Porous alumina material, its preparation and use

Abstract

A porous alumina material, its preparation, and its applications are disclosed. The porous material has substantially regularly distributed spherical or quasi-spherical cavities therein, the cavities having an average diameter of 100-500 nm, and at least some of adjacent cavities are connected via mesopores. The porous alumina material is suitable for use as a support for preparing a heavy residue hydrotreating catalyst or as a support for catalysts used in other polymer catalytic processes.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present application belongs to the field of inorganic materials, and in particular to alumina porous materials, and their preparation and applications.

[0002] [Background technology] Macroporous alumina materials have been widely used in the fields of catalyst carriers, adsorption separation, chromatography, acoustic resistance, and heat-resistant materials due to their relatively large pores, relatively high specific surface area, and good thermal stability. Currently, there are many methods for preparing macroporous alumina materials.

[0003] In U.S. Patent Nos. 4,102,822 and 4,448,896, starch or the like is used as a pore-expanding agent to fill the alumina precursor. After the pore-expanding agent is gasified, ink bottle-shaped macroporous alumina is obtained. The macroporous alumina has small pore openings, a random pore distribution, and a weak mass transfer effect on polymers.

[0004] In Chinese Patent 101890372B, macroporous alumina was prepared using a molten salt solubilization method. The resulting material has large pore diameters and good pore permeability. However, this preparation method uses aluminum nitrate salt and a large amount of oil phase. This preparation process involves a high-temperature and high-pressure reaction environment, which makes it prone to explosions. The resulting macroporous alumina has irregular pores.

[0005] In Article Chem. Mater. (2004, 16: 4245-4256), a porous polymer foam template was prepared by emulsion polymerization, and then Al2O3 precursor was individually loaded into the polymer template. After conversion, the template was removed to obtain a macroporous oxide material. The preparation principle of this method is simple. The resulting macroporous alumina possesses interconnected micropores. The pore diameters range from 1 to 50 μm, and the pore shapes are irregular. However, the preparation of the template requires the use of organic monomers, surfactants, stabilizers, etc. The preparation process is complicated and expensive. Furthermore, the template cannot be reused, and the decomposition of organic matter during incineration of the template causes significant environmental pollution.

[0006] In their paper "Hierarchically ordered meso / macroporous c-alumina for enhanced hydrodesulfurization performance," Microporous and Mesoporous Materials 158 (2012) 1-6, Dezhi Han et al. used colloidal crystals formed by polymethyl methacrylate (PMMA) microspheres as templates. Then, an alumina precursor was filled into the templates, resulting in three-dimensionally ordered macroporous alumina after post-processing. The polymer microsphere templates used in this method generally need to be removed by calcination, which is irreversible and causes environmental pollution. The resulting materials have extremely low crushing strength and are easily shattered, making them unsuitable for fixed-bed reactors.

[0007] Research has shown that in certain applications, such as catalysts for the hydrodemetallization of heavy oils and residues, excessively large pore sizes have little effect on improving catalytic performance. Generally, macropore sizes of 100-300 nm and mesopore sizes of 10-30 nm are required. This improves catalytic performance as a catalyst support. Therefore, it is important to rationally control the pore size of macroporous materials.

[0008] Summary of the Invention In view of the shortcomings of the prior art, the present application provides a porous alumina material, and its preparation and application. The porous alumina material has abundant mesopore structure and internal spherical cavities, and is suitable as a support for a heavy residual oil hydrogenation catalyst. The preparation process is simple, environmentally friendly, and easy to industrially produce.

[0009] To achieve the above object, in one aspect, the present application provides a porous alumina material containing spherical or quasi-spherical cavities distributed substantially regularly therein, the cavities having an average diameter of 100 to 500 nm, and at least some of adjacent cavities communicating with each other via mesopores.

[0010] Preferably, the cavities are distributed substantially within the porous material in a morphology selected from face-centered cubic, body-centered cubic, close-packed hexagonal, or combinations thereof.

[0011] In another aspect, the present application provides a sol-gel method for preparing an alumina porous material, comprising the steps of: 1) mixing an aluminum source, a cavity-forming agent, a polyol, an amide, a polyhydroxy polymer, a solvent, and optional additives, and then adding and mixing a coagulant to obtain a gel; 2) subjecting the gel obtained in step 1) to an aging treatment to obtain an aged material; 3) eluting the aged material obtained in step 2) with an eluent to obtain an eluate and a solid phase material; and 4) drying and optionally calcining the solid phase material obtained in step 3) to obtain a porous material; wherein the cavity-forming agent is selected from a soluble sugar, a soluble alkali metal salt, or a combination thereof; and The cavitating agent is used in an amount of 10-60 g per 100 g of solvent.

[0012] In yet another aspect, there is provided a method of using the alumina porous material of the present application as a catalyst support, the method comprising the step of supporting a catalytically active component on the porous material.

[0013] In yet another aspect, the present application provides a heavy oil hydrogenation catalyst comprising, based on the dry weight of the catalyst, 40-90% of a support and 10-50% of a hydrogenation catalytically active component, wherein the support is an alumina porous material according to the present application.

[0014] The porous alumina material of the present application is suitable for use as a support for preparing a heavy residual oil hydrogenation catalyst or as a support for a catalyst used in other polymer catalyst processes, and has good application effects when used as a support for a residue hydrodemetallization catalyst.

[0015] Other features and advantages of the present invention are explained in detail in the detailed description that follows.

