Porous material with desulfurization and deoxidization dual functions, and preparation method and application thereof

Abstract

This invention relates to the field of raw material purification, and discloses a porous material with dual functions of desulfurization and deoxygenation, and its preparation method. The preparation method of the porous material includes: hydrothermal crystallization of an additive, an alkali source, a silicon-aluminum source, and a metal source, wherein the additive is selected from organic acids capable of forming complexes with the metal in the metal source, or the additive and the metal source are derived from at least one of the following: a complex with a metal central atom and an organic acid anion as a ligand; the silicon-aluminum source is a substance capable of providing Si and / or Al; the weight ratio of the additive, alkali source, and silicon-aluminum source is 0.005–2:0.1–290:1; the amount of the additive is based on the weight of the organic acid anion; and the amount of the alkali source is based on the weight of OH groups. ‑ The amount of the silicon-aluminum source is calculated by weight of Al2O3 and / or SiO2. The porous material of this invention can achieve desulfurization and deoxidation through adsorption, exhibiting high removal performance and good dispersion of metal oxides within the porous material.

Description

Technical Field

[0001] This invention relates to the field of raw material purification, specifically to a porous material with dual functions of desulfurization and deoxygenation and its preparation method. Background Technology

[0002] Deoxidizers and desulfurizers are widely used in industries such as electronics, metallurgy, chemical industry, and petroleum. With the rapid development of science and technology, higher requirements have been placed on their usage conditions and desulfurization depth. In particular, the widespread application of new high-efficiency polyethylene and polypropylene catalysts and metallocene catalysts in polyethylene and polypropylene synthesis technologies has led to strict restrictions on the impurity content of ethylene and propylene raw materials used for polymerization in order to avoid poisoning and deactivation of polyolefin catalysts and to improve product quality.

[0003] In recent years, with the increasing demands for energy conservation and environmental protection, as well as higher requirements for product quality, enterprises have been accelerating their research on desulfurization and deoxygenation technologies while upgrading their equipment and products. The desulfurization and deoxygenation functions of adsorbents are achieved through complexation, van der Waals forces, or chemical reactions between oxygen or sulfur and the adsorbent. Adsorbents offer advantages such as high removal depth, easy regeneration, low cost, and ease of operation. However, problems still exist regarding their adsorption performance (uneven distribution of active components and easy aggregation).

[0004] Therefore, it is of great significance to develop a method for preparing a bifunctional porous material for desulfurization and deoxygenation that has excellent adsorption performance, simple preparation process, and is environmentally friendly. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned problems existing in the prior art and to provide a porous material with dual functions of desulfurization and deoxygenation, its preparation method and application.

[0006] To achieve the above objectives, the present invention provides a method for preparing porous materials, comprising: hydrothermal crystallization of an additive, an alkali source, a silicon-aluminum source, and a metal source, wherein the additive is selected from organic acids capable of forming complexes with metals in the metal source, or the additive and the metal source are derived from at least one of complexes in which the central atom is a metal and the organic acid anion is a ligand; the silicon-aluminum source is a substance capable of providing Si and / or Al; the weight ratio of the additive, the alkali source, and the silicon-aluminum source is 0.005-2:0.1-290:1; the amount of the additive is based on the weight of the organic acid anion; and the amount of the alkali source is based on the weight of OH groups. - The amount of the silicon-aluminum source is measured by weight of Al2O3 and / or SiO2.

[0007] A second aspect of this invention provides a method for preparing a porous material with dual functions of desulfurization and deoxidation. The method includes: hydrothermal crystallization of an alkali source, a silicon source, an aluminum source, and a metal source, wherein the silicon source is calculated as SiO2, the aluminum source as OH...- The weight ratio of the alkali source, the aluminum source (calculated as Al2O3), and the metal source (calculated as metal oxide) is 1:0.1-290:0.001-2.5:0.004-1.5. The metal source includes a first metal source and a second metal source. The first metal source is a Group IB metal source, and the second metal source is a Group VIIB metal source and / or a Group VIII metal source.

[0008] A third aspect of the present invention provides a porous material prepared by the method described above; or, the porous material comprises Si and / or Al and a metal, wherein the XRD pattern of the porous material has characteristic peaks at 12.1±0.2, 21.3±0.2 and 27.7±0.2.

