Aluminosilicate material for use as a catalyst support for heavy oil hydrogenation, its preparation and its application

Abstract

Provided are a silicon-aluminium material, a manufacturing method therefor, and an application thereof. The silicon-aluminium material has an SiO2 / Al2O3 molar ratio of 0.8-1.5, and contains a lamellar structure with an average length of 0.5-2 μm and an average thickness of 30-80 nm, and the calcined form thereof has a specific XRD pattern. The silicon-aluminium material has the characteristics of a large pore volume, a mesoporous-macroporous two-stage gradient pore channel, and high molecular sieve B acid content, displays the crystal characteristics of a molecular sieve, has a low impurity content, and is suitable for use as a catalytic material carrier, in particular being suitable for use as a carrier for heavy oil hydrogenation catalysts.

Description

Silicon-aluminum material comprising a lamellar structure, its manufacturing method and application Technical Field

[0001] The present invention belongs to the technical field of catalytic materials and relates to a silicon-aluminum material, a manufacturing method and an application thereof. Background Art

[0002] Molecular sieves are incorporated into hydrocracking catalyst supports to enhance their cracking performance. However, due to the large molecular weight and high nitrogen content of residual oil feedstock, molecular sieve catalysts are prone to rapid deactivation, limiting their application in residue hydrocracking processes. Macroporous silica-alumina materials offer a suitable pore structure and acidity, good hydrothermal stability, and strong cracking performance, making them particularly suitable for residue hydrocracking processes.

[0003] The manufacturing methods of silicon-aluminum materials generally include sol-gel method, kneading method, impregnation method, etc. Macroporous silicon-aluminum materials are usually manufactured by sol-gel method, which generally uses water glass or silica sol as silicon source. The difficulty in manufacturing macroporous silicon-aluminum materials is that as the silicon dioxide content increases, the pore volume of the silicon-aluminum material gradually decreases, while the sodium content increases significantly. Sodium, as an impurity of silicon-aluminum materials, needs to be removed. Generally, the sodium content needs to be less than 0.5%. Usually, the industry uses more expensive silica sol as a silicon source to reduce the number of subsequent washings to remove sodium, or uses ion exchange to achieve sodium removal, but these sodium removal methods greatly increase the manufacturing cost of silicon-aluminum materials, have poor economic efficiency, and limit their large-scale industrial promotion and application.

[0004] CN201710382457.7 discloses a highly active silicon-aluminum material and a method for manufacturing the same. The active silicon-aluminum material contains 15-45% silicon and 55-85% aluminum by weight of oxides, and has a total BET specific surface area of ​​300-500 m 2 / g, the proportion of micropore specific surface area to the total BET specific surface area is ≯8%, and the average pore diameter is 5-18nm; c represents the Al / Si atomic ratio of the material surface measured by the XPS method, and d represents the Al / Si atomic ratio of the material bulk measured by the XRF method, where c / d = 1.2-1.9.

[0005] CN201710630418.4 discloses a medium- and macroporous silicon-aluminum material and its manufacturing method. The medium- and macroporous silicon-aluminum material has an anhydrous chemical formula of (0-0.3) Na2O: (2-18) Al2O3: (82-98) SiO2, based on the weight of the oxides; its pore volume is 0.8-2 mL / g, and its specific surface area is 150-350 m 2 / g, a maximum pore size of 30-100nm, and a B / L acid ratio of 0.8-2.0. The silicon-aluminum material of the present invention has the characteristics of high pore volume, large pore size, and high B / L acid ratio. At the same time, the manufacturing method of the present invention uses an inexpensive silicon-aluminum source and does not require the addition of an organic template, which is low-cost and simple to operate. The ammonium salt exchange used in the method provided by the present invention is to exchange the solid precipitate obtained by filtration at a weight ratio of precipitate (dry basis): ammonium salt: H2O = 1: (0.1-1): (5-10) at room temperature to 100°C for 1-3 times, each exchange lasting 0.3-1 hour, until the sodium content in the solid precipitate is less than 0.3wt% by weight. The ammonium salt used for the 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, a manufacturing method, and its application. The silicon-aluminum material has a chemical composition, as measured by XRF, of (0-0.3)Na2O·(50-80)SiO2·(20-50)Al2O3, calculated by oxide weight. The XRD spectrum of the silicon-aluminum material exhibits only a single diffuse diffraction peak at 25°-27°, a visible pore diameter between 20-50 nm, and x / y = 0.55-0.75, where x represents the Si / Al atomic ratio as measured by XPS, and y represents the Si / Al atomic ratio as measured by XRF.

[0007] Summary of the Invention

[0008] The inventors of the present invention have discovered that the difficulty in preparing macroporous alumina-silicon materials lies in the fact that as the silica content increases, the pore volume of the alumina-silicon materials gradually decreases, while the sodium content significantly increases. Therefore, it is crucial to effectively reduce the sodium content while ensuring a large pore volume. However, in the prior art methods for manufacturing alumina-silicon materials, in order to reduce the impurity content of the alumina-silicon materials, especially the sodium content, ion exchange methods are used, which is a cumbersome process and increases the manufacturing cost of the alumina-silicon materials. The inventors of the present invention have also discovered that the industry generally uses more expensive silica sol as a silicon source to reduce the number of subsequent washings to remove sodium, or uses ion exchange to remove sodium. However, these sodium removal methods greatly increase the preparation cost of the alumina-silicon materials, are less economical, and limit their large-scale industrial application. Therefore, the inventors of the present invention believe that how to prepare macroporous alumina-silicon materials while reducing the cost of sodium removal is an effective way to prepare alumina-silicon materials with excellent performance and low price. To this end, the inventors of the present invention have discovered a new type of alumina-silicon material after diligent research. The present invention is based on this discovery.

[0009] Specifically, the present invention relates to the following aspects.

[0010] 1. A silicon-aluminum material having a SiO2 / Al2O3 molar ratio of 0.8-1.5 (preferably 1.0-1.4), comprising a lamellar structure having 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 FIG2 in its calcined form,

[0011] Table I

[0012] 2θd-spacing (nm) relative intensity 14.00.12-0.13VS24.30.18-0.19VS34.30.07-0.08S42.60.11-0.13M51.90.10-0.13M66.40.06-0.08M

[0013] Table II

[0014] 2θd-spacing (nm) relative intensity 13.90.12-0.13VS24.20.17-0.18VS310.36-0.38M34.40.08-0.10S39.90.08-0.10M42.50.11-0.12M51.60.12-0.13W57.80.14-0.16W66.40.07-0.09W

[0015] Assuming that the intensity value of the strongest diffraction peak in the XRD pattern is 100, then W = weak, i.e., relative intensity >0 to ≤20, M = medium, i.e., relative intensity >20 to ≤40, S = strong, i.e., relative intensity >40 to ≤60, and VS = very strong, i.e., relative intensity >60 to ≤100.

[0016] 2. The silicon-aluminum material according to any of the above aspects has 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 a specific surface area of ​​260-340 m 2 / g (preferably 260-310m 2 / g), and / or, its pore distribution is: the pore volume of pores with a pore diameter of less than 10 nm accounts for ≤5% of the total pore volume (preferably, the pore volume of pores with a pore diameter of less than 10 nm accounts for ≤3% of the total pore volume), the pore volume of pores with a pore diameter of 10-50 nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of pores with a pore diameter of 10-50 nm accounts for 70%-85% of the total pore volume), the pore volume of pores with a pore diameter of greater than 50 nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of pores with a pore diameter of greater than 50 nm accounts for 12%-25% of the total pore volume), and / or, its average pore diameter is 14-23 nm (preferably 16-21 nm).

[0017] 3. The silicon-aluminum material according to any of the preceding aspects, wherein the content of B acid is greater than 0.08 mmol / g (preferably 0.1-0.2 mmol / g or 0.1-0.15 mmol / g), and / or the ratio of B acid to L acid is 0.2-0.8 (preferably 0.3-0.7), and / or the content of Na2O is less than 0.3 wt% (preferably less than 0.2 wt%), and / or in its silicon nuclear magnetic resonance spectrum, there is an absorption peak at a chemical shift of -87 ppm to -89 ppm, and in its aluminum nuclear magnetic resonance spectrum, there is an absorption peak at a chemical shift of approximately 57 ppm, and / or the calcined form has no diffraction peaks in the low-angle XRD pattern.

[0018] 4. The silicon-aluminum material described in any of the above aspects further comprises a non-lamellar structure, wherein the proportion of the lamellar structure is greater than 3% (preferably greater than 5%, more preferably 10-80% or 10-60%) based on the total volume of the silicon-aluminum material.