[0016] BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are included to provide a further understanding of the present application and are incorporated into the specification. The drawings, along with the following specific embodiments, are used to explain the present application and are not intended to be limiting of the present application. In the accompanying drawings: FIG. 1 shows a scanning electron microscope (SEM) image of the alumina porous material prepared in Example 1 of the present application; FIG. 2 shows an SEM image of the crystal grains on the wall of the internal cavity of the alumina porous material prepared in Example 1 of the present application; Figure 3 shows the mesopore distribution profile of the alumina porous material prepared in Example 1 of the present application; FIG. 4 shows an SEM image of the alumina porous material prepared in Example 2 of the present application; FIG. 5 shows an SEM image of the alumina porous material prepared in Example 3 of the present application; FIG. 6 shows an SEM image of the alumina porous material prepared in Comparative Example 1 of the present application; FIG. 7 shows an SEM image of the alumina porous material prepared in Comparative Example 2 of the present application; FIG. 8 shows an SEM image of the alumina porous material prepared in Comparative Example 3 of the present application; FIG. 9 is a schematic diagram showing the specific forms of distribution of face-centered cubic, body-centered cubic, and tightly packed hexagonal crystals defined in the present application.

[0017] Detailed Description Specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0018] Any specific numerical value disclosed herein (including the endpoints of a numerical range) should not be construed as limited to that exact value, but should also encompass all possible values ​​near that exact value, for example, within ±5% of that exact value. Furthermore, for any disclosed numerical range, the endpoints of the range, the endpoints and specific points within the range, and various specific points within the range can be combined in any way to create one or more new numerical ranges, and these new numerical ranges should also be considered to be specifically disclosed herein.

[0019] Unless otherwise specified, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. If a term is defined herein and that definition differs from the meaning commonly understood by one of ordinary skill in the art, the definition herein shall control.

[0020] In the present application, the term "substantially orderly distribution" is the opposite of a random distribution and indicates that the spherical or quasi-spherical cavities are generally arranged according to a certain pattern or order within the alumina porous material of the present application, for example, generally distributed in the form of face-centered cubic, body-centered cubic, close-packed hexagonal crystals, or a combination thereof.

[0021] In this application, the term "substantially" means that an error within a range generally accepted in the art, for example, an error within ±20%, particularly within ±10%, and more particularly within ±5%, is allowed.

[0022] In the present application, the terms "spherical or quasi-spherical cavities" and "spherical cavity-like macropores" can be used interchangeably, and both refer to spherical or quasi-spherical cavities distributed inside the alumina porous material of the present application.

[0023] As used herein, the term "mesopore" has the meaning generally understood in the art, specifically referring to pores having a pore diameter in the range of 2-50 nm.

[0024] As used herein, the term "micropore" has the meaning generally understood in the art, and specifically refers to pores having a pore diameter of less than 2 nm.

[0025] In this application, the term "quasi-spherical" has the meaning commonly understood in the art, and particularly refers to having substantially spherical morphological characteristics. However, when measuring the "diameter" of a "quasi-spherical body," d0 is defined as half the sum of the obtained maximum and minimum diameters, and the other measured diameter of the "quasi-spherical body" is defined as d. When the value of (d-d0) / d0*100% is within ±20%, particularly within ±10%, and even more particularly within ±5%, it is called "quasi-spherical." When the value of (d-d0) / d0*100% is 0%, it is a perfect sphere.

[0026] In this application, the term "soluble" has the meaning generally understood in the art, specifically, it refers to having a solubility of 10 g or more, preferably 20 g or more, in 100 g of the solvent used at 20°C and 1 atmosphere.

[0027] As used herein, the terms "face-centered cubic," "body-centered cubic," and "close-packed hexagonal" have the meanings commonly understood in the art. As a specific example, a schematic diagram of a specific form can be shown in FIG.

[0028] In this study, the average diameter of the internal cavities, the thickness of the cavity walls, and the size of the crystal grains in the cavity walls of the obtained porous material were measured through SEM images of the obtained porous material. Although SEM images only reveal the surface morphology of the material sample, the sample surface is a random cross-section, which is equivalent to a cross-section formed by cutting the sample in any direction. Therefore, the surface morphology can reflect the internal structural characteristics of the material sample. Then, by measuring the data of the relevant structures displayed in the SEM image, the corresponding data of the internal cavities of the material can be obtained. Specifically, 50 cross-sections of the internal cavities in the SEM image were randomly selected, their diameters were measured, and the average was calculated as the average diameter of the cavities. At the thinnest part of the cavity wall, the thickness between groups of 50 adjacent cavity cross-sections was randomly measured, and the average was used as the thickness of the cavity wall. The diameters of 50 crystal grains on the cavity wall were randomly measured, and the average was used as the average diameter of the crystal grains.

[0029] In this application, except for the contents explicitly described, any undescribed matters or items are applied as they are to those known in the art without any changes. Furthermore, any embodiment described in this specification can be freely combined with one or more other embodiments described in this specification, and the technical solutions or technical ideas formed thereby shall be considered as part of the original disclosure or original record of the present invention, and shall not be considered as new contents not disclosed or anticipated in this specification unless a person skilled in the art considers the combination to be obviously unreasonable.

[0030] All patent and non-patent literature, including but not limited to textbooks and journal articles, referred to herein is hereby incorporated by reference in its entirety.

[0031] As described above, in a first aspect, the present application provides a porous alumina material containing substantially regularly distributed spherical or quasi-spherical cavities therein, the cavities having an average diameter of 100-500 nm, preferably 150-350 nm, and at least some of the adjacent cavities being connected to each other via mesopores.

[0032] According to the present application, the alumina porous material may be in various shapes, such as spheres, rods, sheets, or any other particle shape, and the present application does not have any strict limitations thereon. Preferably, the alumina porous material is in the form of particles, and the particle size is at least 1.0 μm, for example, 1.0-5000 μm.

[0033] According to the present application, a plurality (e.g., at least 10, e.g., 10-10000 / μm 3 ) spherical or quasi-spherical cavities are distributed in a substantially orderly manner within the alumina porous material. Preferably, the cavities are distributed substantially in a morphology selected from face-centered cubic, body-centered cubic, close-packed hexagonal, or a combination thereof. In certain preferred embodiments, the spherical or quasi-spherical cavities are distributed in an orderly manner within the porous material of the present application, preferably in a morphology selected from face-centered cubic, body-centered cubic, close-packed hexagonal, or a combination thereof.