[0009] A fourth aspect of the present invention provides a method for desulfurization and deoxidation, the method comprising: contacting the material to be desulfurized and deoxidized with the aforementioned porous material.

[0010] The fifth aspect of the present invention provides the application of the porous materials described above in desulfurization and deoxygenation.

[0011] Through the above technical solution, the porous material of the present invention can achieve desulfurization and deoxygenation through adsorption, with high removal performance and good dispersion of metal oxides in the porous material. Compared with traditional adsorbents, this one-step synthesis method avoids complex post-processing and saves significant manpower and resources while maintaining comparable performance. Furthermore, the synthesis process avoids the use of organic template agents, thus reducing environmental pollution. The preparation process of the present invention is simple, the composition is easily controlled, and it is easy to scale up. Attached Figure Description

[0012] Figure 1 This is a scanning electron microscope image of a porous material obtained according to a preferred embodiment of the present invention; Figure 2 This is an XRD pattern of a porous material obtained according to a preferred embodiment of the present invention. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] This invention provides a method for preparing porous materials, comprising: hydrothermal crystallization of an additive, an alkali source, a silicon-aluminum source, and a metal source, wherein the additive is selected from organic acids capable of forming complexes with metals in the metal source, or the additive and the metal source are derived from at least one of the following: a central metal atom and an organic acid anion as a ligand; the silicon-aluminum source is a substance capable of providing Si and / or Al; the weight ratio of the additive, the alkali source, and the silicon-aluminum source is 0.005-2:0.1-290:1; the amount of the additive is based on the weight of the organic acid anion; and the amount of the alkali source is based on the weight of OH groups. - The amount of the silicon-aluminum source is measured by weight of Al2O3 and / or SiO2 (Al2O3+SiO2).

[0015] According to the present invention, preferably, the weight ratio of the additive to the silicon-aluminum source is 0.1-1.5, such as 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, and any two of the above values ​​within the range.

[0016] According to the present invention, the additive is selected from organic acids capable of forming complexes with metals in a metal source, or from at least one of the following: the additive and the metal source are derived from a complex with a metal central atom and an organic acid anion as a ligand. It is understood that, according to one embodiment, the additive can react with the metal source to form a complex, preferably at least one of citric acid, tartaric acid, malic acid, oxalic acid, and lactic acid. According to another embodiment, the additive and the metal source are provided by at least one complex, the complex having a metal central atom and an organic acid anion as a ligand. The inventors of the present invention have further discovered that using the above-described additive can further improve the adsorption performance of porous materials.

[0017] According to the present invention, preferably, the weight ratio of the alkali source to the silicon-aluminum source is 0.3-250, such as 0.3, 0.5, 0.5, 1, 20, 50, 80, 100, 120, 150, 180, 200, 220, 250, and values ​​within any two of the above values, and more preferably 0.5-150. The alkali source can be selected from substances commonly found in the art that can hydrolyze to produce hydroxyl groups. Preferably, the alkali source is selected from alkali metal hydroxides and / or ammonia, more preferably at least one of sodium hydroxide, potassium hydroxide, and ammonia. In the present invention, ammonia is usually used in the form of ammonia water.

[0018] According to the present invention, preferably, the silicon-aluminum source is a composite silicon-aluminum source or a silicon source and an aluminum source. It is understood that the silicon-aluminum source in the present invention can exist (use) in the form of a composite silicon-aluminum source, or it can exist (use) in the form of a single silicon source and an aluminum source. The silicon source can be selected from substances commonly available in the art that can provide silicon. For example, the silicon source can be selected from at least one of silicon oxide, silicates, silicate esters, siloxanes, and organosilicon oils, preferably at least one of silica sol, silica, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, and siloxanes. The aluminum source can be selected from substances commonly available in the art that can provide aluminum. For example, the aluminum source can be selected from at least one of aluminum alkoxides, aluminum hydroxide, alumina, and aluminates, preferably at least one of aluminum isopropoxide, boehmite, alumina, sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum chloride, and aluminum sulfate.

