An organic oxide adsorbent, its preparation method and application

Abstract

The present invention provides an organic oxide adsorbent, a preparation method thereof and an application. The preparation method comprises the following steps: preparing seeds by controlling the pH value and a two-stage crystallization process, and then preparing 13X molecular sieve with a high silica-alumina ratio, excellent specific surface area and pore volume through aging treatment and hydrothermal crystallization treatment; then further modifying the surface and structure of the 13X molecular sieve, introducing organosilicon into the 13X molecular sieve through reaction with an organosilicon coupling agent and calcination treatment to improve the dispersibility and stability of the adsorbent, and increasing the adsorption sites through impregnation treatment with a copper salt solution, impregnation treatment with a titanium precursor and secondary calcination treatment to improve the adsorption capacity and selectivity of the adsorbent for organic oxides, thereby obtaining an adsorbent with excellent adsorption performance for organic oxides, and solving the problems of low adsorption capacity of molecular sieve for organic oxides in hydrocarbons, poor selective adsorption performance for organic oxides and narrow application range in the prior art.

Description

Technical Field

[0001] The present invention relates to the technical field of adsorption materials, and in particular, to an organic oxide adsorbent, a preparation method thereof, and an application thereof. Background Art

[0002] The separation of substances by adsorption method has been widely used in petroleum cracking and refinery fluid catalytic cracking. At present, the research on adsorption separation process is mainly applied to the removal of oxygenates in hydrocarbons with C4 and above by adsorption method; in addition, the hydrocarbon products obtained by Fischer-Tropsch synthesis of coal have different carbon number distributions, and the oxygenates in products with different carbon numbers have huge differences in molecular weight and molecular structure. Therefore, there is no adsorbent that is generally applicable to the oxygenates in products with different carbon numbers. Molecular sieve is a kind of aluminosilicate, which has the characteristics of rich pore system, large specific surface area and good thermal stability, and is considered as a preferred adsorbent material for removing oxygenates in olefins. Among them, FAU type (X, Y type) molecular sieves have a pore diameter of about 0.74 nm. In particular, X-type molecular sieves can better remove oxygenate impurities in olefins, and have been studied more and applied in industrial practice. However, when it is used for olefin purification, its adsorption heat is high, its adsorption capacity is weak, and in addition, a part of olefins will be adsorbed during the adsorption purification process. Therefore, it is of great significance to develop a molecular sieve adsorbent with high adsorption capacity, high organic oxide adsorption capacity and high organic oxide adsorption selectivity. Summary of the Invention

[0003] The main object of the present invention is to provide an organic oxide adsorbent, a preparation method thereof, and an application thereof, so as to solve the problems of low adsorption capacity of molecular sieve for organic oxides in hydrocarbons, poor selective adsorption performance of organic oxides, and narrow application range in the prior art.

[0004] To achieve the above object, according to one aspect of the present invention, a preparation method of an organic oxide adsorbent is provided, including the following steps:

[0005] Step S1, mixing a silicon source and water to obtain a silicon-containing material, mixing an aluminum source and water to obtain an aluminum-containing material, stirring and mixing the aluminum-containing material and the silicon-containing material to obtain a first gel-like mother liquor, adjusting the pH value of the first gel-like mother liquor to 8.5-12.5 with sodium hydroxide, and then performing two-stage hydrothermal crystallization treatment to obtain a solution containing 13X molecular sieve seeds; wherein, the crystallization temperature of the first-stage hydrothermal crystallization treatment is 20-60°C, and the crystallization temperature of the second-stage hydrothermal crystallization is 80-120°C;

[0006] Step S2, aging the solution containing 13X molecular sieve seeds, and then performing hydrothermal crystallization treatment at 60-105°C, and filtering, washing, and drying the hydrothermal crystallization product to obtain 13X molecular sieve;

[0007] Step S3: React 13X molecular sieve and organosilicon coupling agent in an organic alcohol solvent to obtain organosilicon-modified 13X molecular sieve. Soak the product of the first calcination treatment with a copper salt solution to obtain 13X molecular sieve impregnated with copper salt solution. Stir and mix the 13X molecular sieve impregnated with copper salt solution with a titanium precursor sol to obtain a mixture. After drying the mixture, perform a second calcination treatment to obtain an organic oxide adsorbent. Among them, the temperature of the first calcination treatment is 400 - 500 °C, and the temperature of the second calcination treatment is 450 - 550 °C.

[0008] Furthermore, the silicon source is selected from one or more of silica sol, tetraethyl orthosilicate, macroporous silica gel, silicon powder, fly ash, and white carbon black, and the aluminum source is selected from one or more of sodium aluminate, pseudo-boehmite, aluminum sulfate, and aluminum nitrate. The weight ratio of the silicon source to the aluminum source is (0.01 - 1.25):1.

[0009] Preferably, in step S1, the mass fraction of the silicon source in the silicon-containing material is 2% - 50%.

[0010] Preferably, in step S1, the silicon source and water are stirred at 20 - 60 °C for 0.1 - 12 h to obtain the silicon-containing material.

[0011] Preferably, in step S1, the mass fraction of the aluminum source in the aluminum-containing material is 15% - 60%.

[0012] Preferably, in step S1, the aluminum source and water are stirred at 20 - 60 °C for 0.1 - 12 h to obtain the aluminum-containing material.

[0013] Preferably, in step S1, the stirring temperature is 20 - 100 °C, and the stirring and mixing is carried out for 0.1 - 24 h to obtain the first gel-like mother liquor.