[0034] According to the present invention, at least some of the adjacent cavities in the porous alumina material are connected through mesopores, and after firing, substantially all of the adjacent cavities are connected through mesopores. Here, "connected through mesopores" means that the pore diameter of the largest communicating pore between adjacent cavities is in the range of 2-50 nm. However, this does not exclude the presence of micropores with a pore diameter of less than 2 nm.

[0035] In a preferred embodiment, the pore diameter corresponding to the peak value of the mesopore distribution peak on the pore distribution profile of the porous material is in the range of 10-30 nm, as measured by the BET nitrogen adsorption method and calculated by the BJH method.

[0036] In a preferred embodiment, the half-width of the pore distribution peak on the mesopore distribution profile of the porous material, as measured by BET nitrogen adsorption and calculated by the BJH method, is 15 nm or less, preferably 1-10 nm, more preferably 1-6 nm, for example 1-5 nm or 1-3 nm.

[0037] In a preferred embodiment, the average thickness of the cavity walls between adjacent cavities within said porous material is 5-100 nm, preferably 10-80 nm, more preferably 10-35 nm.

[0038] In a particularly preferred embodiment, the hollow walls of the cavities are composed of alumina grains with an average diameter of 5-30 nm.

[0039] In some other preferred embodiments, for example, without high temperature calcination treatment, the hollow walls of the cavities are composed of crystalline grains of alumina precursor containing water or hydroxyl groups and organic matter.

[0040] In a preferred embodiment, the porous material has one or more of the following properties: Crushing strength of 8-20N / mm, preferably 10-18N / mm; Measured by the BET method, 200-350m 2 / g, preferably 210-320m 2 specific surface area in / g; 0.5-1.5m measured by the BET method 3 / g, preferably 0.7-1.0m 3 / g pore volume; a porosity of 0.50-0.95, preferably 0.6-0.9, as measured by mercury porosimetry; and 0.1-1.0g / cm 3 , preferably 0.2-0.5g / cm 3 Bulk density of.

[0041] In a second aspect, the present application provides a sol-gel method for preparing an alumina porous material, comprising the steps of: 1) mixing an aluminum source, a cavity-forming agent, a polyol, an amide, a polyhydroxy polymer, a solvent, and optional additives, and then adding and mixing a coagulant to obtain a gel; 2) subjecting the gel obtained in step 1) to an aging treatment to obtain an aged material; 3) eluting the aged material obtained in step 2) with an eluent to obtain an eluate and a solid phase material; and 4) drying and optionally calcining the solid phase material obtained in step 3) to obtain a porous material; wherein the cavitating agent is selected from a soluble sugar, a soluble alkali metal salt, or a combination thereof; the cavitating agent is used in an amount of 10-60 g, preferably 20-60 g, more preferably 30-60 g, per 100 g of solvent.

[0042] In the sol-gel method of the present application, a material mixture undergoes a slow sol-gel reaction via a coagulating agent, and the polyhydroxypolymer causes solid-liquid phase separation to form a gel. Because a large amount of soluble cavity-forming agent is used in the material mixture, when the formed gel undergoes phase separation, the cavity-forming agent migrates into the liquid phase formed by phase separation and eventually aggregates into spherical or quasi-spherical aggregates due to the spontaneous stability of the system. The cavity-forming agent can support the solid phase obtained by phase separation. The added polyol makes the gel network more uniform, provides solid-liquid separation sites, reduces the size of the solid-liquid separation space, and reduces the size of the formed cavities. At the same time, in cooperation with the amide, it can further promote the formation of small-sized cavities and make the distribution of the cavities more uniform. After the gel stabilizes, the soluble materials can be removed by washing the gel with an eluent, and the spaces occupied by the soluble materials form spherical or quasi-spherical cavities. The soluble cavity-forming agent used in this application is non-toxic, inexpensive, readily available, and reusable. The soluble cavitating agent is beneficial in reducing preparation costs.

[0043] In a preferred embodiment, the soluble sugar functioning as a cavitating agent is selected from sucrose, glucose, fructose, maltose or a combination thereof, and the soluble alkali metal salt is selected from an alkali metal nitrate, sulfate or chloride, more preferably the alkali metal is selected from potassium, sodium or a combination thereof.

[0044] In a preferred embodiment, the solvent is selected from a low-carbon alcohol, water, or a combination thereof. According to the present application, the low-carbon alcohol refers to a monohydric alcohol of C5 or less, and is preferably selected from methanol, ethanol, n-propanol, isopropanol, or a combination thereof, and more preferably selected from ethanol, propanol, or a combination thereof. According to the present application, when a mixture of a low-carbon alcohol and water is used as the solvent, the two can be mixed in any ratio.

[0045] In a preferred embodiment, the coagulating agent is selected from substituted or unsubstituted pyridine, alkylene oxide, or a combination thereof. Preferably, the substituted pyridine is selected from alkylpyridine, pyridine chloride, or a combination thereof, and the alkylpyridine is more preferably selected from monomethylpyridine, dimethylpyridine, trimethylpyridine, or a combination thereof; the pyridine chloride is more preferably selected from monochloropyridine, dichloropyridine, trichloropyridine, or a combination thereof. Preferably, the alkylene oxide is selected from ethylene oxide, propylene oxide, or a combination thereof.

[0046] In a preferred embodiment, the eluent is selected from a low-carbon alcohol, water, or a combination thereof, wherein the low-carbon alcohol is a monohydric alcohol of C5 or less, preferably selected from methanol, ethanol, n-propanol, isopropanol, or a combination thereof, more preferably selected from ethanol, propanol, or a combination thereof. According to the present application, when a mixture of low-carbon alcohol and water is used as the eluent, the weight concentration of the low-carbon alcohol is 40% or more.