[0019] According to the present invention, preferably, the weight ratio of Al2O3 to SiO2 in the silicon-aluminum source is 0.001-2.5.

[0020] According to the present invention, preferably, the weight ratio of the metal source to the silicon-aluminum source, calculated as metal oxide, is 0.004-1.5, for example, 0.004, 0.01, 0.05, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, and any two of the above values ​​within the range.

[0021] According to the present invention, preferably, the metal source includes a first metal source and a second metal source, wherein the first metal source is at least one of Group IB metals, more preferably a copper source; and the second metal source is at least one of Group VIIB metals and / or Group VIII metals, more preferably a manganese source and / or a nickel source.

[0022] According to the present invention, preferably, the weight ratio of the first metal source to the second metal source, calculated as oxide, is 0.02-9, and can be 0.02, 0.05, 0.1, 0.2, 0.5, 1, 1.5, 3, 4.5, 6, 7, 8, 9, or any two of the above values, and more preferably 1-5. Using the weight ratio of the first metal source to the second metal source described above in the present invention can further improve the performance of porous materials. According to the present invention, the metal source can be a water-soluble salt commonly used in the art that can provide the metal element; preferably, the metal source is selected from at least one of metal nitrates, acetates, and carbonates.

[0023] According to the present invention, preferably, the amount of water used in the raw material is such that the weight ratio of water to silicon-aluminum source is not greater than 300, more preferably 1-200, such as 1, 5, 10, 20, 30, 50, 80, 100, 130, 150, 180, 200 and any two of the above values ​​forming a range or values ​​within that range.

[0024] According to a preferred embodiment of the present invention, the conditions for hydrothermal crystallization include: a temperature of 60-150°C and a time of 2-60 hours. Preferably, the hydrothermal crystallization temperature is 70-150°C and the time is 3-48 hours. More preferably, the hydrothermal crystallization temperature is 90-140°C and the time is 15-30 hours.

[0025] In this invention, the preparation method further includes aging the crystallization raw material before hydrothermal crystallization. The aging conditions include a temperature of 5-100℃ and a time of 5-20h.

[0026] In this invention, to obtain a stable porous material product, the method further includes drying and calcining the hydrothermally crystallized product after hydrothermal crystallization. Preferably, the drying conditions include a temperature of 110-200℃ and a time of 3-30 hours. Preferably, the calcination conditions include a temperature of 300-500℃ and a time of 2-6 hours.

[0027] This invention also provides a method for preparing a porous material with dual functions of desulfurization and deoxidation. The method includes: hydrothermal crystallization of an alkali source, a silicon source, an aluminum source, and a metal source, wherein the silicon source is calculated as SiO2, and the aluminum source is calculated as OH... - The weight ratio of the alkali source, the aluminum source (calculated as Al2O3), and the metal source (calculated as metal oxide) is 1:0.1-290:0.001-2.5:0.004-1.5. The metal source includes a first metal source and a second metal source. The first metal source is a Group IB metal source, and the second metal source is a Group VIIB metal source and / or a Group VIII metal source.

[0028] In this preparation method, the raw material preferably contains the additives as described above, and the weight ratio of the additives to the silicon source based on SiO2 is preferably 0.005-2, such as 0.005, 0.1, 0.2, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.8, 2 and any two of the above values, and values ​​within the range, more preferably 0.1-1.5.

[0029] According to the present invention, preferably, the silicon source is calculated as SiO2, and the OH group is... - The weight ratio of the alkali source (calculated as Al2O3), the aluminum source (calculated as Al2O3), and the metal source (calculated as metal oxide) is 1:0.3-250:0.005-2:0.05-1.

[0030] According to the present invention, preferably, the weight ratio of the first metal source (calculated as metal oxide) to the silicon source (calculated as SiO2) is 0.05-0.45, such as 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, and any two of the above values ​​within a range. More preferably, the first metal source is selected from a copper source.

[0031] According to the present invention, preferably, the weight ratio of the second metal source (calculated as metal oxide) to the silicon source (calculated as SiO2) is 0.05-0.55, such as 0.05, 0.1, 0.2, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, and any two of the above values ​​within a range. More preferably, the second metal source is selected from a manganese source and / or a nickel source.