[0014] Furthermore, the pH value of the first gel-like mother liquor is 11.8 - 12.5.

[0015] Preferably, in step S1, the pH value of the first gel-like mother liquor is adjusted by adding solid sodium hydroxide or by adding an aqueous solution of sodium hydroxide.

[0016] Furthermore, the crystallization temperature in the second crystallization treatment is more than 40 °C higher than the crystallization temperature in the first crystallization treatment. Preferably, it is 50 - 60 °C higher.

[0017] Preferably, in the first hydrothermal crystallization treatment, the crystallization temperature is 40 - 60 °C, and the crystallization time is 4 - 24 h, more preferably 11 - 24 h.

[0018] Preferably, in the second hydrothermal crystallization treatment, the crystallization temperature is 90 - 100 °C, and the crystallization time is 6 - 48 h, more preferably 18 - 48 h.

[0019] Preferably, the molar ratio of each component in the solution containing the 13X molecular sieve seeds is: SiO 2 / Al 2 O 3 =(0.01 - 6):1, Na 2 O / SiO 2 =(0.01 - 4.0):1, H 2 O / SiO 2 =(1.0 - 50.0):1.

[0020] Furthermore, in step S2, the aging treatment is carried out under stirring conditions, the temperature of the aging treatment is 20 - 100 °C, and the time of the aging treatment is 0.1 - 24 h.

[0021] Preferably, in step S2, the time of the hydrothermal crystallization treatment is 0.1 - 36 h.

[0022] Preferably, in step S2, the hydrothermal crystallization product is filtered and washed to neutral, and then dried to constant weight at 80 - 120 °C to obtain the 13X molecular sieve.

[0023] Furthermore, in step S3, the organosilicon coupling agent is selected from one or more of methyltriethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane, tetraethyl orthosilicate, ethoxysilane, tetraethyl silicate, 3-aminopropyltriethoxysilane, and the organic alcohol solvent is selected from one or more of ethanol, propanol, and butanol.

[0024] Preferably, in step S3, the mass ratio of the 13X molecular sieve, the organosilicon coupling agent, and the organic alcohol solvent is 1:(0.002 - 0.05):(0.8 - 2).

[0025] Preferably, in step S3, the reaction temperature is 15 - 40 °C, and the reaction time is 1 - 10 h.

[0026] Preferably, in step S3, the time of the first calcination treatment is 0.5 - 4 h.

[0027] Furthermore, in step S3, the copper salt is selected from one or more of copper nitrate, copper chloride, and copper acetate.

[0028] Preferably, in step S3, the concentration of the copper salt is 0.1 - 2 mol / L, and the time of the soaking treatment is 6 - 48 h.

[0029] Furthermore, in step S3, the titanium source in the titanium precursor sol is selected from one or more of tetrabutyl titanate, titanium orthosilicate, or diisopropoxybis(acetylacetonato)titanium.

[0030] Preferably, in step S3, the titanium precursor sol is formed by mixing a titanium source, ethanol, and water.

[0031] More preferably, in step S3, the titanium source, ethanol and water are stirred and mixed at 50-70 °C for 1-6 h to form a titanium precursor sol.

[0032] More preferably, in step S3, ethanol and water are first mixed to form a mixed solvent, and then the titanium source is added for mixing.

[0033] More preferably, in step S3, the titanium source, ethanol and water are mixed in a mass ratio of 1:(3-7):(0.5-1.5).

[0034] Preferably, in step S3, the temperature of the drying treatment is 90-110 °C, and the time of the drying treatment is 6-18 h.

[0035] Preferably, in step S3, the time of the second calcination treatment is 0.5-4 h.

[0036] According to another aspect of the present invention, an organic oxide adsorbent is provided, which is prepared according to the preparation method of the organic oxide adsorbent as above.

[0037] According to another aspect of the present invention, the application of the above organic oxide adsorbent in removing organic oxides in hydrocarbons is provided.

[0038] Preferably, the hydrocarbon is a hydrocarbon product obtained by Fischer-Tropsch synthesis of coal or an olefin product obtained by petroleum cracking.

[0039] Preferably, the organic oxide is selected from one or more of alcohols, aldehydes, ketones, and carboxylic acids having 1-21 carbon atoms.

[0040] By applying the technical solution of the present invention, seeds are prepared by controlling the pH value and the two-stage crystallization process, and then a 13X molecular sieve with a high silicon-aluminum ratio, excellent specific surface area and pore volume is prepared through aging treatment and hydrothermal crystallization treatment. The prepared 13X molecular sieve has a high silicon source utilization rate and can provide more adsorption sites; then the surface and structure of the 13X molecular sieve are further modified to obtain an organic oxide adsorbent with a high silicon-aluminum ratio, high specific surface area and high pore volume. The surface and structure modification includes introducing organosilicon into the 13X molecular sieve through reaction with an organosilicon coupling agent and calcination treatment to improve the dispersibility and stability of the adsorbent, and increasing the adsorption sites through impregnation treatment with a copper salt solution, impregnation treatment with a titanium precursor and secondary calcination treatment to improve the adsorption capacity and selectivity of the adsorbent for organic oxides, and an adsorbent with excellent adsorption performance for organic oxides is obtained.