[0047] In the method of the present application, the aluminum source may be any aluminum source commonly used in the art and suitable for preparing porous alumina materials by the sol-gel method, and the present application does not have any strict limitations in this regard. In a preferred embodiment, the aluminum source is selected from aluminum chloride, aluminum nitrate, aluminum sulfate, or a combination thereof.

[0048] In a preferred embodiment, the polyhydroxy polymer is selected from polyethylene glycol, polyvinyl alcohol, or a combination thereof and has a viscosity average molecular weight of 50,000-200,000.

[0049] In a preferred embodiment, the polyol is selected from ethylene glycol, propylene glycol, butylene glycol, glycerol, isopropanol, pentaerythritol, or mixtures thereof in any proportion, preferably propylene glycol and glycerol.

[0050] In a preferred embodiment, the amide is selected from formamide, acetamide, dimethylformamide, diethylformamide, or a combination thereof.

[0051] In a preferred embodiment, said step 1) is carried out at a temperature of 10-60°C.

[0052] In a preferred embodiment, based on the weight of the gel obtained in step 1), the gel comprises 10-35% by weight, preferably 15-30% by weight, of an aluminum source, 10-40% by weight, preferably 15-30% by weight, of a cavitating agent, 0.1-2.5% by weight, preferably 0.5-1.5% by weight, of a polyol, 0.1-2.5% by weight, preferably 0.2-2.0% by weight, of an amide, 0.1-2.5% by weight, preferably 0.2-2.0% by weight, of a polyhydroxypolymer, 20-70% by weight, preferably 25-60% by weight, of a solvent, 15-35% by weight, preferably 20-30% by weight, of a coagulant, and 0-20% by weight, preferably 0-15% by weight, of additives.

[0053] According to the present application, in step 1), the obtained material can be modified by adding an additive containing Ce, Zr, Ti, Zr, Si, La, and / or P, preferably selected from water-soluble or water-dispersible precursors of Ce, Zr, Ti, La, silicon, and phosphorus. In a particularly preferred embodiment, the additive is selected from soluble salts of Ce, Zr, Ti, and La, preferably selected from nitrates, sulfates, and chlorides of these metals. In another preferred embodiment, the additive is selected from alkoxides, silicate esters, and phosphoric acid of Zr and Ti.

[0054] In a preferred embodiment, the aging conditions in step 2) include an aging temperature of 10-60°C, preferably 20-40°C, and an aging time of 1-72 hours, preferably 12-60 hours.

[0055] In a preferred embodiment, the elution in step 3) is carried out as follows: the aged material is immersed in an eluent at 10-100°C for a period of generally 1-72 hours, preferably 24-48 hours, followed by solid-liquid separation. Preferably, the solid-liquid separation is carried out by a method selected from filtration, centrifugation, gravity settling, or a combination thereof. The obtained solid phase material is dried and calcined in step 4) to obtain the desired porous material. The liquid phase material is treated at low temperature or by evaporation, and the cavity-forming agent can be crystallized and precipitated to achieve repeated use.

[0056] In the method of the present application, the drying in step 4) can be conventional hot air drying or vacuum drying. In a preferred embodiment, the drying temperature is 10-150°C, preferably 30-60°C, and drying is carried out until no obvious liquid is present, preferably for 0.5-48 hours.

[0057] According to the present application, the porous material obtained in step 4) may be optionally calcined. Without calcination, residual cavity-forming agents may still exist in some pores (e.g., pores connecting adjacent cavities) of the obtained porous material, and the porous material may also contain abundant moisture or hydroxyl groups in the crystal grains of the alumina precursor, which are easily removed at high temperatures. This reduces the pore volume and porosity of the obtained porous material. After calcination, the aforementioned residual substances are substantially removed. Therefore, the pore volume and porosity of the obtained porous material are improved. In a preferred embodiment, the calcination conditions in step 4) include a temperature of 300-950°C, preferably 400-850°C, more preferably 550-750°C, and a calcination time of 0.5-48 hours, preferably 1-24 hours, more preferably 1-6 hours.

[0058] In a third aspect, there is provided an alumina porous material prepared by the method of the present application.

[0059] In a fourth aspect, there is provided the use of the alumina porous material according to the present application as a catalyst support, in particular as a heavy oil hydrogenation catalyst support.

[0060] In a fifth aspect, there is provided a method for using the alumina porous material according to the present application as a catalyst support, the method comprising the step of supporting a catalytically active component on the porous material.

[0061] In a preferred embodiment, the catalyst is a heavy oil hydrogenation catalyst, and the catalytically active component is a hydrogenation catalytically active component, preferably selected from Co, Mo, Ni, W, or a combination thereof.

[0062] In a sixth aspect, there is provided a heavy oil hydrogenation catalyst comprising, based on the dry weight of the catalyst, 40-90% of a support and 10-50% of a hydrogenation catalytically active component, wherein the support is an alumina porous material according to the present application.

[0063] In a preferred embodiment, the hydrogenation catalytically active component is selected from Co, Mo, Ni, W or a combination thereof.

[0064] In certain preferred embodiments, the present application provides the following technical solutions: 1. A spherical hollow macroporous alumina material, characterized in that spherical hollow macropores are uniformly distributed in a honeycomb shape within the alumina material, the macropores have diameters in the range of 100-450 nm, the spherical hollow macropores are connected via mesopores, the mesopores have pore sizes in the range of 10-30 nm, the mesopore size distribution is concentrated, and the half-width of the peak of the pore distribution is 3 nm or less.

[0065] 2. The spherical hollow-like macropore alumina according to item 1, characterized in that the thickness of the pore wall of the spherical hollow-like macropore is 5-50 nm, preferably 10-35 nm.

[0066] 3. The spherical hollow-like macropore alumina according to item 1, characterized in that the pore walls of the spherical hollow-like macropores are composed of small alumina crystal grains of 5-30 nm.