[0032] According to a preferred embodiment of the present invention, the weight ratio of the first metal source to the second metal source, calculated as metal oxide, is 0.02-9, such as 0.02, 0.05, 0.1, 0.2, 0.3, 0.5, 0.6, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 7, 8, 9, and values ​​within any range formed by two of the above values, and is further preferably 1-5. When the weight ratio of the first metal source to the second metal source is within the above range, the prepared desulfurization and deoxidation bifunctional porous material has a better desulfurization and deoxidation effect.

[0033] According to the present invention, the metal source can be a water-soluble salt commonly used in the art that can provide the metal element. Preferably, the metal source is selected from at least one of the metal nitrates, acetates and carbonates.

[0034] In this invention, the silicon source can be selected from substances commonly used in the art that can provide silicon. For example, the silicon source is selected from at least one of silicon oxide, silicates, silicate esters, siloxanes and organosilicon oils, preferably at least one of silica sol, silica, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and siloxanes.

[0035] In this invention, the aluminum source can be selected from substances commonly available in the art that can provide aluminum. The aluminum source can be selected from at least one of aluminum alkoxides, aluminum hydroxide, aluminum oxide, and aluminates, preferably at least one of aluminum isopropoxide, boehmite, aluminum oxide, sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum chloride, and aluminum sulfate.

[0036] In this invention, in order to obtain porous materials with better desulfurization and deoxygenation effects, the crystallization raw material may also contain an alkali source, which is selected from alkali metal hydroxides and / or ammonia, preferably at least one of sodium hydroxide, potassium hydroxide and ammonia.

[0037] According to the present invention, preferably, the amount of water used in the hydrothermal crystallization system is such that the weight ratio of water to silicon source (based on SiO2) is not greater than 300, preferably 1-200.

[0038] In this invention, the conditions for hydrothermal crystallization are the same as the temperature and time provided in the first aspect above, and will not be repeated here.

[0039] The present invention also provides a porous material, which is prepared by the method described above; or, the porous material comprises Si and / or Al and a metal, wherein the XRD pattern of the porous material has characteristic peaks at 12.1±0.2, 21.3±0.2 and 27.7±0.2.

[0040] According to the present invention, preferably, the porous material contains 5-75% by weight of Si and / or Al based on Al2O3 and / or SiO2, and 5-80% by weight of metal based on metal oxides.

[0041] Preferably, the metal in the porous material of the present invention includes a first metal and a second metal, wherein the first metal is selected from group IB metals and the second metal is a group VIIB metal and / or a group VIII metal.

[0042] Preferably, in the porous material of the present invention, the weight ratio of the first metal to the second metal, calculated as oxide, is 0.02-9, more preferably 1-5.

[0043] Preferably, in the porous material of the present invention, the first metal is Cu, and the second metal is Mn and / or Ni.

[0044] In this invention, the porous material includes Si, Al, and metals present in the form of oxides.

[0045] Preferably, the porous material of the present invention is spherical.

[0046] Preferably, the mesopore specific surface area of ​​the porous material of the present invention is 300-700 m². 2 / g, more preferably 400-700m 2 / g.

[0047] Preferably, the total pore volume of the porous material of the present invention is 0.2-0.6 cm³. 3 / g, more preferably 0.3-0.5cm 3 / g.

[0048] Preferably, the mesopore volume of the porous material of the present invention is 0.15-0.55 cm³. 3 / g, more preferably 0.3-0.5cm 3 / g.

[0049] Preferably, the average pore size of the porous material of the present invention is 0.3-20 nm, more preferably 0.3-15 nm.

[0050] The present invention also provides a method for desulfurization and deoxygenation, the method comprising: contacting the material to be desulfurized and deoxygenated with the porous material described above.

[0051] In this invention, there are no special requirements for the amount of porous material used. The adsorption capacity of sulfur and oxygen per 100g of porous material is ≥10g. Therefore, when using the porous material for desulfurization and deoxygenation, those skilled in the art can determine the amount of porous material based on the adsorption capacity. Generally, the amount of porous material used is 10-100g per cubic meter of material.