[0041] The adsorbent prepared by the method of the present invention has a high silicon-aluminum ratio, a high specific surface area and a high pore volume, and has excellent adsorption performance for organic oxides, and can efficiently adsorb and remove organic oxides in the Fischer-Tropsch synthesis alkene products or organic oxides in hydrocarbon fuels or chemical products. Detailed implementation mode

[0042] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0043] As described in the background art, there are problems in the prior art of the present invention that the molecular sieve has a low adsorption capacity for organic oxides in hydrocarbons, poor selective adsorption performance for organic oxides, and a narrow scope of application. To solve the above problems, a method for preparing an organic oxide adsorbent is provided, which includes the following steps:

[0044] Step S1: Mix a silicon source and water to obtain a silicon-containing material, mix an aluminum source and water to obtain an aluminum-containing material, stir and mix the aluminum-containing material and the silicon-containing material to obtain a first gel-like mother liquor, adjust the pH value of the first gel-like mother liquor to 8.5-12.5 with sodium hydroxide, and then perform two-stage hydrothermal crystallization treatment to obtain a solution containing 13X molecular sieve seeds; wherein, the crystallization temperature of the first-stage hydrothermal crystallization treatment is 20-60°C, and the crystallization temperature of the second-stage hydrothermal crystallization is 80-120°C;

[0045] Step S2: Aging the solution containing 13X molecular sieve seeds, then performing hydrothermal crystallization treatment at 60-105°C, and filtering, washing and drying the hydrothermal crystallization product to obtain 13X molecular sieve;

[0046] Step S3: React 13X molecular sieve and an organosilicon coupling agent in an organic alcohol solvent to obtain an organosilicon-modified 13X molecular sieve, soak the product of the first calcination treatment with a copper salt solution to obtain a 13X molecular sieve impregnated with a copper salt solution, stir and mix the 13X molecular sieve impregnated with the copper salt solution and a titanium precursor sol to obtain a mixture, dry the mixture and then perform a second calcination treatment to obtain an organic oxide adsorbent; wherein, the temperature of the first calcination treatment is 400-500°C, and the temperature of the second calcination treatment is 450-550°C.

[0047] In order to obtain a high-performance organic oxide adsorbent, the present invention provides a preparation method of an organic oxide adsorbent. By controlling the pH value and a two-stage crystallization process to prepare seeds, and then through aging treatment and hydrothermal crystallization treatment, a 13X molecular sieve with a high silicon-aluminum ratio, excellent specific surface area and pore volume is prepared. The prepared 13X molecular sieve has a high silicon source utilization rate and can provide more adsorption sites. Then, the surface and structure of the 13X molecular sieve are further modified to obtain an organic oxide adsorbent with a high silicon-aluminum ratio, high specific surface area and high pore volume. The surface and structure modification includes introducing organosilicon into the 13X molecular sieve through reaction with an organosilicon coupling agent and calcination treatment to improve the dispersibility and stability of the adsorbent, and increasing the adsorption sites through impregnation treatment with a copper salt solution, impregnation treatment with a titanium precursor and secondary calcination treatment to improve the adsorption capacity and selectivity of the adsorbent for organic oxides, thereby obtaining an adsorbent with excellent adsorption performance for organic oxides. The adsorbent prepared by the method of the present invention has a high silicon-aluminum ratio, high specific surface area and high pore volume, and has excellent adsorption performance for organic oxides, and can efficiently adsorb and remove organic oxides in Fischer-Tropsch synthesis alkene products, hydrocarbon fuels or chemical products.

[0048] In a preferred embodiment, the silicon source is selected from one or more of silica sol, tetraethyl orthosilicate, coarse pore silica gel, silicon powder, fly ash, and white carbon black, and the aluminum source is selected from one or more of sodium aluminate, pseudo-boehmite, aluminum sulfate, and aluminum nitrate. The weight ratio of the silicon source to the aluminum source is (0.01-1.25):1. In order for the two to react fully and form an organic oxide adsorbent with a high silicon-aluminum ratio and specific surface area, preferably in step S1, the mass fraction of the silicon source in the silicon-containing material is 2%-50%; preferably in step S1, the silicon source and water are stirred at 20-60°C for 0.1-12 h to obtain an aluminum-containing material; preferably in step S1, the mass fraction of the aluminum source in the aluminum-containing material is 15%-60%; preferably in step S1, the aluminum source and water are stirred at 20-60°C for 0.1-12 h to obtain an aluminum-containing material; preferably in step S1, the mixture is stirred at a stirring temperature of 20-100°C for 0.1-24 h to obtain a first gel-like mother liquor.

[0049] In a preferred embodiment, the pH value of the first gel-like mother liquor is 11.8-12.5, which is beneficial to the reaction of the silicon source and the aluminum source and further generates seeds with high crystallinity, stable crystal form and structure in the two-stage thermal crystallization treatment, so as to further generate a 13X molecular sieve with a high silicon-aluminum ratio, specific surface area and pore volume. Preferably in step S1, the pH value of the first gel-like mother liquor is adjusted by adding solid sodium hydroxide or by adding an aqueous solution of sodium hydroxide.