[0067] 4. The spherical hollow-like macroporous alumina according to item 1, characterized in that the crushing strength is 8-20N / mm, preferably 10-15N / mm.

[0068] 5.Specific surface area is 250-350m 2 / g and pore volume is 0.5-1.5m 3 / g, and the porosity of the macropores is 0.50-0.95.

[0069] 6. A method for preparing spherical hollow macroporous alumina, comprising: homogeneously mixing an aluminum source, a soluble sugar, a polyol, an amide, polyethylene glycol, and a solvent, adding a coagulant, and homogeneously mixing to obtain a gel; aging the gel, dissolving the aged material, and drying and calcining the solid phase to obtain spherical hollow macroporous alumina; wherein the solvent is a low-carbon alcohol and / or water, and the coagulant is pyridine and / or ethylene oxide.

[0070] 7. The method according to item 6, wherein the aluminum source is one or more of aluminum chloride, aluminum nitrate, and aluminum sulfate.

[0071] 8. The method according to item 6, wherein the low-carbon alcohol is one or more of a C5 or lower alcohol, preferably methanol, ethanol, n-propanol, and isopropanol.

[0072] 9. The method according to item 6, wherein the soluble sugar is one or more of sucrose, glucose, and fructose.

[0073] 10. The method according to item 6, wherein the viscosity average molecular weight of the polyethylene glycol is 50,000-200,000.

[0074] 11. The method according to item 6, wherein the polyol is one or more of ethylene glycol, propylene glycol, butylene glycol, glycerol, isopropanol, and pentaerythritol.

[0075] 12. The method according to item 6, wherein the amide is one or more of formamide, acetamide, dimethylformamide and diethylformamide.

[0076] 13. The method according to item 6, characterized in that the aluminum source is 10%-35%, the soluble sugar is 10%-40%, the polyol is 0.1%-2.5%, the amide is 0.1%-2.5%, the polyethylene glycol is 0.1%-2.5%, the solvent is 20%-70%, and the coagulant is 15%-35% based on the weight of the gel.

[0077] 14. The method according to item 6, wherein the aging conditions include an aging temperature of 10-40°C, preferably 20-30°C, and an aging time of 1 hour-72 hours, preferably 12 hours-60 hours.

[0078] 15. The method according to item 6, wherein the elution step comprises immersing the aged material in an eluent for 1 hour to 72 hours, followed by solid-liquid separation, wherein the eluent is a low-carbon alcohol and / or water, and the low-carbon alcohol is one or more monohydric alcohols of C5 or less.

[0079] 16. A carrier for a heavy residual oil hydrogenation catalyst, comprising the spherical cavity-like macroporous alumina of any one of items 1 to 5, or the spherical cavity-like macroporous alumina prepared by the method of any one of items 6 to 15.

[0080] 17. Use of the spherical hollow-like macroporous alumina of any one of items 1-5 in a heavy oil hydrogenation process. [Example] The present application is further described below with reference to examples, but the present application is not limited thereto.

[0081] In the following examples and comparative examples: In the SEM image of the obtained porous material, 50 cross sections of the internal cavities were randomly selected, their diameters were measured, and the average value was calculated as the average diameter of the cavities; the thickness between 50 adjacent cross sections of the cavity at the thinnest part of the cavity wall was randomly measured, and the average value was used as the thickness of the cavity wall; and the diameters of 50 crystal grains on the cavity wall were randomly measured, and the average value was used as the average diameter of the crystal grains.

[0082] The specific surface area and pore volume of the obtained porous material were measured by the BET method, and the porosity was measured by mercury intrusion porosimetry. The mesopore diameter of the porous material was measured by the BET nitrogen adsorption method and calculated by the BJH method. The mesopore distribution profile of the porous material was obtained by the BJH method, with dV / dD on the vertical axis and pore diameter on the horizontal axis. The half-width of the pore distribution peak is the range of pore diameters at half the height of the pore distribution peak.

[0083] The crushing strength of the porous material is tested according to HG T 2782-2011, and the bulk density is tested according to GB / T 23771-2009.

[0084] Example 1 Water, absolute ethanol, aluminum chloride, glycerol, formamide, polyethylene glycol (viscosity average molecular weight 100,000), and sucrose were mixed uniformly at room temperature (25°C), and then ethylene oxide was added. The weight percentages of each component in the mixture were 15% water, 15% ethanol, 20% aluminum chloride, 1% glycerol, 1% formamide, 22% sucrose, 1% polyethylene glycol, and 25% ethylene oxide. After uniform mixing, the resulting gel was aged at 30°C for 48 hours. The aged mixture was then immersed in ethanol for 48 hours. After immersion was completed and the liquid phase was removed, the aged mixture was dried at 60°C until no significant weight loss was observed. The resulting product was then calcined at 550°C for 3 hours and then cooled to room temperature to obtain the porous alumina material of the present invention.

[0085] An SEM image of the porous material is shown in Figure 1, and an SEM image of the crystal grains on the wall is shown in Figure 2. The average diameter of the internal cavities of the porous material is 175 nm, the average thickness of the wall is 21 nm, the average diameter of the crystal grains on the wall is 6 nm, the shape of the cavities is quasi-spherical, and they are arranged in a substantially face-centered cubic form. The porous material has a specific surface area of ​​315 m 2 / g, pore volume 0.86m 3 / g, porosity 0.82, pore diameter corresponding to the peak value of the mesopore distribution peak of 19 nm, half-width of the mesopore distribution peak of 2.27 nm (shown in Figure 3), and crushing strength of 1.68 N / mm.