[0019] 5. A method for manufacturing a silicon-aluminum material, comprising the following steps in sequence:

[0020] (1) adding an acidic aluminum source to a silicon source to obtain a mixture A,

[0021] (2) contacting the mixture A with a basic aluminum source in the presence of water to obtain a slurry B, and

[0022] (3) The slurry B is subjected to hydrothermal treatment to obtain the silicon-aluminum material.

[0023] 6. The manufacturing method according to any of the preceding aspects, wherein in step (1), the 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 one or more selected from water-soluble silicates, water glass, and silica sol, preferably water glass), and / or the silicon source is used in the form of an aqueous solution, and the concentration of the silicon source (in terms of SiO2) is 5-30 wt% (preferably 15-30 wt%) based on the total weight of the aqueous solution, and / or the 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 one or more selected from aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate), 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 (preferably 30-80 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 1:1-9:1 (preferably 1:1-7:1).

[0024] 7. The manufacturing method according to any of the preceding aspects, wherein in step (1), an acid is further added (preferably the acidic aluminum source is added to the silicon source, and then the acid is added to obtain the mixture A), and / or the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid), and / or the acid is used in the form of an aqueous solution, and the concentration of the acid is 2-6 wt% (preferably 2-5 wt%) based on the total weight of the aqueous solution, and / or the amount of the acid added is such that the pH value of the mixture A is 2-4 (preferably 3-4).

[0025] 8. The manufacturing method according to any of the preceding aspects, wherein in step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, in particular an alkali metal metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate), and / or the alkaline aluminum source is used in the form of an aqueous solution, and the concentration of the alkaline aluminum source (in terms of Al2O3) is 130-350 g / L (preferably 150-250 g / L) based on the total weight of the aqueous solution, and / or the amount of the mixture A is 40-80 vol% (preferably 45-75 vol%) based on the total volume of the mixture A, the alkaline aluminum source and water, and / or the amount of the mixture A is 50-80 vol% (preferably 50-60 vol%) based on the total volume of the mixture A, the alkaline aluminum source and water. Based on the total volume, the amount of the alkaline aluminum source is 10-30 vol% (preferably 12-25 vol%), and / or, based on the total volume of the mixture A, the alkaline aluminum source and water, the amount of water is 10-30 vol% (preferably 10-25 vol%), and / or, the mixture A and the alkaline aluminum source are added to the water successively or simultaneously (preferably, the mixture A and the alkaline aluminum source are added to the water in parallel), and / or, the addition flow rate of the mixture A is 15-50 mL / min (preferably 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 7.5-10.5 (preferably 8.0-10.5, more preferably 8.5-10.5).

[0026] 9. The manufacturing method according to any one of the preceding aspects, wherein in step (2), a water-soluble carbonate is further added (preferably, the mixture A and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added to obtain the slurry B), and / or the 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 water-soluble carbonate is used in the form of a solid, and / or the amount of the water-soluble carbonate added is such that the pH value of the slurry B is 10.5-12 (preferably 11-12).

[0027] 10. The manufacturing method described in any of the preceding aspects, wherein in step (3), the silicon-aluminum material is separated from the reaction system of the hydrothermal treatment (such as by filtration or centrifugation), washed to neutrality, and then dried, and / or the drying conditions include: a drying temperature of 100-150°C and a drying time of 6-10 hours.

[0028] 11. The production method according to any of the preceding aspects, wherein in step (1), the temperature is 25-50°C (preferably 25-40°C) and the pressure is normal pressure, and / or, in step (2), the temperature is 50-90°C (preferably 50-80°C) and the pressure is normal pressure, and / or, 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), and / or, in step (3), the initial time of the hydrothermal treatment is t0, and the time when the reaction system reaches the maximum viscosity during the hydrothermal treatment is t max , Δt=t max -t0, the time of the hydrothermal treatment (in h) is from Δt+1 to Δt+20 (preferably from Δt+2 to Δt+12, in particular from Δt+4 to Δt+8), and / or, in step (3), the time of the hydrothermal treatment is 6-20 h (preferably 8-12 h).

[0029] 12. The manufacturing method described in any of the preceding aspects, wherein an auxiliary agent (preferably one or more selected from phosphorus, boron and titanium) is further added, and / or the weight content of the auxiliary agent in terms of oxide is 1-8wt% (preferably 2-6wt%), relative to the total weight of the silicon-aluminum material 100wt%.

[0030] 13. A catalytic material comprising an active metal component and the silicon-aluminum material described in any one of the preceding aspects or the silicon-aluminum material manufactured according to the manufacturing method described in any one of the preceding aspects.

[0031] 14. The catalytic material according to any of the preceding aspects, wherein the active metal component is a metal component having hydrogenation activity (preferably selected from at least one of Group VIB metals and Group VIII metals of the Periodic Table, in particular selected from at least one of Mo, W, Ni and Co), and / or, based on the total weight of the catalytic material, the weight percentage content of the active metal component (in terms of oxide) is 5-30 wt% (preferably 5-25 wt%).

[0032] 15. A hydrogenation method comprising the step of subjecting a hydrocarbon-containing material to a hydrogenation reaction in the presence of the catalytic material according to any one of the preceding aspects.

[0033] 16. The hydrogenation method according to any of the preceding aspects, wherein the hydrocarbon-containing material is selected from at least one of diesel, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry, and / or the reaction conditions of the 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 , the hydrogen-to-oil volume ratio is 100-1000.

[0034] Technical Effects

[0035] (1) The silicon-aluminum material provided by the present invention has the characteristics of large pore volume, mesopore-macropore two-level gradient pore channels, and high molecular sieve B acid content. The appearance of the lamellar structure causes the silicon-aluminum material to begin to show the crystal characteristics of molecular sieves, with low impurity content (especially low sodium content), and is suitable for use as a catalytic material carrier, especially suitable for use as a carrier for heavy oil hydrogenation catalyst.

[0036] (2) In the method for manufacturing the silicon-aluminum material provided by the present invention, the silicon source is contacted with the acidic aluminum source, and in particular, in the preferred case, further contacted with an acid, so that the cations (sodium ions, etc.) encapsulated in the ring or cage of the silica polymer in the silicon source are released, and the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, so that the sodium ions are effectively separated from the silica gel group. The addition of the acidic aluminum source plays a role in isolating the free cations, making the subsequent removal of the cations (sodium ions) easier, greatly reducing the difficulty of subsequent washing and removing sodium and reducing the amount of water used for washing. More importantly, the cations (sodium ions) can be effectively removed, and the acidic sites occupied by Na can be restored, so that the silicon-aluminum material has higher acidity.

[0037] (3) In the method for manufacturing the silicon-aluminum material provided by the present invention, the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, providing a crystal nucleus for the subsequent reaction, promoting the increase of the grain size of the manufactured silicon-aluminum material, and being conducive to the formation of a silicon-aluminum material with a large pore volume and a large pore size.

[0038] (4) In the method for manufacturing the silicon-aluminum material provided by the present invention, under preferred circumstances, the pH value of the slurry B is adjusted by adding a water-soluble carbonate, and then during the treatment process at a certain temperature and a certain pressure, the morphology of the slurry system changes from the initial fluid state to a thixotropic state similar to a gel, which is manifested as the viscosity of the reaction system gradually increasing and reaching a peak value. After a period of treatment, it changes back to a fluid state, which is manifested as the viscosity of the reaction system gradually decreasing. In the process of changing to a thixotropic state similar to a gel, the silicon-aluminum material and water form a variable silicon-aluminum-oxygen network structure, which is conducive to the manufacture of a silicon-aluminum material with a large pore volume.

[0039] (5) Under the conditions of adjusting the SiO2 / Al2O3 ratio and high hydrothermal temperature, the added carbonate promotes the directional growth of the lamellar structure of silicon and aluminum grains. As the treatment time increases, the lamellar structure content increases. The formation of the lamellar structure changes the bonding mode of Si and Al, promoting the increase of the B acid content. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG1 is a SEM photograph of the silicon-aluminum material manufactured in Example 1 of the present invention.

[0041] FIG2 is an XRD pattern of the silicon-aluminum material obtained in Example 1 of the present invention (as the hydrothermal treatment time, h1=8 hours, h2=16 hours).

[0042] FIG3 is a silicon nuclear magnetic resonance spectrum of the silicon-aluminum material obtained in Example 1 of the present invention (as the hydrothermal treatment time, h1=8 hours, h2=16 hours).