[0050] In a preferred embodiment, the crystallization temperature in the second-stage crystallization treatment is more than 40 °C higher than that in the first-stage crystallization treatment, preferably 50 - 60 °C higher. Two-stage hydrothermal crystallization treatment is adopted. Among them, the high-silica-alumina ratio 13X molecular sieve seeds generated in the first-stage crystallization treatment further grow and optimize in the first-stage crystallization treatment to form a solution of 13X molecular sieve seeds with a complete, uniform structure and a high specific surface area. Using the above-mentioned higher temperature difference is beneficial to optimizing the adsorption property of the organic oxide with a higher specific surface area. Preferably, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40 - 60 °C, and the crystallization time is 4 - 24 h, more preferably 11 - 24 h. Preferably, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 90 - 100 °C, and the crystallization time is 6 - 48 h, more preferably 18 - 48 h. Preferably, the molar ratio of each component in the solution containing 13X molecular sieve seeds is: SiO 2 / Al 2 O 3 =(0.01 - 6):1, Na 2 O / SiO 2 =(0.01 - 4.0):1, H 2 O / SiO 2 =(1.0 - 50.0):1, which is beneficial to the subsequent growth to form 13X molecular sieve with high adsorption performance. Preferably, both two-stage hydrothermal crystallization treatments are carried out in a hydrothermal reaction kettle.

[0051] In order to obtain 13X molecular sieve with a more regular and uniform structure, in a preferred embodiment, in step S2, the aging treatment is carried out under stirring conditions, the temperature of the aging treatment is 20 - 100 °C, and the time of the aging treatment is 0.1 - 24 h. Preferably, in step S2, the time of the hydrothermal crystallization treatment is 0.1 - 36 h. Preferably, in step S2, after filtering the hydrothermal crystallization product and washing it to neutral, it is dried to constant weight at 80 - 120 °C to obtain 13X molecular sieve.

[0052] In order to obtain a higher coupling efficiency and coupling effect, in a preferred embodiment, in step S3, the organosilicon coupling agent is selected from one or more of methyltriethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane, tetraethyl orthosilicate, ethoxysilane, tetraethyl orthosilicate, 3-aminopropyltriethoxysilane, and the organic alcohol solvent is selected from one or more of ethanol, propanol, and butanol. Preferably, in step S3, the mass ratio of 13X molecular sieve, organosilicon coupling agent, and organic alcohol solvent is 1:(0.002 - 0.05):(0.8 - 2). Preferably, in step S3, the reaction temperature is 15 - 40 °C, and the reaction time is 1 - 10 h. Preferably, in step S3, the time of the first calcination treatment is 0.5 - 4 h.

[0053] In a preferred embodiment, in step S3, the copper salt is selected from one or more of copper nitrate, copper chloride, and copper acetate; preferably in step S3, the concentration of the copper salt is 0.1-2 mol / L, and the soaking treatment time is 6-48 h, so as to obtain a higher adsorption capacity and selectivity of the organic oxide while improving the utilization rate of the copper salt raw material.

[0054] In a preferred embodiment, in step S3, the titanium source in the titanium precursor sol is selected from one or more of tetrabutyl titanate, titanium orthosilicate, and diisopropoxydiacetylacetone titanium; preferably in step S3, the titanium precursor sol is formed by mixing a titanium source, ethanol, and water. Using ethanol and water as solvents can form a homogeneous titanium precursor sol, and the solvents are green and environmentally friendly; more preferably in step S3, the titanium source, ethanol, and water are stirred and mixed at 50-70 °C for 1-6 h to form a titanium precursor sol; more preferably in step S3, ethanol and water are first mixed to form a mixed solvent, and then the titanium source is added for mixing; more preferably in step S3, the titanium source, ethanol, and water are mixed in a mass ratio of 1:(3-7):(0.5-1.5); preferably in step S3, the drying treatment temperature is 90-110 °C, and the drying treatment time is 6-18 h; preferably in step S3, the second calcination treatment time is 0.5-4 h.

[0055] According to another aspect of the present invention, an organic oxide adsorbent is provided, which is prepared according to the above preparation method of the organic oxide adsorbent. The prepared organic oxide adsorbent has excellent specific surface area and pore volume, which helps to improve the performance of the adsorbent in various applications, such as gas separation, pollutant removal, and catalysis and other fields.

[0056] According to another aspect of the present invention, the application of the above organic oxide adsorbent in removing organic oxides in hydrocarbons is provided; preferably the hydrocarbon is a hydrocarbon product synthesized by Fischer-Tropsch synthesis of coal or an olefin product obtained by petroleum cracking; preferably the organic oxide is selected from one or more of alcohols, aldehydes, ketones, and carboxylic acids having 1-21 carbon atoms. The obtained organic oxide adsorbent has a high adsorption capacity and selectivity for the organic oxides in them, especially for the organic oxides in hydrocarbon products with various carbon numbers synthesized by Fischer-Tropsch synthesis or olefin products with various carbon numbers in petroleum cracking, especially C1-C15 organic oxides, having high adsorption efficiency, high capacity, and high selectivity.

[0057] The following further describes the present application in detail with specific examples, and these examples should not be construed as limiting the scope claimed by the present application.

[0058] Example 1

[0059] A preparation method of an organic oxide adsorbent is as follows:

[0060] Step 1: Dissolve 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) in 36.0 g of deionized water. After pretreatment at 25°C and 500 rpm for 1 hour in a sealed autoclave, a silicon-containing material is obtained;

[0061] Dissolve 24 g of aluminum sulfate in 18.0 g of deionized water and stir at 25°C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0062] Dropwise add the aluminum-containing material solution to the silicon-containing material and continue stirring at 60°C for 8 h to obtain a gel solution;

[0063] Dissolve 6.74 g of sodium hydroxide in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and add it to the gel solution until the pH value is 12 to obtain a gel solution;

[0064] Place the gel solution in a hydrothermal reaction kettle for two-stage hydrothermal crystallization treatment. In the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40°C and the crystallization time is 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95°C and the crystallization time is 24 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO 2 / Al 2 O 3 =1.5:1, Na 2 O / SiO 2 =1.6:1, H 2 O / SiO 2 =32:1.