[0086] Example 2 Water, anhydrous ethanol, aluminum chloride, propylene glycol, acetamide, polyethylene glycol (viscosity average molecular weight 200,000), and fructose were mixed uniformly at room temperature (25°C), and then propylene oxide was added. The weight percentages of each component in the mixture were 30% water, 30% ethanol, 14% aluminum chloride, 1% propylene glycol, 1.5% acetamide, 10% fructose, 1% polyethylene glycol, and 12.5% ​​propylene oxide. After uniform mixing, the resulting gel was aged at 40°C for 48 hours, and the aged mixture was then immersed in ethanol for 48 hours. After immersion was completed and the liquid phase was removed, the aged mixture was dried at 45°C until no significant weight loss was observed. The resulting product was then calcined at 650°C for 3 hours and then cooled to room temperature to obtain the porous alumina material of the present invention.

[0087] The SEM image of the obtained porous material is shown in Figure 4. The average diameter of the internal cavities of the porous material is 280 nm, the average thickness of the cavity walls is 52 nm, the average diameter of the crystal grains of the cavity walls is 19 nm, the shape of the cavities is quasi-spherical, and they are arranged in a substantially face-centered cubic form. The porous material has a specific surface area of ​​275 m 2 / g, pore volume 0.75m 3 / g, porosity 0.84, pore diameter corresponding to the peak value of the mesopore distribution peak 16 nm, half-width of the mesopore distribution peak 1.7 nm, and crushing strength 15.7 N / mm.

[0088] Example 3 Water, absolute ethanol, aluminum chloride, butanediol, N,N-dimethylformamide, polyethylene glycol (viscosity average molecular weight 50,000), and glucose were mixed uniformly at 40°C, followed by the addition of a mixture of pyridine and propylene oxide. The resulting mixture contained 18% water, 19% ethanol, 23% aluminum chloride, 2% butanediol, 1% N,N-dimethylformamide, 2% polyethylene glycol, 20% glucose, and 15% of the mixture of pyridine and propylene oxide (1:1 mass ratio). After uniform mixing, the resulting gel product was aged at 20°C for 72 hours. The aged mixture was then immersed in ethanol for 24 hours. After immersion was completed and the liquid phase was removed, the aged mixture was dried at 60°C until no significant weight loss was observed. The resulting product was then calcined at 750°C for 3 hours and cooled to room temperature to obtain the alumina porous material of the present invention.

[0089] The SEM image of the obtained porous material is shown in Figure 5. The average diameter of the internal cavities of the porous material was 2.10 nm, the average thickness of the cavity walls was 1.8 nm, the average diameter of the crystal grains of the cavity walls was 27 nm, the shape of the cavities was quasi-spherical, and they were arranged in a substantially face-centered configuration. The specific surface area of ​​the porous material was 212 m 2 / g, and the pore volume is 0.76 m 3 / g, the porosity is 0.68, the pore diameter corresponding to the peak value of the mesopore distribution peak is 21 nm, the half-width of the mesopore distribution peak is 2.1 nm, and the crushing strength is 16.5 N / mm.

[0090] Example 4 Water, absolute ethanol, aluminum chloride, butanediol, N,N-dimethylformamide, polyvinyl alcohol (viscosity average molecular weight 100,000), and sodium chloride were mixed uniformly at 40°C, and then butylene oxide was added. The weight percentages of each component in the mixture were 18% water, 19% ethanol, 23% aluminum chloride, 2% butanediol, 1% N,N-dimethylformamide, 2% polyvinyl alcohol, 20% sodium chloride, and 15% butylene oxide. After uniform mixing, the resulting gel product was aged at 20°C for 48 hours. The aged mixture was then immersed in ethanol for 24 hours. After immersion was completed and the liquid phase was removed, the aged mixture was dried at 50°C until no significant weight loss was observed. The resulting product was then calcined at 750°C for 3 hours and cooled to room temperature to obtain the alumina porous material of the present invention.

[0091] The average diameter of the internal cavities of the obtained porous material is 185 nm, the average thickness of the cavity walls is 26 nm, the average diameter of the crystal grains of the cavity walls is 24 nm, the shape of the cavities is quasi-spherical, and they are arranged in a substantially face-centered cubic form. 2 / g, pore volume 0.76 m 3 / g, porosity 0.71, pore diameter corresponding to the peak value of the mesopore distribution peak 20 nm, half-width of the mesopore distribution peak 1.7 nm, and crushing strength 17.5 N / mm.

[0092] Example 5 The same as in Example 1, except that 5% cerium chloride was added, the amounts of water and anhydrous ethanol used were each reduced by 2.5%, and other contents were unchanged. The properties of the resulting material were similar to those of Example 1, indicating that the cerium modification did not significantly adversely affect the aforementioned physicochemical properties of the porous alumina material of the present invention. Meanwhile, other test results indicated that the high-temperature stability of the cerium-modified alumina was improved. Furthermore, when the calcination conditions of Example 1 and this example were changed to a calcination temperature of 850°C and a calcination time of 6 hours, the former product underwent a clear crystal transformation, almost completely converting from the γ phase to the δ phase, while the latter product only partially converted to the δ phase.

[0093] Example 6 The same as in Example 1, except that 5% ethyl orthosilicate was added, the amounts of water and absolute ethanol used were each reduced by 2.5%, and other contents remained unchanged. The properties of the obtained material were similar to those of Example 1, indicating that the modification of silicon element does not have a significant adverse effect on the aforementioned physicochemical properties of the alumina porous material of the present invention. Meanwhile, other test results show that the material obtained after silicon modification produces a small amount of B acid, while the product obtained in Example 1 only contains L acid.

[0094] Comparative Example 1 An alumina porous material was prepared according to Example 1, except that the sucrose content was reduced to 1.5%. The SEM image of the resulting alumina material is shown in Figure 6. The SEM image shows that randomly distributed worm-like pores were formed, and the substantially orderly distributed internal cavities described herein were not formed.

[0095] Comparative Example 2 An alumina porous material was prepared according to Example 1, except that glycerol was not added. The SEM image of the obtained alumina material is shown in Figure 7, and the average diameter of its internal cavities was more than 1 μm and was poor in uniformity.