[0043] FIG4 is the NMR aluminum spectrum of the silicon-aluminum material obtained in Example 1 of the present invention (as the hydrothermal treatment time, h1=8 hours, h2=16 hours).

[0044] FIG5 is a small-angle XRD pattern of the silicon-aluminum material manufactured in Example 1 of the present invention. DETAILED DESCRIPTION

[0045] The specific embodiments of the present invention are described in detail below. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0046] 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 have the meanings commonly understood by those skilled in the art. In the event of conflict, the definitions in this specification will prevail.

[0047] When this specification uses the prefix "well known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, the objects introduced by the prefix include those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become generally recognized in the art to be suitable for similar purposes.

[0048] In the context of this specification, unless otherwise specified, both the silicon-aluminum material and the catalyst are calcined prior to measurement, sometimes referred to as "calcined form." Here, the calcination conditions include: calcination at 600°C for at least 3 hours in an air atmosphere.

[0049] In the context of this specification, the pore volume, specific surface area, average pore diameter and pore distribution of the silica-alumina material and catalyst are measured using a low-temperature nitrogen adsorption method.

[0050] In the context of this specification, the total acid, B acid and L acid of the silica-alumina material and catalyst are measured using the pyridine infrared adsorption method.

[0051] In the context of this specification, the sodium oxide, aluminum oxide and silicon dioxide contents of the silicon-aluminum material are measured using fluorescence analysis.

[0052] In the context of this specification, the active metal content of a catalyst is measured spectrophotometrically.

[0053] In the context of this specification, the wear index is measured using the air jet method.

[0054] In the context of this specification, X-ray diffraction (XRD) characterization was performed using a D / max2500 X-ray diffraction analyzer produced by RIGAKU, Japan, with an operating voltage of 40 kV, an operating current of 40 mA, a scanning range of 10 (°) to 70 (°), a step size of 0.06 (°), and a scanning rate of 0.21 (°)·min -1 .

[0055] In the context of this specification, the small-angle XRD characterization was performed using a D / max2500 X-ray diffraction analyzer produced by RIGAKU, Japan, with an operating voltage of 40 kV, an operating current of 40 mA, a scanning range of 1.5 (°) to 8 (°), a step size of 0.01 (°), and a scanning rate of 0.02 (°)·min -1

[0056] In the context of this specification, sample morphology characterization (SEM) was performed using a JXM-7500F field emission scanning electron microscope produced by JEOL Ltd., with an operating voltage of 6.5 eV, an acceleration voltage of 5.0 kV, and a magnification of 30,000 times.

[0057] In the context of this specification, solid-state nuclear magnetic 27 Al MAS NMR experiments were performed on a Bruker-Avance III-400 solid-state NMR spectrometer. 1 H and 27 The resonance frequencies of the Al nucleus are 399.33 and 104.05 MHz, respectively. 27 Al MAS NMR was performed using a single pulse small plate rotation (<π / 12, 0.21 μs) technique on a 4 mm double resonance probe with a pulse delay of 1 s. The chemical shift of the 27Al spectrum was calibrated using 1 M Al(NO3)3.

[0058] In the context of this specification, solid-state nuclear magnetic 29 Si MAS NMR experiments were performed on a Varian Infinity plus-600 solid-state NMR spectrometer. 1 H and 29 The resonant frequencies of the Si core are 599.51 and 120.35 MHz, respectively. 29 Si MAS NMR was acquired using a single-pulse high-power decoupling technique on a 7.5 mm double-resonance probe with a π / 2 pulse width of 6.1 μs, a pulse delay time of 80 s, and a rotation speed of 5 kHz. 29 The chemical shift of Si spectrum was calibrated with kaolin (-91.5 ppm).

[0059] In the context of this specification, the average particle size of the silicon-aluminum material is obtained by taking an average of 20 different images magnified 30,000 times by SEM.

[0060] In the context of this specification, the average particle size of the primary particles of the silicon-aluminum material is obtained by taking an average of 20 different images magnified 30,000 times by SEM.

[0061] In the context of this specification, the average length and average thickness of the lamellar structure are obtained by taking 20 different pictures magnified 30,000 times by SEM.

[0062] In the context of this specification, the viscosity of the reaction system can be measured by any method without particular limitation, as long as an effective comparison can be made with the extension of the reaction time.

[0063] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight and pressure is gauge pressure.

[0064] In the context of this specification, any two or more embodiments of the present invention may be arbitrarily combined, and the technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the scope of protection of the present invention.

[0065] According to one embodiment of the present invention, a silicon-aluminum material is provided, wherein the SiO2 / Al2O3 molar ratio thereof is 0.8-1.5 (preferably 1.0-1.4).

[0066] According to one embodiment of the present invention, the silicon-aluminum material comprises a lamellar 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), which can be confirmed by SEM images.

[0067] According to one embodiment of the present invention, the calcined form of the silicon-aluminum material has an XRD pattern substantially as shown in Table I below.

[0068] Table I

[0069] 2θd-spacing (nm) relative intensity 14.00.12-0.13VS24.30.18-0.19VS34.30.07-0.08S42.60.11-0.13M51.90.10-0.13M66.40.06-0.08M

[0070] Table 1 (preferred)

[0071] 2θd-spacing (nm) relative intensity 14.00.117 VS 24.30.190 VS 34.30.078 S 42.60.121 M 51.90.106 M 66.40.079 M

[0072] According to one embodiment of the present invention, the calcined form of the silicon-aluminum material preferably has an XRD pattern substantially as shown in Table II below.

[0073] Table II

[0074] 2θd-spacing (nm) relative intensity 13.90.12-0.13VS24.20.17-0.18VS310.36-0.38M34.40.08-0.10S39.90.08-0.10M42.50.11-0.12M51.60.12-0.13W57.80.14-0.16W66.40.07-0.09W

[0075] Table II (preferred)

[0076] 2θd-spacing (nm) relative intensity 13.90.125VS24.20.171VS310.373M34.40.077S39.90.086M42.50.114M51.60.124W57.80.142W66.40.079W

[0077] According to the present invention, assuming that the intensity value of the strongest diffraction peak in the XRD pattern is 100, then W = weak, i.e., relative intensity >0 to ≤20, M = medium, i.e., relative intensity >20 to ≤40, S = strong, i.e., relative intensity >40 to ≤60, and VS = very strong, i.e., relative intensity >60 to ≤100.

[0078] According to one embodiment of the present invention, the calcined form of the silicon-aluminum material has an XRD pattern substantially as shown in FIG. 2 .

[0079] According to one embodiment of the present invention, the pore volume of the 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).

[0080] According to one embodiment of the present invention, the specific surface area of ​​the silicon-aluminum material is 260-340m 2 / g (preferably 260-310m 2 / g).

[0081] According to one embodiment of the present invention, the pore distribution of the silicon-aluminum material is: the pore volume of pores with a pore diameter of less than 10 nm accounts for ≤5% of the total pore volume (preferably, the pore volume of pores with a pore diameter of less than 10 nm accounts for ≤3% of the total pore volume), the pore volume of pores with a pore diameter of 10-50 nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of pores with a pore diameter of 10-50 nm accounts for 70%-85% of the total pore volume), and the pore volume of pores with a pore diameter of more than 50 nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of pores with a pore diameter of more than 50 nm accounts for 12%-25% of the total pore volume).

[0082] According to one embodiment of the present invention, the average pore size of the silicon-aluminum material is 14-23 nm (preferably 16-21 nm).

[0083] According to one embodiment of the present invention, the B acid content of the silicon-aluminum material is greater than 0.08 mmol / g (preferably 0.1-0.2 mmol / g or 0.1-0.15 mmol / g).

[0084] According to one embodiment of the present invention, the ratio of B acid to L acid of the silicon-aluminum material is 0.2-0.8 (preferably 0.3-0.7).

[0085] According to one embodiment of the present invention, the Na2O content of the silicon-aluminum material is less than 0.3 wt% (preferably less than 0.2 wt%).

[0086] According to one embodiment of the present invention, the average particle size of the silicon-aluminum material is 30-100 nm (preferably 30-80 nm).

[0087] According to one embodiment of the present invention, the silicon-aluminum material has an absorption peak at a chemical shift of -87 ppm to -89 ppm in its silicon nuclear magnetic resonance spectrum, indicating that the silicon-oxygen tetrahedron is directly connected to the three aluminum-oxygen tetrahedrons.

[0088] According to one embodiment of the present invention, the 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 tetracoordinated framework aluminum in the material.