[0065] Step 2: Age the solution containing 13X molecular sieve seeds at 60°C for 12 h, then carry out hydrothermal crystallization treatment at 80°C for 12 h. Filter, wash the hydrothermal crystallization product to neutrality, and dry it at 100°C to constant weight to obtain 13X molecular sieve.

[0066] Step 3: Add 50 g of carbon-modified 13X molecular sieve and 0.5 g of methyltriethoxysilane to 49.5 g of absolute ethanol, stir and react at room temperature for 4 hours, then filter, and calcine the filtered molecular sieve at 450°C for 2 hours;

[0067] Immerse the calcined 13X molecular sieve in an aqueous solution of copper nitrate at 1 mol / L at room temperature for 24 hours;

[0068] Drop 10 g of tetrabutyl titanate into a mixed solvent of 50 g of ethanol and 10 g of distilled water, and stir at 60°C for 3 hours to obtain a titanium precursor sol;

[0069] The 13X molecular sieve after being soaked in the copper salt solution described above was added to the titanium precursor sol. After stirring evenly, the mixture was dried at 100 °C for 12 hours, and then heated to 500 °C at a heating rate of 5 °C / min in a kiln and calcined for 2 hours;

[0070] The calcined product was dried by a vacuum drying device for 12 hours to obtain a molecular sieve organic oxide adsorbent.

[0071] Example 2

[0072] Step 1: 1 g of silicon powder was dissolved in 18 g of deionized water, and after being pretreated at 25 °C and 500 rpm for 1 hour in a closed reaction kettle, a silicon-containing material was obtained;

[0073] 12 g of aluminum nitrate was dissolved in 18.0 g of deionized water and stirred at 35 °C and 500 rpm for 1 hour to prepare an aluminum-containing material;

[0074] The aluminum-containing material was added dropwise to the silicon-containing material, and stirring was continued at 50 °C for 6 hours to obtain a gel solution;

[0075] An aqueous solution of sodium hydroxide prepared by dissolving 2 g of sodium hydroxide in 36 g of deionized water was added to the gel solution until the pH value reached 11.8 to obtain a gel solution;

[0076] The gel solution was transferred to a hydrothermal reaction kettle for two-stage hydrothermal crystallization treatment. In the first-stage hydrothermal crystallization treatment, the crystallization temperature was 50 °C and the crystallization time was 14 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature was 100 °C and the crystallization time was 18 hours to obtain a solution containing 13X molecular sieve seeds. In the solution containing 13X molecular sieve seeds, the molar ratio of each component was: SiO 2 / Al 2 O 3 = 0.6:1, Na 2 O / SiO 2 = 3:1, H 2 O / SiO 2 = 20:1.

[0077] Step 2: The solution containing 13X molecular sieve seeds was aged at 20 °C for 0.1 h, then subjected to hydrothermal crystallization treatment at 60 °C for 0.1 h. The hydrothermal crystallization product was filtered, washed to neutrality, and dried to constant weight at 80 °C to obtain 13X molecular sieve.

[0078] Step 3: 50 g of carbon-modified 13X molecular sieve and 0.1 g of isopropyltrimethoxysilane were added to 40 g of absolute ethanol, and the mixture was stirred and reacted at 15 °C for 1 hour, then filtered. The filtered molecular sieve was calcined at 400 °C for 0.5 hour;

[0079] The calcined 13X molecular sieve was immersed in an aqueous solution of copper chloride at 0.1 mol / L at room temperature for 24 hours;

[0080] 10 g of titanium orthosilicate was added dropwise to a mixed solvent of 30 g of ethanol and 5 g of distilled water, and stirred at 50 °C for 1 hour to obtain a titanium precursor sol;

[0081] The 13X molecular sieve after soaking in the copper salt solution was added to the titanium precursor sol. After stirring evenly, the mixture was dried at 90 °C for 6 hours, and then heated to 450 °C at a heating rate of 5 °C / min in a kiln and calcined for 0.5 hour;

[0082] Example 3

[0083] A preparation method of an organic oxide adsorbent, the specific steps are as follows:

[0084] Step 1, dissolve 0.17 g of silicon powder in 6 g of deionized water, and pretreat it at 25 °C and 200 rpm for 1 hour in a closed reaction kettle to obtain a silicon-containing material;

[0085] Dissolve 12 g of aluminum nitrate in 18.0 g of deionized water, and stir at 35 °C and 200 rpm for 1 hour to prepare an aluminum-containing material;

[0086] Add the aluminum source solution to the silicon-containing material, and stir at 100 °C for 24 hours to obtain a gel solution;

[0087] An aqueous solution of sodium hydroxide prepared by dissolving 0.9 g of sodium hydroxide in 6 g of deionized water was added to the gel solution until the pH value was 12.5. Then, the prepared gel was poured into a hydrothermal reaction kettle for two-stage crystallization. First, crystallize at 60 °C for 24 hours, and then raise the temperature to 120 °C for a crystallization reaction of 48 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO 2 / Al 2 O 3 =0.1:1, Na 2 O / SiO 2 =4:1, H 2 O / SiO 2 =1:1.