[0052] The porous material of this invention is suitable for various common materials containing S and O, wherein the S content in the material is ≤10 g / m³. 3 (e.g., 0.01-10g / m) 3 The content of O is ≤10g / m 3 (e.g., 0.01-10 g / m) 3 ).

[0053] The porous material of the present invention is particularly suitable for removing sulfur (including hydrogen sulfide and various organic forms of sulfur) and trace amounts of oxygen from gases and organic liquids. Preferably, the material is a liquid or gas containing sulfur (S) and / or oxygen (O).

[0054] The present invention does not have any special requirements for the contact conditions. In a preferred embodiment, the contact conditions include: a temperature of 0-200°C and a time of 0.01-1h.

[0055] Finally, the present invention also provides the application of the porous materials described above in desulfurization and deoxygenation.

[0056] Example 1 Aluminum hydroxide, sodium hydroxide, copper nitrate, nickel nitrate, water and citric acid were mixed evenly, and then 15g of tetraethyl orthosilicate was added. The prepared solution was stirred at room temperature for 4 hours and allowed to stand for 12 hours to age. The aged solution was then placed in a crystallization kettle with a polytetrafluoroethylene liner and crystallized at 130℃ for 1 day. The weight ratios of the components are as follows: R1 / SiO2=0.23, Al2O3 / SiO2=0.08; H2O / SiO2=100; CuO / SiO2=0.53; NiO / SiO2=0.3; R2 / SiO2=0.11, where R1 and R2 represent sodium hydroxide and citric acid, respectively.

[0057] The obtained crystallized product was washed, centrifuged, and dried at 110℃ for 24 hours to obtain a solid sample, which was then calcined at 400℃ for 4 hours to obtain a porous material. Elemental analysis showed that the elemental composition of the porous material is shown in Table 1.

[0058] SEM images show that the obtained product is a spherical desulfurization and deoxidation bifunctional porous material.

[0059] Example 2 Alumina, sodium hydroxide, copper nitrate, nickel nitrate, water and malic acid were mixed evenly, and then 14.4g of an aqueous solution containing 30% silica sol was added. The prepared solution was stirred at room temperature for 4 hours and allowed to stand for aging for 15 hours. The aged solution was then placed in a crystallization kettle with a polytetrafluoroethylene liner and crystallized at 110℃ for 1 day. The weight ratios of the components are as follows: R1 / SiO2=0.21, Al2O3 / SiO2=0.08; H2O / SiO2=110; CuO / SiO2=0.53; NiO / SiO2=0.3; R2 / SiO2=0.11, where R1 and R2 represent sodium hydroxide and citric acid, respectively.

[0060] The obtained crystallized product was washed, centrifuged, and dried at 120℃ for 18 hours to obtain a solid sample, which was then calcined at 450℃ for 3 hours to obtain a porous material. Elemental analysis showed that the elemental composition of the porous material is shown in Table 1.

[0061] Example 3 Aluminum hydroxide, sodium hydroxide, copper nitrate, nickel nitrate, water and citric acid were mixed evenly, and then 15g of tetraethyl orthosilicate was added. The prepared solution was stirred at room temperature for 4 hours and allowed to stand for 12 hours to age. The aged solution was then placed in a crystallization kettle with a polytetrafluoroethylene liner and crystallized at 130℃ for 1 day. The weight ratios of the components are as follows: R1 / SiO2=0.52, Al2O3 / SiO2=1; H2O / SiO2=50; CuO / SiO2=0.22; NiO / SiO2=0.24; R2 / SiO2=0.11, where R1 and R2 represent sodium hydroxide and citric acid, respectively.

[0062] The obtained crystallized product was washed, centrifuged, and dried at 110℃ for 24 hours to obtain a solid sample, which was then calcined at 450℃ for 4 hours to obtain a porous material. Elemental analysis showed that the elemental composition of the porous material is shown in Table 1.

[0063] Example 4 Porous materials were prepared according to the method of Example 1, except that citric acid was not added as an additive.

[0064] Example 5 Porous materials were prepared according to the method of Example 1, except that the additive was polyethylene glycol (PEG).

[0065] Example 6 Porous materials were prepared according to the method of Example 1, except that the weight ratio of the additive to SiO2 was 1.5 (the amount of additive was 5g).