[0089] According to one embodiment of the present invention, the calcined form of the silicon-aluminum material has no diffraction peaks in the small-angle XRD pattern, indicating that there are no characteristic peaks of molecular sieves.

[0090] According to one embodiment of the present invention, the silicon-aluminum material further comprises a non-lamellar structure. This can also be confirmed by SEM images. Here, the non-lamellar structure is an aggregate of multiple silicon-aluminum primary particles, exhibiting characteristics of amorphous silicon-aluminum. In addition, the average particle size of the silicon-aluminum primary particles is generally 5-25 nm (preferably 10-25 nm).

[0091] According to one embodiment of the present invention, based on the total volume of the silicon-aluminum material, the proportion of the lamellar structure is greater than 3% (preferably greater than 5%, more preferably 10-80% or 10-60%).

[0092] According to one embodiment of the present invention, a method for manufacturing a silicon-aluminum material is also provided. The manufacturing method can be used to manufacture the silicon-aluminum material as described above in this specification.

[0093] According to one embodiment of the present invention, the manufacturing method comprises the following steps in sequence:

[0094] (1) adding an acidic aluminum source to a silicon source to obtain a mixture A,

[0095] (2) contacting the mixture A with a basic aluminum source in the presence of water to obtain a slurry B, and

[0096] (3) The slurry B is subjected to hydrothermal treatment to obtain the silicon-aluminum material.

[0097] According to the present invention, in step (1), the acidic aluminum source is added to the silicon source rather than adding the silicon source to the acidic aluminum source, which would otherwise result in the generation of a large amount of precipitates.

[0098] According to one embodiment of the present invention, in the manufacturing method, in step (1), the 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 one or more selected from water-soluble silicates, water glass, and silica sol, preferably water glass).

[0099] According to one embodiment of the present invention, in the manufacturing method, the silicon source is used in the form of an aqueous solution. The concentration of the silicon source (calculated 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.

[0100] According to one embodiment of the present invention, in the manufacturing method, the 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 one or more selected from aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate).

[0101] According to one embodiment of the present invention, in the manufacturing method, 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 (preferably 30-80 g / L) based on the total weight of the aqueous solution.

[0102] According to one embodiment of the present invention, in the manufacturing method, the weight ratio of the silicon source (calculated as SiO2) to the acidic aluminum source (calculated as Al2O3) is 1:1-9:1 (preferably 1:1-7:1).

[0103] According to one embodiment of the present invention, in the manufacturing method, in order to achieve a better technical effect of the present invention, especially to obtain a silicon-aluminum material with a larger pore volume and a lower impurity content, in step (1), an acid is also added (preferably, the acidic aluminum source is added to the silicon source, and then the acid is added to obtain the mixture A).

[0104] According to one embodiment of the present invention, in the production method, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, preferably sulfuric acid).

[0105] According to one embodiment of the present invention, in the manufacturing method, the acid is used in the form of an aqueous solution. Based on the total weight of the aqueous solution, the concentration of the acid is 2-6 wt% (preferably 2-5 wt%).

[0106] According to one embodiment of the present invention, in the manufacturing method, the amount of the acid added is such that the pH value of the mixture A is 2-4 (preferably 3-4).

[0107] According to one embodiment of the present invention, in the manufacturing method, in step (1), generally speaking, the aluminum content of the mixture A is 5-20 gAl2O3 / L in terms of Al2O3, and the silicon content is 5-40 gSiO2 / L in terms of SiO2.

[0108] According to one embodiment of the present invention, in the manufacturing method, in step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, in particular an alkali metal aluminate, more preferably one or more selected from sodium aluminate and potassium aluminate, preferably sodium aluminate).

[0109] According to one embodiment of the present invention, in the production method, the basic aluminum source is used in the form of an aqueous solution. The concentration of the basic aluminum source (calculated as Al2O3) is 130-350 g / L (preferably 150-250 g / L) based on the total weight of the aqueous solution, and the caustic ratio is generally 1.15-1.35, preferably 1.15-1.30.

[0110] According to one embodiment of the present invention, in the manufacturing method, the amount of the mixture A is 40-80 vol% (preferably 45-75 vol%) based on the total volume of the mixture A, the basic aluminum source and water.

[0111] According to one embodiment of the present invention, in the manufacturing method, the amount of the basic aluminum source is 10-30 vol% (preferably 12-25 vol%) based on the total volume of the mixture A, the basic aluminum source and water.

[0112] According to one embodiment of the present invention, in the manufacturing method, the amount of water used is 10-30 vol% (preferably 10-25 vol%) based on the total volume of the mixture A, the basic aluminum source and water.

[0113] According to one embodiment of the present invention, in the manufacturing method, the mixture A and the alkaline aluminum source are added to water sequentially or simultaneously (preferably, the mixture A and the alkaline aluminum source are added to water in parallel).

[0114] According to one embodiment of the present invention, in the manufacturing method, the addition flow rate of the mixture A is 15-50 mL / min (preferably 20-40 mL / min).

[0115] According to one embodiment of the present invention, in the manufacturing method, the addition flow rate of the basic aluminum source is controlled so that the pH value of the slurry B is maintained at 7.5-10.5 (preferably 8.0-10.5, more preferably 8.5-10.5).

[0116] According to one embodiment of the present invention, in the manufacturing method, in order to achieve a better technical effect of the present invention, especially to obtain a silicon-aluminum material with a larger pore volume, in step (2), a water-soluble carbonate is also added (preferably, the mixture A and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added to obtain the slurry B).

[0117] According to one embodiment of the present invention, in the manufacturing method, the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate, preferably sodium carbonate).

[0118] According to one embodiment of the present invention, in the production method, the water-soluble carbonate is used in the form of a solid.

[0119] According to one embodiment of the present invention, in the manufacturing method, the amount of the water-soluble carbonate added is such that the pH value of the slurry B is 10.5-12 (preferably 11-12).

[0120] According to one embodiment of the present invention, in the manufacturing method, in step (3), the silicon-aluminum material is separated from the reaction system of the hydrothermal treatment, washed to neutrality, and then dried. Here, the washing can adopt a conventional washing method in the art, preferably washing with deionized water, and more preferably washing at 50°C-90°C. In addition, the separation can adopt any means in the art that can achieve separation of liquid-solid two-phase materials, such as filtration, centrifugal separation, etc. Specifically, in the present invention, filtration separation can be used for separation, and after separation, solid phase material and liquid phase material are obtained. The solid phase material is washed and dried to obtain the silicon-aluminum material.

[0121] According to one embodiment of the present invention, in the manufacturing method, the drying conditions include: a drying temperature of 100-150° C., and a drying time of 6-10 hours.

[0122] According to one embodiment of the present invention, in the manufacturing method, in step (1), the temperature is 25-50° C. (preferably 25-40° C.), and the pressure is normal pressure.

[0123] According to one embodiment of the present invention, in the manufacturing method, in step (2), the temperature is 50-90° C. (preferably 50-80° C.), and the pressure is normal pressure.

[0124] According to one embodiment of the present invention, in the manufacturing method, in step (3), the temperature is 180-300°C (preferably 180-280°C, more preferably 180-250°C), and the pressure is 0.1-0.5MPa (preferably 0.1-0.3MPa).

[0125] According to one embodiment of the present invention, in the manufacturing method, in order to achieve a better technical effect of the present invention, especially to obtain a lamellar structure with a higher ratio, in step (3), the initial time of the hydrothermal treatment is t0, and the time when the reaction system of the hydrothermal treatment reaches the maximum viscosity is t max , Δt=t max -t0, the time of the hydrothermal treatment (in hours) is from Δt+1 to Δt+20 (preferably from Δt+2 to Δt+12, particularly 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 hydrothermal treatment can be 6-20 hours (preferably 8-12 hours).

[0126] According to one embodiment of the present invention, in the manufacturing method, an auxiliary agent, such as one or more of P2O5, B2O3 or TiO2, can be added according to actual needs. To this end, these precursors can be added in the form of water-soluble inorganic salts during the reaction of step (1). As the inorganic salts, specific examples include borates, sulfates or nitrates. In addition, the amount of these auxiliary agents added can be arbitrarily adjusted according to the requirements of subsequent catalysts, etc. In general, the weight content of these auxiliary agents in terms of oxides is generally 1-8wt%, preferably 2-6wt%, relative to the total weight of the silicon-aluminum material 100wt%.

[0127] According to one embodiment of the present invention, a catalytic material is also provided, comprising an active metal component and the silicon-aluminum material as described above in this specification or the silicon-aluminum material manufactured according to the manufacturing method as described above in this specification.