[0088] Step 2, age the solution containing 13X molecular sieve seeds at 100 °C for 24 h, then carry out hydrothermal crystallization treatment at 105 °C for 36 h. The hydrothermal crystallization product was filtered, washed to neutral, and dried to constant weight at 120 °C to obtain 13X molecular sieve.

[0089] (3) Add 50 g of carbon-modified 13X molecular sieve and 2.5 g of tetraethyl orthosilicate to 100 g of absolute ethanol, stir and react at 40 °C for 10 hours, then filter, and calcine the filtered molecular sieve at 500 °C for 4 hours;

[0090] Immerse the calcined 13X molecular sieve in an aqueous solution of copper acetate at 2 mol / L at room temperature for 24 hours;

[0091] Drop 10 g of diisopropoxydiacetylacetone titanium into a mixed solvent of 70 g of ethanol and 15 g of distilled water, stir at 70 °C for 6 hours to obtain a titanium precursor sol;

[0092] Add the 13X molecular sieve soaked in the copper salt solution to the titanium precursor sol, stir evenly, dry the mixture at 110 °C for 18 hours, and then heat it to 550 °C at a heating rate of 5 °C / min in a kiln and calcine for 4 hours;

[0093] Dry the calcined product in a vacuum drying equipment for 12 hours to obtain an organic oxide adsorbent.

[0094] Example 4

[0095] The difference from Example 1 is only that Step 1 is different. Specifically, Step 1 is as follows:

[0096] Take 14.65 g of tetraethyl orthosilicate and mix it with 36 g of deionized water, pre-treat it in a closed reactor at 25 °C and 800 rpm for 1 hour to obtain a silicon-containing material;

[0097] Dissolve 12 g of aluminum nitrate in 18.0 g of deionized water and stir at 35 °C and 800 rpm for 1 hour to obtain an aluminum-containing material;

[0098] Gradually add the aluminum-containing material to the silicon-containing material and mix and stir at 20 °C for 0.1 hour to prepare a gel solution;

[0099] Dissolve 0.56 g of sodium hydroxide in 6 g of deionized water to make a sodium hydroxide aqueous solution, pour it into the gel solution until the pH value is 8.5, and introduce the prepared gel into a hydrothermal reaction kettle to perform a segmented crystallization reaction: first set the crystallization temperature to 20 °C and keep it for 4 hours; then raise it to 80 °C and keep the crystallization for 6 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO 2 / Al 2 O 3 = 2.5:1, Na 2 O / SiO 2 = 0.1:1, H 2 O / SiO2 = 40:1.

[0100] Example 5

[0101] The difference from Example 1 is only that in step (3), methyltriethoxysilane is replaced by 3-aminopropyltriethoxysilane.

[0102] Example 6

[0103] The difference from Example 1 is only that in the second hydrothermal crystallization treatment, the crystallization temperature is 70 °C.

[0104] Example 7

[0105] The difference from Example 1 is only that in the second hydrothermal crystallization treatment, the crystallization temperature is 120 °C.

[0106] Example 8

[0107] The difference from Example 1 is only that in step (1), the pH value of the gel solution is adjusted to 8.5.

[0108] Comparative Example 1

[0109] The difference from Example 1 is only that in step one, only the first-stage hydrothermal crystallization treatment is carried out. Specifically, step one is as follows:

[0110] Step one: Dissolve 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) in 36.0 g of deionized water, and pre-treat it at 25 °C and 500 rpm for 1 hour in a closed reaction kettle to obtain a silicon-containing material;

[0111] Dissolve 24 g of aluminum sulfate in 18.0 g of deionized water, and stir it at 25 °C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0112] Dropwise add the aluminum-containing material liquid to the silicon-containing material, and continue to stir at 60 °C for 8 h to obtain a gel solution;

[0113] Dissolve 6.74 g of sodium hydroxide in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and add it to the gel solution until the pH value is 12 to obtain a gel solution;

[0114] Put the gel solution into a hydrothermal reaction kettle, carry out hydrothermal crystallization treatment, the crystallization temperature is 40 °C, and the crystallization time is 12 hours to obtain a solution containing 13X molecular sieve seeds.

[0115] Comparative Example 2

[0116] The difference from Example 1 is only that in step one, only the second-stage hydrothermal crystallization treatment is carried out. Specifically, step one is as follows:

[0117] Step 1: Dissolve 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) in 36.0 g of deionized water. After pretreatment at 25°C and 500 rpm for 1 hour in a closed reactor, a silicon-containing material is obtained;

[0118] Dissolve 24 g of aluminum sulfate in 18.0 g of deionized water and stir at 25°C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0119] Dropwise add the aluminum-containing material liquid to the silicon-containing material and continue stirring at 60°C for 8 h to obtain a gel solution;

[0120] Dissolve 6.74 g of sodium hydroxide in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and add it to the gel solution until the pH value reaches 12 to obtain a gel solution;

[0121] Place the gel solution in a hydrothermal reactor for hydrothermal crystallization treatment. The crystallization temperature is 95°C and the crystallization time is 24 hours to obtain a solution containing 13X molecular sieve seeds.