[0066] Example 7 Porous materials were prepared according to the method in Example 1, except that the alkali source was replaced with ammonia (NH3 concentration of 22%).

[0067] Example 8 Porous materials were prepared according to the method of Example 1, except that the amount of alkali source was adjusted to a weight ratio of alkali source to silicon-aluminum source of 250.

[0068] Example 9 Porous materials were prepared according to the method of Example 1, except that nickel nitrate was replaced with manganese nitrate. Elemental analysis showed that the elemental composition of the porous materials is shown in Table 1.

[0069] Example 10 Porous materials were prepared according to the method of Example 1, except that manganese nitrate, copper nitrate, and nickel nitrate were added, wherein the weight ratio of the metal source to the silicon source (calculated as SiO2) was MnO / SiO2=0.1; CuO / SiO2=0.53; and NiO / SiO2=0.2.

[0070] Example 11 Porous materials were prepared according to the method of Example 1, except that nickel nitrate was replaced with iron nitrate.

[0071] Comparative Example 1 Porous materials were prepared according to the method of Example 1, except that no alkali source was added.

[0072] Comparative Example 2 Porous materials were prepared according to the method of Example 1, except that the additive was the inorganic acid HCl.

[0073] Comparative Example 3 Porous materials were prepared according to the method of Example 1, except that nickel nitrate was replaced with zinc nitrate.

[0074] Comparative Example 4 The porous material is prepared using the traditional two-step calcination method, and the specific steps are as follows: Aluminum hydroxide, sodium hydroxide, and water were mixed evenly, and then 15g of tetraethyl orthosilicate was added. The prepared solution was stirred at room temperature for 4 hours and allowed to stand for aging for 12 hours. The aged solution was placed in a crystallization kettle with a polytetrafluoroethylene liner and crystallized at 130℃ for 1 day. Then, it was dried (110℃, 24h) and calcined (400℃, 4h) to obtain a porous material. Copper nitrate and nickel nitrate were impregnated onto the porous material by equal volume, and after drying (110℃, 24h) and calcining (400℃, 4h), a metal-modified porous material was obtained.

[0075] The weight ratios of the components are as follows: R1 / SiO2=0.23, Al2O3 / SiO2=0.08; H2O / SiO2=100; CuO / SiO2=0.53; NiO / SiO2=0.5; R2 / SiO2=0.11, where R1 and R2 represent sodium hydroxide and citric acid, respectively.

[0076] Table 1

[0077] Test Example 1 The morphology and structure of the porous materials obtained in the above embodiments and comparative examples were analyzed and characterized, and the results are shown in Table 2.

[0078] The morphology of the material was observed using a scanning electron microscope (SEM, model S-4800 field emission scanning electron microscope), and the XRD pattern of the porous material was determined using an X'Pert PRO X-ray diffractometer, with 2θ = 5-60° and a step size of 0.02°. The mesoporous specific surface area, total pore volume, mesoporous pore volume, and average pore size of the porous material were determined by N2 adsorption / desorption curves, and the results are shown in Table 2. The SEM images of the porous material obtained in Example 1 are shown below. Figure 1 As shown; the XRD pattern of the material obtained in Example 1 is as follows. Figure 2 As shown. Although not shown, the SEM images and XRD patterns of other embodiments are similar to those of the other embodiments. Figure 1 resemblance.

[0079] Table 2

[0080] Test Example 2 The porous materials obtained in the above embodiments and comparative examples were used for desulfurization and deoxygenation. The specific steps were as follows: The porous materials were placed in naphtha containing 30 g / L hydrogen sulfide and 30 g / L oxygen (the amount of the porous material was 170 g per cubic meter of naphtha), stirred at room temperature for 30 minutes, and the sulfur and oxygen content in the naphtha before and after adsorption was measured using a sulfur-nitrogen analyzer and a trace oxygen detector. The desulfurization rate and deoxygenation rate were calculated. The results are shown in Table 3.