[0128] According to one embodiment of the present invention, the active metal component is a metal component having hydrogenation activity (preferably at least one selected from Group VIB metals and Group VIII metals of the Periodic Table, in particular at least one selected from Mo, W, Ni and Co).

[0129] According to one embodiment of the present invention, based on the total weight of the catalytic material, the weight percentage content of the active metal component (calculated as oxide) is 5-30 wt% (preferably 5-25 wt%).

[0130] According to one embodiment of the present invention, there is also provided a hydrogenation method, comprising the step of subjecting a hydrocarbon-containing material to a hydrogenation reaction in the presence of the catalytic material as described above in this specification.

[0131] According to one embodiment of the present invention, the hydrocarbon-containing material is selected from at least one of diesel, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry oil.

[0132] According to one embodiment of the present invention, the reaction conditions of the 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 , the hydrogen-to-oil volume ratio is 100-1000.

[0133] Example

[0134] The present invention is further described in detail below with reference to examples, but the present invention is not limited to these examples.

[0135] In the following examples and comparative examples, all pharmaceutical agents and raw materials are either commercially available or can be manufactured according to existing knowledge.

[0136] Example 1

[0137] (1) Silicon aluminum material manufacturing

[0138] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0139] 1.44L of 50gSiO2 / L silica sol solution was added to a container. While stirring, 1L of 50gAl2O3 / L aluminum sulfate solution was slowly added. During this process, aluminum hydroxide colloid was generated, but the solution remained liquid. Next, 1mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification process to obtain mixed solution A.

[0140] 700 mL of deionized water was added to a 5000 mL reactor as bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80°C, mixed solution A was added to the reactor at 28 mL / min. At the same time, the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, the amount of sodium aluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210°C, the treatment pressure was 0.4 MPa, and the treatment was carried out for 8 hours (equivalent to Δt + 6 hours). The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6 hours, and the dried sample PO-1 was obtained. The silicon-alumina material P-1 was calcined at 600°C for 5 hours, and its properties are shown in Table 1.

[0141] According to the SEM photograph (Figure 1), the silicon-aluminum material includes a lamellar structure and a non-lamellar structure, and its average particle size is 50nm. The average length of the lamellar structure is 1.0μm, the average thickness is 50nm, and it accounts for 35% of the total volume of the silicon-aluminum material. According to measurements, the SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.21. In addition, the XRD spectrum of the calcined form of the silicon-aluminum material is shown in Figure 2, showing the crystal structure, and with the extension of the hydrothermal treatment time (h1=8 hours above, h2=16 hours below), each diffraction peak gradually becomes stronger, indicating that the proportion of the lamellar structure in the silicon-aluminum material gradually increases. In the nuclear magnetic resonance silicon spectrum of the silicon-aluminum material (Figure 3), there is an absorption peak near the chemical shift of -87ppm, and with the extension of the hydrothermal treatment time (h1=8 hours, h2=16 hours), the absorption peak gradually becomes stronger. The aluminum nuclear magnetic resonance spectrum of the silicon-aluminum material (Figure 4) shows an absorption peak near a chemical shift of 57 ppm, and this absorption peak gradually intensifies with increasing hydrothermal treatment time (h1 = 8 hours, h2 = 16 hours). The calcined silicon-aluminum material exhibits no diffraction peaks in the low-angle XRD pattern (Figure 5).

[0142] (2) Manufacturing of hydrogenation catalysts

[0143] Take 500g of the manufactured PO-1 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z1 with a particle size of 0.3-0.8mm.

[0144] 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. Heat and stir until completely dissolved. Then, dilute the solution to 1000 mL with distilled water to obtain Solution L1. Carrier Z1 was saturated with Solution L1, dried at 110°C for 2 hours, and calcined at 450°C for 3 hours to obtain Catalyst C1. Specific properties are shown in Table 2.

[0145] Example 2

[0146] Other conditions were the same as those in Example 1, except that the silica sol was replaced with a water glass solution, the concentration was adjusted to 58 g SiO2 / L, the flow rate of the mixed solution A was 15 mL / min, and the deionized water in the reactor was heated to 80°C to obtain a dry sample of the silicon-alumina material PO-2, which was calcined at 600°C for 5 h to obtain the silicon-alumina material P-2, whose properties are shown in Table 1.

[0147] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.44 and comprises a lamella structure with an average length of 1.5 μm and an average thickness of 61 nm, and the lamella structure accounts for 54% of the total volume of the silicon-aluminum material.

[0148] Take 500g of the manufactured PO-2 silica-alumina dry sample, add 21.4g of acetic acid (85wt%) and 410g of water, mix evenly and then form into balls. The balled sample is calcined at 600℃ for 5h to obtain a carrier Z2 with a particle size of 0.3-0.8mm.

[0149] The support Z2 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 580°C for 3 h to obtain the catalyst C2. The specific properties are shown in Table 2.

[0150] Example 3

[0151] Other conditions were the same as those in Example 1, except that the pH of the reaction was controlled to 9.0 by adjusting the flow rate of sodium aluminate, 53 g of sodium carbonate was added to the reactor under stirring to adjust the pH to 11.0, the treatment temperature was 280°C, and the treatment pressure was 0.4 MPa to obtain a dried silicon-alumina sample PO-3, which was calcined at 600°C for 5 h to obtain a silicon-alumina material P-3, the properties of which are shown in Table 1.

[0152] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.19 and comprises a lamella structure with an average length of 1.4 μm and an average thickness of 56 nm, and the lamella structure accounts for 40% of the total volume of the silicon-aluminum material.

[0153] Take 500g of the manufactured PO-3 silica-alumina dry sample, add 10.0g of methyl cellulose and 450g of water, mix evenly and form into balls. The balled sample is calcined at 600°C for 5h to obtain a carrier Z3 with a particle size of 0.3-0.8mm.

[0154] The support Z3 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 480°C for 4 h to obtain the catalyst C3. The specific properties are shown in Table 2.

[0155] Example 4

[0156] Other conditions were the same as in Example 1, except that 1 mol / L dilute sulfuric acid solution was not added for acidification. A dry silicon-alumina sample PO-4 was prepared and calcined at 600° C. for 5 h to obtain silicon-alumina material P-4, the properties of which are shown in Table 1.

[0157] Take 500g of the manufactured PO-4 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain a carrier Z4 with a particle size of 0.3-0.8mm.

[0158] The support Z4 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst C4. The specific properties are shown in Table 2.

[0159] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.19, and the material comprises a lamella structure with an average length of 1.5 μm and an average thickness of 32 nm, and the lamella structure accounts for 15% of the total volume of the silicon-aluminum material.

[0160] Example 5

[0161] Other conditions were the same as those in Example 1, except that the sodium aluminate caustic ratio was adjusted to 1.20, the colloid pH was adjusted to 6.0, and a silicon-alumina dry sample PFO-5 was prepared. The silicon-alumina material P-5 was obtained by calcining at 600°C for 5 h. The properties of the material are shown in Table 1.

[0162] Take 500g of the manufactured PO-5 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z5 with a particle size of 0.3-0.8mm.

[0163] The support Z5 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst C5. The specific properties are shown in Table 2.

[0164] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.19 and comprises a lamella structure with an average length of 1.0 μm and an average thickness of 20 nm, and the lamella structure accounts for 10% of the total volume of the silicon-aluminum material.

[0165] Example 6

[0166] Other conditions were the same as in Example 1, except that the water-soluble carbonate was replaced with sodium hydroxide to prepare a dried alumina-silica sample PFO-6, which was calcined at 600°C for 5 h to obtain alumina-silica material P-6, the properties of which are shown in Table 1.

[0167] Take 500g of the manufactured PO-6 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z6 with a particle size of 0.3-0.8mm.

[0168] The support Z6 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst C6. The specific properties are shown in Table 2.

[0169] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.19 and comprises a lamella structure with an average length of 0.8 μm and an average thickness of 15 nm, and the lamella structure accounts for 5% of the total volume of the silicon-aluminum material.

[0170] Example 7

[0171] Other conditions were the same as in Example 1, except that no water-soluble carbonate was added to adjust the pH value. A dried silica-alumina sample PFO-7 was prepared and calcined at 600°C for 5 h to obtain silica-alumina material P-7, the properties of which are shown in Table 1.

[0172] Take 500g of the manufactured PO-7 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z7 with a particle size of 0.3-0.8mm.

[0173] The support Z7 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst C7. The specific properties are shown in Table 2.