[0122] Comparative Example 3

[0123] The difference from Example 1 is only that Step 3 is not carried out. The specific steps are as follows:

[0124] Step 1: Dissolve 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) in 36.0 g of deionized water. After pretreatment at 25°C and 500 rpm for 1 hour in a closed reactor, a silicon-containing material is obtained;

[0125] Dissolve 24 g of aluminum sulfate in 18.0 g of deionized water and stir at 25°C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0126] Dropwise add the aluminum-containing material liquid to the silicon-containing material and continue stirring at 60°C for 8 h to obtain a gel solution;

[0127] Dissolve 6.74 g of sodium hydroxide in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and add it to the gel solution until the pH value reaches 12 to obtain a gel solution;

[0128] Place the gel solution in a hydrothermal reactor for two-stage hydrothermal crystallization treatment. In the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40°C and the crystallization time is 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95°C and the crystallization time is 24 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO 2 / Al 2 O 3 =1.5:1, Na 2 O / SiO2 = 1.6:1, H 2 O / SiO 2 = 32:1.

[0129] Step 2: The solution containing 13X molecular sieve seeds was aged at 60 °C for 12 h, then hydrothermally crystallized at 80 °C for 12 h. The hydrothermal crystallization product was filtered, washed until neutral, and dried to a constant weight at 100 °C to obtain 13X molecular sieve.

[0130] Comparative Example 4

[0131] The difference from Example 1 is only that in Step 3, the soaking treatment with copper salt solution is not carried out. The specific steps are as follows:

[0132] Step 1: 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) was dissolved in 36.0 g of deionized water, and after pretreatment at 25 °C and 500 rpm for 1 hour in a closed reaction kettle, a silicon-containing material was obtained;

[0133] 24 g of aluminum sulfate was dissolved in 18.0 g of deionized water and stirred at 25 °C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0134] The aluminum-containing material liquid was added dropwise to the silicon-containing material and stirred at 60 °C for 8 h to obtain a gel solution;

[0135] 6.74 g of sodium hydroxide was dissolved in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and added to the gel solution until the pH value was 12 to obtain a gel solution;

[0136] The gel solution was placed in a hydrothermal reaction kettle for two-stage hydrothermal crystallization treatment. In the first-stage hydrothermal crystallization treatment, the crystallization temperature was 40 °C and the crystallization time was 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature was 95 °C and the crystallization time was 24 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component was: SiO 2 / Al 2 O 3 = 1.5:1, Na 2 O / SiO 2 = 1.6:1, H 2 O / SiO 2 = 32:1.

[0137] Step 2: The solution containing 13X molecular sieve seeds was aged at 60 °C for 12 h, then hydrothermally crystallized at 80 °C for 12 h. The hydrothermal crystallization product was filtered, washed until neutral, and dried to a constant weight at 100 °C to obtain 13X molecular sieve.

[0138] Step 3: Add 50 g of carbon-modified 13X molecular sieve and 0.5 g of methyltriethoxysilane to 49.5 g of absolute ethanol, stir and react at room temperature for 4 hours, then filter, and calcine the filtered molecular sieve at 450 °C for 2 hours;

[0139] Drop 10 g of tetrabutyl titanate into a mixed solvent of 50 g of ethanol and 10 g of distilled water, and stir at 60 °C for 3 hours to obtain a titanium precursor sol;

[0140] Add the calcined 13X molecular sieve to the titanium precursor sol, stir evenly, dry the mixture at 100 °C for 12 hours, and then heat it to 500 °C at a heating rate of 5 °C / min in a kiln and calcine for 2 hours;

[0141] Dry the calcined product in a vacuum drying equipment for 12 hours to obtain a molecular sieve organic oxide adsorbent.

[0142] Comparative Example 5

[0143] The difference from Example 1 is only that in Step 3, the treatment of the titanium precursor sol is not carried out, and the specific steps are as follows:

[0144] Step 1: Dissolve 21.0 g of silica sol (mass fraction of silicon dioxide is 30%) in 36.0 g of deionized water, and pretreat it at 25 °C and 500 rpm for 1 hour in a closed reaction kettle to obtain a silicon-containing material;

[0145] Dissolve 24 g of aluminum sulfate in 18.0 g of deionized water, and stir at 25 °C and 500 rpm for 1 h to obtain an aluminum-containing material;

[0146] Drop the aluminum-containing material liquid into the silicon-containing material, and continue to stir at 60 °C for 8 h to obtain a gel solution;

[0147] Dissolve 6.74 g of sodium hydroxide in 36 g of deionized water to make an aqueous solution of sodium hydroxide, and add it to the gel solution until the pH value is 12 to obtain a gel solution;

[0148] Put the gel solution into a hydrothermal reaction kettle and carry out two-stage hydrothermal crystallization treatment. In the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40 °C and the crystallization time is 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95 °C and the crystallization time is 24 hours to obtain a solution containing 13X molecular sieve seeds. Among them, in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO 2 / Al 2 O 3 =1.5:1, Na 2 O / SiO 2 =1.6:1, H 2 O / SiO2 = 32:1.

[0149] Step 2: The solution containing 13X molecular sieve seeds was aged at 60 °C for 12 h, then hydrothermally crystallized at 80 °C for 12 h. The hydrothermal crystallization product was filtered, washed until neutral, and dried to constant weight at 100 °C to obtain 13X molecular sieve.

[0150] Step 3: 50 g of carbon-modified 13X molecular sieve and 0.5 g of methyltriethoxysilane were added to 49.5 g of absolute ethanol, and the mixture was stirred at room temperature for 4 h, then filtered. The filtered molecular sieve was calcined at 450 °C for 2 h;

[0151] The calcined 13X molecular sieve was immersed in an aqueous solution of copper nitrate at 1 mol / L at room temperature for 24 h;

[0152] The 13X molecular sieve soaked in the copper salt solution was dried at 100 °C for 12 h, and then heated to 500 °C at a heating rate of 5 °C / min in a kiln and calcined for 2 h;

[0153] The calcined product was dried by a vacuum drying device for 12 h to obtain a molecular sieve organic oxide adsorbent.