[0096] Comparative Example 3 An alumina porous material was prepared according to Example 1, except that formamide and glycerol were not added. The SEM image of the obtained alumina material is shown in Figure 8. The internal cavities are unevenly distributed, and the substantially ordered distribution described in this application cannot be formed. The average diameter of the cavities is too large, generally exceeding 5 μm, and the uniformity is very poor.

[0097] Comparative Example 4 An alumina porous material was prepared according to Example 1, except that the gel product was directly dried and calcined without being subjected to a dissolution treatment. Under these conditions, sucrose was not dissolved but was retained in the sample, causing it to burn during calcination, generating thick smoke that pollutes the environment. In addition, the gas produced by the sugar combustion destroyed the cavity structure, destroying the uniformity of the cavity size and the order of the arrangement.

[0098] Comparative Example 5 Three-dimensionally ordered macroporous alumina was prepared according to the method described in Section 2 of Micropor. Mesopor. Mater (2012, 158:1-6). After calcination at 550 °C for 3 hours, the crush strength of the resulting material was 2.3 N / mm. When used in a high-pressure environment, the material was too brittle and easily crushed. Furthermore, the half-width of the mesopore distribution was 26 nm, indicating a relatively broad pore distribution.

[0099] Application example 1 The alumina porous material prepared in Example 1 was used as a carrier and impregnated with an equal volume of a metal salt composite solution formed from ammonium molybdate, basic nickel carbonate, and phosphoric acid. The material was dried at 120°C for 5 hours and then calcined at 500°C for 3 hours to obtain an oxide-type Ni-Mo / Al2O3 hydrogenation catalyst having the composition shown in Table 1 (where P is calculated as PO, and the mass content is 1.2%).

[0100] Test Example 1 The effectiveness of the hydrogenation catalyst obtained in Example 1 when used in the hydrodemetallization of residue was tested and compared with a reference catalyst, the commercially available hydrodemetallization catalyst FZC-204.

[0101] Catalytic performance evaluation: Maoming mixed residue (main characteristics of the raw residue: residual carbon content 11.2%, (Ni + V) content 93 μg / g, sulfur content 2.89%) was used as the raw material to evaluate the catalytic performance in a 200 mL fixed-bed reactor. The operating conditions were as follows: after sulfurization of the catalyst, the raw material reaction temperature was 380 °C, the hydrogen partial pressure was 15 MPa, and the space velocity was 0.4 h -1 The test equipment was operated for 300 hours, and after the catalytic activity stabilized, oil samples were taken and tested for the content of Ni and V impurities. The test results are shown in Table 1.

[0102] [Table 1]

[0103] The results in Table 1 show that the overall catalytic performance of the hydrogenation catalyst of Application Example 1, which is based on the alumina porous material of the present application, in terms of demetallization, desulfurization, and carbon residue removal is superior to that of the reference catalyst.

[0104] Although the preferred embodiments of the present application have been described in detail above, the present application is not limited to the specific details of the above embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and all of these simple modifications fall within the scope of protection of the present application.

[0105] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe the various possible combinations.

[0106] It should be noted that various embodiments of the present application can be combined in any manner, and as long as they do not deviate from the concept of the present application, they should also be considered to be included in the present application. [Brief explanation of the drawings]

[0107] [Figure 1]FIG. 1 shows a scanning electron microscope (SEM) image of the porous alumina material prepared in Example 1 of the present application. [Figure 2] FIG. 2 shows an SEM image of crystal grains on the walls of the internal cavities of the porous alumina material produced in Example 1 of the present application. [Figure 3] FIG. 3 shows the mesopore distribution profile of the alumina porous material prepared in Example 1 of the present application. [Figure 4] FIG. 4 shows an SEM image of the porous alumina material prepared in Example 2 of the present application. [Figure 5] FIG. 5 shows an SEM image of the porous alumina material prepared in Example 3 of the present application. [Figure 6] FIG. 6 shows an SEM image of the porous alumina material produced in Comparative Example 1 of the present application. [Figure 7] FIG. 7 shows an SEM image of the porous alumina material produced in Comparative Example 2 of the present application. [Figure 8] FIG. 8 shows an SEM image of the porous alumina material produced in Comparative Example 3 of the present application. [Figure 9] 1 is a schematic diagram showing specific forms of distribution of face-centered cubic, body-centered cubic, and tightly packed hexagonal crystals defined in the present application.

Claims

1. A porous alumina material comprising substantially regularly distributed spherical or quasi-spherical cavities therein, the cavities having an average diameter of 100-500 nm, preferably 150-350 nm, and at least some of the adjacent cavities being in communication with each other via mesopores.

2. 2. The porous material according to claim 1, wherein the mesopores are measured by the Brunauer, Emmett, and Teller (BET) nitrogen adsorption method and calculated by the BJH method, and the pore diameter corresponding to the peak value of the mesopore distribution peak on the pore distribution profile of the porous material is in the range of 10 to 30 nm.

3. 10. The porous material of claim 1, wherein the cavities are distributed substantially within the porous material in a morphology selected from face-centered cubic, body-centered cubic, close-packed hexagonal, or a combination thereof.

4. The porous material according to any one of the preceding claims, wherein the mesopores have a half-width at half maximum of a mesopore distribution peak on a pore distribution profile of the porous material, as measured by the BET nitrogen adsorption method and calculated by the BJH method, of 15 nm or less, preferably 1 to 10 nm, more preferably 1 to 6 nm.

5. 10. A porous material according to any one of the preceding claims, wherein the average thickness of the cavity walls between adjacent cavities is 5-100 nm, preferably 10-80 nm, more preferably 10-35 nm.

6. The porous material according to any one of the preceding claims, wherein the hollow walls are composed of alumina crystal grains having an average diameter of 5-30 nm, or the hollow walls are composed of crystal grains of an alumina precursor containing water or hydroxyl groups and an organic substance.