[0174] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.19, and it cannot form a lamellar structure.

[0175] Example 8

[0176] Other conditions were the same as in Example 1, except that ammonium carbonate was added to adjust the pH to 9.5, and a dried alumina-silica sample PFO-8 was prepared. The alumina-silica material P-7 was obtained by calcining at 600°C for 5 h. The properties of the alumina-silica material are shown in Table 1.

[0177] Take 500g of the manufactured PO-8 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z8 with a particle size of 0.3-0.8mm.

[0178] The carrier Z8 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst C8. The specific properties are shown in Table 2.

[0179] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20 and comprises a lamella structure with an average length of 0.6 μm and an average thickness of 20 nm, and the lamella structure accounts for 3% of the total volume of the silicon-aluminum material.

[0180] Example 9

[0181] (1) Silicon aluminum material manufacturing

[0182] Prepare an aluminum sulfate solution with a concentration of 60gAl2O3 / L and a water glass solution with a modulus of 3.0. Prepare a dilute nitric acid solution with a concentration of 2mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.30 and a concentration of 130gAl2O3 / L.

[0183] 1.4L of 80gSiO2 / L silica sol solution was added to a container. While stirring, 1L of 60gAl2O3 / L aluminum sulfate solution was slowly added. During this process, aluminum hydroxide colloid was generated, but the solution remained liquid. A 2mol / L dilute nitric acid solution was then added to adjust the pH to 4.0, completing the acidification process to obtain mixed solution A.

[0184] A 5000mL reactor was filled with 1000mL of deionized water as the bottom water. Stirring and heating were initiated. After the deionized water was heated to 60°C, Mixed Solution A was added to the reactor at a rate of 20mL / min. The prepared sodium metaaluminate solution was added concurrently. The pH of the reaction was controlled at 9.5 by adjusting the sodium metaaluminate flow rate, while maintaining the slurry temperature and pH in the reactor constant. After the reaction was completed, 620mL of sodium metaaluminate was added to the reactor, and the pH was adjusted to 11.0 by adding 84g of ammonium bicarbonate to the reactor under stirring. The slurry was placed in the reactor and treated at a temperature of 230°C and a pressure of 0.5MPa for 10 hours under stirring. The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 150°C for 4 hours, and dried to obtain the dried sample PFO-9. This was then calcined at 600°C for 5 hours to obtain the silicon-alumina material P-9. Its properties are shown in Table 1.

[0185] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.35 and comprises a lamella structure with an average length of 1.44 μm and an average thickness of 59 nm, and the lamella structure accounts for 48% of the total volume of the silicon-aluminum material.

[0186] (2) Manufacturing of hydrogenation catalysts

[0187] Take 500g of the manufactured PFO-9 silica-alumina dry sample, add 7g of sesbania powder and 31.3g of nitric acid (65wt%), and 410g of water, mix well and then form into balls. The balled sample is calcined at 550℃ for 5h to obtain a carrier Z9 with a particle size of 0.3-0.8mm.

[0188] 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. Heat and stir until completely dissolved. Then, dilute the solution to 2000 mL with distilled water to obtain Solution L2. Support Z9 was saturated with Solution L2, dried at 110°C for 4 hours, and calcined at 500°C for 3 hours to obtain Catalyst C9. Specific properties are shown in Table 2.

[0189] Example 10

[0190] Other conditions were the same as those in Example 4, except that 600 mL of water was added to the reactor, the gelation temperature was adjusted to 80° C., 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° C., the treatment pressure was 0.4 MPa, and a dried silica-alumina sample PFO-10 was obtained. The silica-alumina material PF-10 was obtained by calcining at 600° C. for 5 h. The properties of the silica-alumina material are shown in Table 1.

[0191] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.34 and comprises a lamella structure with an average length of 1.41 μm and an average thickness of 58 nm, and the lamella structure accounts for 44% of the total volume of the silicon-aluminum material.

[0192] Take 500g of the prepared PFO-10 silica-alumina dry sample, add 15g of sesbania powder and 470g of water, mix well and form into balls. The balled sample is calcined at 750°C for 3h to obtain carrier Z10 with a particle size of 0.3-0.8mm.

[0193] The support Z10 was saturated with the solution L2, dried at 110°C for 2 h, and calcined at 550°C for 3 h to obtain the catalyst C10. The specific properties are shown in Table 2.

[0194] Comparative Example 1

[0195] (1) Silicon aluminum material manufacturing

[0196] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8 for use; prepare a sodium aluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L for use.

[0197] A 5000mL reactor was filled with 700mL of deionized water as the bottom water. Stirring and heating were initiated. After the deionized water was heated to 80°C, aluminum sulfate and silica sol were added to the reactor at 25mL / min and 28mL / min, respectively. The prepared sodium metaaluminate solution was added concurrently. The reaction pH was controlled at 8.3 by adjusting the sodium metaaluminate flow rate, and the slurry temperature and pH in the reactor were maintained constant. After the reaction was completed, 325mL of sodium metaaluminate was added, and 75g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The slurry was placed in a reactor and stirred at a temperature of 210°C and a pressure of 0.4MPa for 8 hours (equivalent to Δt + 6 hours). The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6 hours, and dried to obtain the dried sample PFO-1. This was then calcined at 600°C for 5 hours to obtain the silica-alumina material PF-1. Its properties are shown in Table 1.

[0198] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM photo, and all of them are non-lamellar structures.

[0199] (2) Manufacturing of hydrogenation catalysts

[0200] Take 500g of the prepared PFO-1 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain the carrier ZF1 with a particle size of 0.3-0.8mm.

[0201] The support ZF1 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst CF1. The specific properties are shown in Table 2.

[0202] Comparative Example 2

[0203] (1) Silicon aluminum material manufacturing

[0204] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0205] Measure 1L of aluminum sulfate solution with a concentration of 50gAl2O3 / L into a container, and slowly add 1.44L of silica sol solution with a concentration of 50gSiO2 / L under stirring. During the process, a large amount of aluminum hydroxide gel with poor fluidity is generated. Then, 1mol / L dilute sulfuric acid solution is added, and the pH is adjusted to 3.5 to complete the acidification treatment to obtain mixed solution A.

[0206] 700 mL of deionized water was added to a 5000 mL reactor as the bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80°C, mixed solution A was added to the reactor at 28 mL / min. At the same time, the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, the amount of sodium aluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210°C, the treatment pressure was 0.4 MPa, and the treatment was carried out for 8 hours (equivalent to Δt + 6 hours). The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6 hours, and the dried sample PFO-2 was obtained. The silicon-aluminum material PF-2 was calcined at 600°C for 5 hours, and its properties are shown in Table 1.

[0207] (2) Manufacturing of hydrogenation catalysts

[0208] Take 500g of the prepared PFO-2 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain the carrier ZF2 with a particle size of 0.3-0.8mm.

[0209] The carrier ZF2 was saturated with solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain catalyst CF2. The specific properties are shown in Table 2.

[0210] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.19, and no lamellar structure can be seen from the SEM photo, and all of them are non-lamellar structures.

[0211] Comparative Example 3

[0212] (1) Silicon aluminum material manufacturing

[0213] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0214] 1.44L of 50gSiO2 / L silica sol solution was added to a container. While stirring, 1L of 50gAl2O3 / L aluminum sulfate solution was slowly added. During this process, aluminum hydroxide colloid was generated, but the solution remained liquid. Next, 1mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification process to obtain mixed solution A.

[0215] 700 mL of deionized water was added to a 5000 mL reactor as bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80 ° C, mixed solution A was added to the reactor at 28 mL / min. At the same time, the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the flow rate of sodium aluminate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, the amount of sodium aluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor, washed with hot water at 90 ° C until the liquid was neutral, dried at 120 ° C for 6 h, and the dried sample PFO-1 was obtained. The silicon-aluminum material PF-3 was obtained by calcining at 600 ° C for 5 h. Its properties are shown in Table 1.

[0216] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM photo, and all of them are non-lamellar structures.

[0217] (2) Manufacturing of hydrogenation catalysts

[0218] Take 500g of the prepared PFO-3 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain a carrier ZF3 with a particle size of 0.3-0.8mm.

[0219] The carrier ZF3 was saturated with solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain catalyst CF3. The specific properties are shown in Table 2.

[0220] Comparative Example 4

[0221] (1) Silicon aluminum material manufacturing

[0222] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0223] 1.44 L of 50 g SiO2 / L silica sol solution was measured and added to a container. Under stirring, 325 mL of sodium aluminate solution was slowly added, followed by 1 mol / L dilute sulfuric acid solution, and the pH was adjusted to 3.5. During the process, a large amount of aluminum hydroxide gel was generated with poor fluidity, forming suspension A.