[0081] Table 3

[0082] The examples and comparative examples show that the porous materials prepared using the examples of the present invention have better desulfurization and deoxidation effects. Examples 1-3 show that the preferred raw material ratios and preparation conditions of the present invention result in the best desulfurization and deoxidation effects. Comparing Examples 1 and Examples 4-6, it can be seen that using the types and amounts of additives described in the present invention can prepare porous materials with better desulfurization and deoxidation effects. Comparing Examples 1 and Examples 9-11, it can be seen that when the metal source is within the preferred range of the present invention, the prepared porous materials have better desulfurization and deoxidation effects.

[0083] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing porous materials, characterized in that, The method includes: hydrothermal crystallization of an additive, an alkali source, a silicon-aluminum source, and a metal source, wherein the additive is selected from at least one of an organic acid capable of forming a complex with a metal in the metal source, or the additive and the metal source are derived from a complex with a metal central atom and an organic acid anion as a ligand; the silicon-aluminum source is a substance capable of providing Si and / or Al; the weight ratio of the additive, the alkali source, and the silicon-aluminum source is 0.005-2:0.1-290:1; the amount of the additive is based on the weight of the organic acid anion; and the amount of the alkali source is based on the weight of OH groups. - The amount of the silicon-aluminum source is measured by weight of Al2O3 and / or SiO2.

2. The method according to claim 1, wherein, The weight ratio of the additive to the silicon-aluminum source is 0.1-1.5; And / or, the additive is selected from at least one of citric acid, tartaric acid, malic acid, oxalic acid and lactic acid.

3. The method according to claim 1, wherein, The weight ratio of the alkali source to the silicon-aluminum source is 0.3-250, preferably 0.5-150; And / or, the alkali source is selected from alkali metal hydroxides and / or ammonia; Preferably, the alkali source is selected from at least one of sodium hydroxide, potassium hydroxide, and ammonia.

4. The method according to claim 1, wherein, The silicon-aluminum source is a composite silicon-aluminum source or a silicon source and an aluminum source; And / or, the weight ratio of Al2O3 to SiO2 in the silicon-aluminum source is 0.001-2.

5.

5. The method according to claim 1, wherein, The weight ratio of the metal source (based on metal oxides) to the silicon-aluminum source is 0.004-1.

5. And / or, the metal source includes a first metal source and a second metal source, wherein the first metal source is a Group IB metal source and the second metal source is a Group VIIB metal source and / or a Group VIII metal source; Preferably, the weight ratio of the first metal source to the second metal source, calculated as oxides, is 0.02-9, more preferably 1-5; Preferably, the first metal source is a copper source; Preferably, the second metal source is a manganese source and / or a nickel source.

6. The method according to claim 1, wherein, Water is added during the hydrothermal crystallization process, and the amount of water used is such that the weight ratio of water to silicon-aluminum source is no more than 300, preferably 1-200.

7. The method according to claim 1, wherein, The conditions for hydrothermal crystallization include: a temperature of 60-150℃ and a time of 2-60h; Preferably, the conditions for hydrothermal crystallization include: a temperature of 70-150℃ and a time of 3-48h; Preferably, the method further includes aging the crystallization raw material before hydrothermal crystallization, wherein the aging conditions include a temperature of 5-100℃ and a time of 5-20h. Preferably, the method further includes drying and calcining the hydrothermal crystallization product after hydrothermal crystallization; More preferably, the drying conditions include: a temperature of 110-200°C and a time of 3-30 hours; More preferably, the calcination conditions include: a temperature of 300-500℃ and a time of 2-6 hours.

8. A method for preparing a porous material with dual functions of desulfurization and deoxygenation, characterized in that, The method includes: hydrothermal crystallization of an alkali source, a silicon source, an aluminum source, and a metal source, wherein the silicon source is calculated as SiO2, the aluminum source is calculated as OH... - The weight ratio of the alkali source, the aluminum source (calculated as Al2O3), and the metal source (calculated as metal oxide) is 1:0.1-290:0.001-2.5:0.004-1.

5. The metal source includes a first metal source and a second metal source. The first metal source is a Group IB metal source, and the second metal source is a Group VIIB metal source and / or a Group VIII metal source.