7. 10. The porous material according to any one of the preceding claims, wherein the porous material has one or more of the following properties: a crush strength of 8-20 N / mm, preferably 10-18 N / mm; Measured by the BET method, 200-350m ２ / g, preferably 210-320m ２ / g specific surface area; Measured by the BET method, 0.5-1.5 m ３ / g, preferably 0.7-1.0 m ３ / g pore volume; a porosity, measured by mercury porosimetry, of 0.50-0.95, preferably 0.6-0.9; and 0.1-1.0g / cm ３ , preferably 0.2-0.5 g / cm ３ Bulk density of.

8. A sol-gel method for preparing a porous alumina material, comprising the steps of: 1) mixing an aluminum source, a cavity-forming agent, a polyol, an amide, a polyhydroxy polymer, a solvent, and optional additives, and then adding and mixing a coagulant to obtain a gel; 2) subjecting the gel obtained in step 1) to an aging treatment to obtain an aged material; 3) eluting the aged material obtained in step 2) with an eluent to obtain an eluate and a solid phase material; and 4) drying and optionally calcining the solid phase material obtained in step 3) to obtain a porous material; wherein the cavitating agent is selected from a soluble sugar, a soluble alkali metal salt, or a combination thereof, preferably, the soluble sugar is selected from sucrose, glucose, fructose, maltose, or a combination thereof, and the soluble alkali metal salt is selected from an alkali metal nitrate, sulfate, or chloride, more preferably, the alkali metal is selected from potassium, sodium, or a combination thereof; and The cavitating agent is used in an amount of 10-60 g, preferably 20-60 g, more preferably 30-60 g, per 100 g of solvent; The solvent is preferably selected from a low carbon alcohol, water, or a combination thereof; The coagulating agent is preferably selected from substituted or unsubstituted pyridine, alkylene oxide or a combination thereof, wherein the substituted pyridine is preferably selected from alkylpyridine, chlorinated pyridine or a combination thereof, the alkylpyridine is more preferably selected from monomethylpyridine, dimethylpyridine, trimethylpyridine or a combination thereof, and the chlorinated pyridine is more preferably selected from monochloropyridine, dichloropyridine, trichloropyridine or a combination thereof; The eluent is preferably selected from a low carbon alcohol, water, or a combination thereof.

9. 9. The method of claim 8, having one or more of the following features: The aluminum source is selected from aluminum chloride, aluminum nitrate, aluminum sulfate, or a combination thereof; The low carbon alcohol is ５ Selected from the following alcohols, preferably selected from methanol, ethanol, n-propanol, isopropanol, or combinations thereof; The polyhydroxy polymer is selected from polyethylene glycol, polyvinyl alcohol, or a combination thereof and has a viscosity average molecular weight of 50,000-200,000; The polyol is selected from ethylene glycol, propylene glycol, butylene glycol, glycerol, isopropanol, pentaerythritol, or combinations thereof; The amide is selected from formamide, acetamide, dimethylformamide, diethylformamide, or combinations thereof.

10. 10. The method according to claim 8 or 9, wherein the gel comprises, based on the weight of the gel obtained in step 1), 10-35% by weight, preferably 15-30% by weight, of the aluminum source, 10-40% by weight, preferably 15-30% by weight, of the cavitating agent, 0.1-2.5% by weight, preferably 0.5-1.5% by weight, of the polyol, 0.1-2.5% by weight, preferably 0.2-2.0% by weight, of the amide, 0.1-2.5% by weight, preferably 0.2-2.0% by weight, of the polyhydroxypolymer, 20-70% by weight, preferably 25-60% by weight, of the solvent, 15-35% by weight, preferably 20-30% by weight, of the coagulant, and 0-20% by weight, preferably 0-15% by weight, of the additives.

11. 11. The method according to any one of claims 8 to 10, wherein the additive is selected from water-soluble or water-dispersible precursors of Ce, Zr, Ti, La, Si and P, preferably selected from soluble salts of Ce, Zr, Ti and La, such as nitrates, sulfates and chlorides of these metals, or preferably selected from alkoxides, silicates and phosphates of Zr and Ti.

12. The method according to any one of claims 8 to 11, wherein the conditions of the aging treatment in step 2) comprise an aging temperature of 10-90°C, preferably 20-60°C; and an aging time of 1-72 hours, preferably 12-60 hours.

13. The leaching in step 3) is carried out by immersing the aged material in a leaching agent at 10-100°C for 1-72 hours, preferably 24-48 hours, followed by solid-liquid separation; 13. The method of any one of claims 8 to 12, wherein the solid-liquid separation is preferably carried out by a method selected from filtration, centrifugation, gravity settling, or a combination thereof.

14. The drying conditions in step 4) include a temperature of 10-150°C, preferably 30-90°C, and a time of 0.5-48 hours; and The method according to any one of claims 8 to 13, wherein the calcination conditions in step 4) comprise a temperature of 300-950°C, preferably 450-850°C, more preferably 550-750°C, and a time of 0.5-48 hours, preferably 2-24 hours, more preferably 1-6 hours.

15. 15. A porous alumina material prepared by the method of any one of claims 8 to 14.

16. a step of supporting a catalytically active component on the porous material, 16. The method for using the porous alumina material according to any one of claims 1 to 7 or 15 as a catalyst support, wherein the catalyst is preferably a heavy oil hydrogenation catalyst, and the catalytically active component is a hydrogenation catalytically active component, preferably selected from Co, Mo, Ni, W or a combination thereof.

17. A heavy oil hydrogenation catalyst comprising, based on the dry weight of the catalyst, 40-90% of a support and 10-50% of a catalytically active component for hydrogenation, wherein the support is the porous alumina material according to any one of claims 1 to 7 or 15, and preferably the catalytically active component for hydrogenation is selected from Co, Mo, Ni, W, or a combination thereof.

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