. The manufacturing method of claim 8, wherein an additive is also added, and / or the weight content of the aforementioned additive, calculated as oxide, is 1-8 wt% relative to 100 wt% of the total weight of the aforementioned silicon-aluminum material.

21. The manufacturing method of claim 8, wherein the aforementioned additive is one or more selected from phosphorus, boron and titanium, and / or the weight content of the aforementioned additive, calculated as oxide, is 2-6 wt% relative to 100 wt% of the total weight of the aforementioned silicon-aluminum material.

22. A catalytic material comprising an active metal component and a silicon-aluminum material as claimed in claim 1 or a silicon-aluminum material manufactured according to the manufacturing method of claim 8.

23. The catalytic material of claim 22, wherein the aforementioned active metal component is a metal component with hydrogenation activity, and / or, based on the total weight of the aforementioned catalytic material, the aforementioned active metal component, as an oxide, has a weight percentage content of 5-30 wt%.

24. The catalytic material of claim 22, wherein the aforementioned active metal component is at least one selected from Group VIB and Group VIII metals of the periodic table, and / or, based on the total weight of the aforementioned catalytic material, the aforementioned active metal component, as an oxide, has a weight percentage content of 5-25 wt%.

25. A hydrogenation method comprising the step of hydrogenating a hydrocarbon-containing material in the presence of a catalyst as described in claim 22.

26. The hydrogenation method of claim 25, wherein the aforementioned hydrocarbon-containing material is selected from at least one of diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry, and / or the reaction conditions for the aforementioned hydrogenation reaction include: The reaction pressure is 5-20 MPaG, the reaction temperature is 300-450℃, the liquid hourly space velocity is 0.1-1.5 h⁻¹, and the hydrogen-to-oil volume ratio is 100-1000.

27. The silicon-aluminum material of claim 1 has an XRD pattern in its calcination state that is substantially as shown in Table II below, Table II.

28. The silicon-aluminum material of claim 1, having a calcined form having an XRD pattern substantially as shown in Figure 2, wherein h2 > h1.

Images