9. The method according to claim 8, wherein, Silicon source as SiO2, OH - The weight ratio of the alkali source (calculated as Al2O3), the aluminum source (calculated as Al2O3), and the metal source (calculated as metal oxide) is 1:0.3-250:0.005-2:0.05-1. And / or, the first metal source is selected from a copper source; And / or, the second metal source is selected from a manganese source and / or a nickel source; And / or, the weight ratio of the first metal source (calculated as metal oxide) to the silicon source (calculated as SiO2) is 0.05-0.45; And / or, the weight ratio of the second metal source (calculated as metal oxide) to the silicon source (calculated as SiO2) is 0.05-0.55; And / or, the weight ratio of the first metal source to the second metal source, calculated as metal oxide, is 0.02-9, preferably 1-5.

10. The method according to claim 8, wherein, The silicon source is selected from at least one of silicon oxide, silicate, silicate ester, siloxane and organosilicon oil; And / or, the aluminum source is selected from at least one of aluminum alkoxides, aluminum hydroxide, aluminum oxide, and aluminates; And / or, the alkali source is selected from alkali metal hydroxides and / or ammonia, preferably at least one of sodium hydroxide, potassium hydroxide and ammonia.

11. The method according to any one of claims 8-10, wherein, The silicon source is selected from at least one of silica sol, silica, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate. And / or, the aluminum source is selected from at least one of aluminum isopropoxide, boehmite, alumina, sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum chloride, and aluminum sulfate; And / or, the metal source is selected from at least one of the metal nitrates, acetates and carbonates.

12. The method according to claim 8, wherein, In the hydrothermal crystallization system, the amount of water used is such that the weight ratio of water to silicon source (based on SiO2) is no greater than 300, preferably 1-200.

13. The method according to claim 8, wherein, The conditions for hydrothermal crystallization include: a temperature of 60-150℃ and a time of 2-60h; Preferably, the conditions for hydrothermal crystallization include: a temperature of 70-150℃ and a time of 3-48h; Preferably, the method further includes aging the crystallization raw material before hydrothermal crystallization, wherein the aging conditions include a temperature of 5-100℃ and a time of 5-20h. Preferably, the method further includes drying and calcining the hydrothermal crystallization product after hydrothermal crystallization; More preferably, the drying conditions include: a temperature of 110-200°C and a time of 3-30 hours; More preferably, the calcination conditions include: a temperature of 300-500℃ and a time of 2-6 hours.

14. A porous material, characterized in that, The porous material is prepared by the method described in any one of claims 1-13; Alternatively, the porous material may include Si and / or Al as well as metals, and the XRD patterns of the porous material may have characteristic peaks at 12.1±0.2, 21.3±0.2, and 27.7±0.

2.

15. The porous material according to claim 14, wherein, The content of Si and / or Al, calculated as Al2O3 and / or SiO2, is 5-75% by weight; the content of metal, calculated as metal oxides, is 5-80% by weight. And / or, the metal includes a first metal and a second metal, wherein the first metal is a Group IB metal and the second metal is a Group VIIB metal and / or a Group VIII metal; Preferably, the weight ratio of the first metal to the second metal, calculated as oxides, is 0.02-9, more preferably 1-5; Preferably, the first metal is Cu; Preferably, the second metal is Mn and / or Ni.

16. The porous material according to claim 14, wherein, Si, Al and metals exist in the form of oxides; And / or, the porous material is spherical; And / or, the mesoporous specific surface area of ​​the porous material is 300-700 m². 2 / g; And / or, the total pore volume of the porous material is 0.2-0.6 cm³. 3 / g; And / or, the mesopore volume of the porous material is 0.15-0.55 cm³. 3 / g; And / or, the average pore size of the porous material is 0.3-20 nm.

17. A method for desulfurization and deoxygenation, characterized in that, The method includes contacting the material to be desulfurized and deoxidized with the porous material described in any one of claims 14-16.

18. The method according to claim 17, wherein, The amount of the porous material used is 10-100g per cubic meter of material; And / or, the content of S in the material is ≤10g / m³ 3 The content of O is ≤10g / m 3 ; And / or, the material is a liquid or gas containing sulfur and / or oxygen; And / or, the contact conditions include: a temperature of 0-200°C and a time of 0.01-1h.

19. The application of the porous material according to any one of claims 14-16 in desulfurization and deoxidation.

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