[0224] 1L of aluminum sulfate solution with a concentration of 50gAl2O3 / L. During this process, aluminum hydroxide colloid is formed, but the solution remains liquid. Next, 1mol / L dilute sulfuric acid solution is added to adjust the pH to 3.5, completing the acidification process to obtain mixed solution A.

[0225] 700 mL of deionized water was added to a 5000 mL reactor as bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80 ° C, suspension A was added to the reactor at 28 mL / min. At the same time, 1 L of aluminum sulfate solution with a concentration of 50 g Al2O3 / L was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the flow rate of sodium metaaluminate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210 ° C, the treatment pressure was 0.4 MPa, and the treatment was carried out for 8 hours (equivalent to Δt + 6 hours). The treated slurry was washed with hot water at 90 ° C until the liquid was neutral, dried at 120 ° C for 6 hours, and the dried sample PF0-4 was obtained. The silicon-alumina material PF-4 was calcined at 600 ° C for 5 hours, and its properties are shown in Table 1.

[0226] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM photo, and all of them are non-lamellar structures.

[0227] (2) Manufacturing of hydrogenation catalysts

[0228] Take 500g of the prepared PFO-4 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain a carrier ZF4 with a particle size of 0.3-0.8mm.

[0229] 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. Heat and stir until completely dissolved. Then, dilute the solution to 1000 mL with distilled water to obtain Solution L1. The carrier ZF4 was saturated with Solution L1, dried at 110°C for 2 hours, and calcined at 450°C for 3 hours to obtain Catalyst CF4. Specific properties are shown in Table 2.

[0230] Comparative Example 5

[0231] (1) Silicon aluminum material manufacturing

[0232] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0233] 1.44L of 50gSiO2 / L silica sol solution was added to a container. While stirring, 1L of 50gAl2O3 / L aluminum sulfate solution was slowly added. During this process, aluminum hydroxide colloid was generated, but the solution remained liquid. Next, 1mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification process to obtain mixed solution A.

[0234] Mixed solution A was added to a 5000mL reactor at 28mL / min, and the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature in the reactor was kept constant at 80°C and pH by heating in a water bath. After the reaction was completed, 325mL of sodium aluminate was used, and 75g of ammonium carbonate was added to the reactor under stirring to adjust the pH to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210°C, the treatment pressure was 0.4MPa, and the treatment was performed for 8h (equivalent to Δt+6 hours). The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6h, and the dried sample PFO-5 was obtained. The silicon-aluminum material PF-5 was obtained by calcining at 600°C for 5h, and its properties are shown in Table 1.

[0235] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.20.

[0236] (2) Manufacturing of hydrogenation catalysts

[0237] Take 500g of the manufactured PF0-5 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain a carrier ZF5 with a particle size of 0.3-0.8mm.

[0238] 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. Heat and stir until completely dissolved. Then, dilute the solution to 1000 mL with distilled water to obtain Solution L1. The carrier ZF5 was saturated with Solution L1, dried at 110°C for 2 hours, and calcined at 450°C for 3 hours to obtain Catalyst CF5. Specific properties are shown in Table 2.

[0239] Comparative Example 6

[0240] (1) Silicon aluminum material manufacturing

[0241] Prepare aluminum sulfate solution with a concentration of 50gAl2O3 / L and dilute sulfuric acid solution with a concentration of 1mol / L. Prepare sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0242] Weigh 72g of silica into a container, then slowly add 1L of aluminum sulfate solution (50gAl2O3 / L) and stir to form a suspension. Next, add 1mol / L dilute sulfuric acid solution and adjust the pH to 3.5 to complete the acidification process, yielding Suspension A.

[0243] 700 mL of deionized water was added to a 5000 mL reactor as bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80 ° C, mixed solution A was added to the reactor at 28 mL / min. At the same time, the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, the amount of sodium aluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210 ° C, the treatment pressure was 0.4 MPa, and the treatment was carried out for 8 hours (equivalent to Δt + 6 hours). The treated slurry was washed with hot water at 90 ° C until the liquid was neutral, dried at 120 ° C for 6 hours, and the dried sample PF0-6 was obtained. The silicon-aluminum material PF-6 was calcined at 600 ° C for 5 hours, and its properties are shown in Table 1.

[0244] The SiO2 / Al2O3 molar ratio of the silicon-aluminum material is 1.20, and no lamellar structure can be seen from the SEM photo.

[0245] Comparative Example 7

[0246] (1) Silicon aluminum material manufacturing

[0247] Prepare an aluminum sulfate solution with a concentration of 50gAl2O3 / L and a silica sol solution with a concentration of 50gSiO2 / L and a modulus of 2.8. Prepare a dilute sulfuric acid solution with a concentration of 1mol / L. Prepare a sodium metaaluminate solution with a caustic ratio of 1.25 and a concentration of 160gAl2O3 / L.

[0248] 1.44L of 50gSiO2 / L silica sol solution was added to a container. While stirring, 1L of 50gAl2O3 / L aluminum sulfate solution was slowly added. During this process, aluminum hydroxide colloid was generated, but the solution remained liquid. Next, 1mol / L dilute sulfuric acid solution was added to adjust the pH to 3.5, completing the acidification process to obtain mixed solution A.

[0249] 700 mL of deionized water was added to a 5000 mL reactor as bottom water, stirring was started and heating was carried out. After the deionized water was heated to 80°C, mixed solution A was added to the reactor at 28 mL / min. At the same time, the prepared sodium aluminate solution was added in parallel. The pH of the reaction was controlled to 8.3 by adjusting the sodium aluminate flow rate, and the slurry temperature and pH value in the reactor were kept constant. After the reaction was completed, the amount of sodium aluminate was 325 mL, and 75 g of ammonium carbonate was added to the reactor under stirring to adjust the pH value to 10.8. The above slurry was placed in a reactor and, under stirring, the treatment temperature was 210°C, the treatment pressure was 0.4 MPa, and the treatment was carried out for 3 hours (equivalent to Δt + 1 hour). The treated slurry was washed with hot water at 90°C until the liquid was neutral, dried at 120°C for 6 hours, and the dried sample PFO-7 was obtained. The silicon-aluminum material PF-7 was calcined at 600°C for 5 hours, and its properties are shown in Table 1.

[0250] The silicon-aluminum material has a SiO2 / Al2O3 molar ratio of 1.20 and comprises a lamella structure with an average length of 0.85 μm and an average thickness of 25 nm, and the lamella structure accounts for 2% of the total volume of the silicon-aluminum material.

[0251] (2) Manufacturing of hydrogenation catalysts

[0252] Take 500g of the prepared PFO-7 silica-alumina dry sample, add 10g of sesbania powder, 12.15g of citric acid, and 420g of water, mix well and then form into balls. The balled sample is calcined at 650℃ for 4h to obtain carrier Z7 with a particle size of 0.3-0.8mm.

[0253] The carrier Z7 was saturated with the solution L1, dried at 110°C for 2 h, and calcined at 450°C for 3 h to obtain the catalyst CF7. The specific properties are shown in Table 2.

[0254] Table 1 Properties of silicon-aluminum materials (Example)

[0255]

[0256] Table 1 Properties of silicon-aluminum materials (comparative example)

[0257]

[0258] Table 2 Properties of Catalysts (Examples)

[0259]

[0260] Table 2 Properties of Catalysts (Comparative Example)

[0261]

[0262] The catalysts were evaluated for activity in an autoclave. The properties of the feedstock oil and the 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 Comparative Example 1 are shown in Table 4.

[0263] Table 3 Raw oil properties and evaluation conditions

[0264] Item Value Raw Oil Properties Sulfur, % 5.76 Residual Carbon, % 24.86 Nickel + Vanadium / μg·g -1 214.38>500℃ Residue oil yield, %93.2 Process conditions Reaction temperature / ℃420 Reaction pressure / MPa15 Oil volume ratio13:1 Reaction time / h1

[0265] Table 4 Catalyst evaluation results (Example)

[0266]

[0267] Table 5 Catalyst evaluation results (Comparative Example)

[0268]

[0269] The data in the tables demonstrate that the silica-alumina material produced using the present invention exhibits a large pore volume, a small proportion of pores <10 nm, a low sodium oxide content, and a high Br(OH) acid content. The hydrogenation catalyst produced using this silica-alumina material exhibits increased impurity removal and residue conversion compared to the catalyst produced in the comparative example, making it particularly suitable for use as a heavy oil or residue oil hydrogenation catalyst.

Claims

1. A silicon-aluminum material, wherein SiO 2 / Al 2 O 3 The molar ratio is 0.8-1.5 (preferably 1.0-1.4), comprising a lamellar 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 its calcined form has an XRD pattern substantially as shown in Table I or Table II below, preferably its calcined form has an XRD pattern substantially as shown in Figure 2, Table I 2θd-spacing (nm) relative intensity 14.00.12-0.13VS24.30.18-0.19VS34.30.07-0.08S42.60.11-0.13M51.90.10-0.13M66.40.06-0.08M Table II 2θd-spacing (nm)Relative intensity13.90.12-0.13VS24.20.17-0.18VS310.36-0.38M34.40.08-0.10S39.90.08-0.10M42.50.11-0.12M51.60.12-0.13W57.80.14-0.16W66.40.07-0.09W Assuming that the intensity value of the strongest diffraction peak in the XRD spectrum is 100, then W = weak, that is, relative intensity >0 to ≤20, M = medium, that is, relative intensity >20 to ≤40, S = strong, that is, relative intensity >40 to ≤60, VS = very strong, that is, relative intensity >60 to ≤100.

2. The silicon-aluminum material according to claim 1, wherein the pore volume is not less than 1.1 mL / g (preferably greater than 1.15 mL / g, more preferably 1.15-1.5 mL / g), and / or the specific surface area is 260-340 m 2 / g (preferably 260-310m 2 / g), and / or, its pore distribution is: the pore volume of pores with a pore diameter of <10nm accounts for ≤5% of the total pore volume (preferably, the pore volume of pores with a pore diameter of <10nm accounts for ≤3% of the total pore volume), the pore volume of pores with a pore diameter of 10-50nm accounts for 65%-85% of the total pore volume (preferably, the pore volume of pores with a pore diameter of 10-50nm accounts for 70%-85% of the total pore volume), the pore volume of pores with a pore diameter of >50nm accounts for 10%-30% of the total pore volume (preferably, the pore volume of pores with a pore diameter of >50nm accounts for 12%-25% of the total pore volume), and / or, its average pore diameter is 14-23nm (preferably 16-21nm).

3. The silicon-aluminum material according to claim 1, wherein the B acid content is greater than 0.08 mmol / g (preferably 0.1-0.2 mmol / g or 0.1-0.15 mmol / g), and / or the B acid to L acid ratio is 0.2-0.8 (preferably 0.3-0.7), and / or the Na 2 The O content is less than 0.3wt% (preferably less than 0.2wt%), and / or, in its silicon nuclear magnetic resonance spectrum, there is an absorption peak at a chemical shift of -88ppm to -94ppm, and in its aluminum nuclear magnetic resonance spectrum, there is an absorption peak near a chemical shift of 57ppm, and / or, its calcined form has no diffraction peaks in the small-angle XRD spectrum.

4. The silicon-aluminum material according to claim 1 further comprises a non-lamellar structure, wherein the proportion of the lamellar structure is greater than 3% (preferably greater than 5%, more preferably 10-80% or 10-60%) based on the total volume of the silicon-aluminum material.

5. A method for manufacturing a silicon-aluminum material, sequentially The following steps are involved: (1) adding an acidic aluminum source to a silicon source to obtain a mixture A, (2) contacting the mixture A with a basic aluminum source in the presence of water to obtain a slurry B, and (3) The slurry B is subjected to hydrothermal treatment to obtain the silicon-aluminum material.

6. The method of claim 5, wherein in step (1), the 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 one or more selected from water-soluble silicates, water glass, and silica sol, preferably water glass), and / or the silicon source is used in the form of an aqueous solution, and the silicon source (in the form of SiO2) is 1:1, based on the total weight of the aqueous solution. 2 The concentration of the acidic aluminum source is 5-30wt% (preferably 15-30wt%), and / or the 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 one or more selected from aluminum sulfate, aluminum nitrate, and aluminum chloride, preferably aluminum sulfate), and / or the acidic aluminum source is used in the form of an aqueous solution, and the acidic aluminum source (in terms of Al2O3) is 10-20wt% based on the total weight of the aqueous solution. 2 O 3 The concentration of the silicon source (in terms of SiO 2 ) and the acidic aluminum source (in terms of Al 2 O 3 The weight ratio of the above-mentioned components is 1:1-9:1 (preferably 1:1-7:1).

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

8. The production method according to claim 5, wherein in step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, in particular an alkali metal aluminate, more preferably one or more selected from sodium aluminate and potassium aluminate, preferably sodium aluminate), and / or the alkaline aluminum source is used in the form of an aqueous solution, and the alkaline aluminum source (in the form of Al2O3) is 1.5wt% based on the total weight of the aqueous solution. 2 O 3 The concentration of the mixture A is 130-350 g / L (preferably 150-250 g / L), and / or, based on the total volume of the mixture A, the alkaline aluminum source and water, the amount of the mixture A is 40-70 vol% (preferably 40-65 vol%), and / or, based on the total volume of the mixture A, the alkaline aluminum source and water, the amount of the alkaline aluminum source is 20-40 vol% (preferably 25-40 vol%), and / or, based on the total volume of the mixture A, the alkaline aluminum source and water, the amount of water is 10-2 0vol% (preferably 13-20vol%), and / or, the mixture A and the alkaline aluminum source are added to the water successively or simultaneously (preferably, the mixture A and the alkaline aluminum source are added to the water in parallel), and / or, the addition flow rate of the mixture A is 15-50mL / min (preferably 20-40mL / 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 7.5-10.5 (preferably 8.0-10.5, and more preferably 8.5-10.5).

9. The manufacture method according to claim 5, wherein in step (2), a water-soluble carbonate is further added (preferably, the mixture A and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added to obtain the slurry B), and / or the 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 water-soluble carbonate is used in the form of a solid, and / or the amount of the water-soluble carbonate added is such that the pH value of the slurry B is 10.5-12 (preferably 11-12).

10. The manufacturing method according to claim 5, wherein in step (3), the silicon-aluminum material is separated from the reaction system of the hydrothermal treatment (such as by filtration or centrifugal separation), washed to neutrality, and then dried, and / or the drying conditions are include: The drying temperature is 100-150°C and the drying time is 6-10 hours.

11. The manufacturing method according to claim 5, wherein in step (1), the temperature is 25-50° C. (preferably 25-40° C.) and the pressure is normal pressure, and / or, in step (2), the temperature is 50-90° C. (preferably 50-80° C.) and the pressure is normal pressure, and / or, 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), and / or, in step (3), the initial time of the hydrothermal treatment is t 0 The time when the reaction system of the hydrothermal treatment reaches the maximum viscosity is t max , Δt=t max -t 0 , the time of the hydrothermal treatment (in h) is from Δt+1 to Δt+20 (preferably from Δt+2 to Δt+12, in particular from Δt+4 to Δt+8), and / or, in step (3), the time of the hydrothermal treatment is 6-20 h (preferably 8-12 h).

12. The manufacturing method according to claim 5, wherein an auxiliary agent (preferably selected from one or more of phosphorus, boron and titanium) is further added, and / or the weight content of the auxiliary agent in terms of oxide is 1-8wt% (preferably 2-6wt%), relative to the total weight of the silicon-aluminum material 100wt%.

13. A catalytic material comprising an active metal component and the silicon-aluminum material according to claim 1 or the silicon-aluminum material manufactured according to the manufacturing method according to claim 5.

14. The catalytic material of claim 13, wherein the active metal component is a metal component having hydrogenation activity (preferably selected from at least one of Group VIB metals and Group VIII metals of the Periodic Table, in particular selected from at least one of Mo, W, Ni and Co), and / or, based on the total weight of the catalytic material, the weight percentage content of the active metal component (in terms of oxide) is 5-30 wt% (preferably 5-25 wt%).

15. A hydrogenation method, comprising the step of subjecting a hydrocarbon-containing material to a hydrogenation reaction in the presence of the catalytic material according to claim 13.

16. The hydrogenation method according to claim 15, wherein the hydrocarbon-containing material is selected from at least one of diesel, wax oil, heavy oil, coal tar, ethylene tar, and catalytic oil slurry, and / or the reaction conditions of the hydrogenation reaction are include: The reaction pressure is 5-20MPaG, the reaction temperature is 300-450℃, and the liquid hourly volume space velocity is 0.1-1.5h -1 , the volume ratio of hydrogen to oil is 100-1000.

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