[0154] I. The silicon-aluminum ratio and specific surface area of the organic oxide adsorbents prepared in the examples and comparative examples were tested respectively, and the results are shown in Table 1.

[0155] II. The adsorption performance of the organic oxide adsorbents prepared in the examples and comparative examples was tested. The specific steps are as follows: Using the Fischer-Tropsch synthesis product as the adsorption object, passing it through a fixed bed containing the adsorbent, and monitoring the changes in the product concentration and the concentration of organic oxide impurities before and after passing through the bed layer. The removal rate of organic oxide impurities and the product loss rate were calculated. Among them, the adsorption temperature was 55 °C, the pressure was 1 atm, the weight ratio of the adsorbent to the Fischer-Tropsch synthesis product was 1:10, the adsorbent loading was 1 g, the sample entered the fixed bed reactor at a flow rate of 10 ml / min, and the adsorption time was 2 h. The contents of each component in the Fischer-Tropsch synthesis product before treatment (by weight percentage) are shown in Table 2.

[0156] Table 1

[0157]

[0158]

[0159] Table 2

[0160]

[0161] As can be seen from Table 1, the molecular sieve organic oxide adsorbents prepared in Examples 1 to 8 of the present invention have high silica-alumina ratio, high specific surface area and high pore volume. Specifically, the silica-alumina ratio is 2.2 to 2.9, and the pore volume is between 0.39 cm 3 / g and 0.5 cm 3 / g, and the specific surface area is between 800 m 2 / g and 910 m 2 / g. Among them, compared with Comparative Examples 1 and 2 using a single-stage crystallization process, Example 1 using a two-stage crystallization significantly increases the specific surface area of the adsorbent; from the data of Example 1 and Comparative Examples 3 to 5, it can be seen that by organosilicon modification treatment, copper salt solution impregnation treatment, titanium precursor sol impregnation treatment and secondary calcination treatment, the adsorption sites of the organic oxide can be increased and the product loss can be reduced.

[0162] As can be seen from Table 2, the molecular sieve organic oxide adsorbents prepared in Examples 1 to 8 have good adsorption effects on the organic oxygen compounds in the products with different carbon numbers of Fischer-Tropsch synthesis, and hardly adsorb the alkane products and olefin products of Fischer-Tropsch synthesis, and have high adsorption capacity and good selectivity for organic oxygen compounds.

[0163] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing an organic oxide adsorbent, characterized in that: The steps include: Step S1, mixing a silicon source and water to obtain a silicon-containing material, mixing an aluminum source and water to obtain an aluminum-containing material, stirring and mixing the aluminum-containing material and the silicon-containing material to obtain a first gel-like mother liquor, adjusting the pH value of the first gel-like mother liquor to 8.5-12.5 using sodium hydroxide, and then performing two-stage hydrothermal crystallization treatment to obtain a solution containing 13X molecular sieve seeds; wherein the crystallization temperature of the first stage hydrothermal crystallization treatment is 20-60° C., and the crystallization temperature of the second stage hydrothermal crystallization is 80-120° C.; the molar ratio of each component in the solution containing 13X molecular sieve seeds is: SiO2 / Al2O3=(0.01-6):1, Na2O / SiO2=(0.01-4.0):1, H2O / SiO2=(1.0-50.0):1; Step S2, subjecting the solution containing the 13X molecular sieve seed crystals to an aging treatment, and then subjecting the solution to a hydrothermal crystallization treatment at 60-105° C., filtering, washing, and drying the hydrothermal crystallization product to obtain a 13X molecular sieve; Step S3, reacting the 13X molecular sieve and the organosilicon coupling agent in an organic alcohol solvent to obtain an organosilicon-modified 13X molecular sieve, soaking the product of the first calcination treatment in a copper salt solution to obtain a 13X molecular sieve impregnated with a copper salt solution, stirring and mixing the 13X molecular sieve impregnated with the copper salt solution and a titanium precursor sol to obtain a mixture, drying the mixture and then calcining it for a second time to obtain an organic oxide adsorbent; wherein the temperature of the first calcination treatment is 400-500°C, and the temperature of the second calcination treatment is 450-550°C.

2. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: The silicon source is selected from one or more of silica sol, tetraethyl orthosilicate, macroporous silica gel, silicon powder, fly ash, and white carbon black; the aluminum source is selected from one or more of sodium aluminate, pseudo-boehmite, aluminum sulfate, and aluminum nitrate; and the weight ratio of the silicon source to the aluminum source is (0.01-1.25):

1.

3. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: In the step S1, the mass fraction of the silicon source in the silicon-containing material is 2% to 50%.

4. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: In the step S1, the silicon source and the water are stirred at 20 to 60° C. for 0.1 to 12 hours to obtain the silicon-containing material.

5. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: In the step S1, the mass fraction of the aluminum source in the aluminum-containing material is 15% to 60%.

6. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: In the step S1, the aluminum source and the water are stirred at 20 to 60° C. for 0.1 to 12 hours to obtain the aluminum-containing material.

7. The method for preparing an organic oxide adsorbent according to claim 1, characterized in that: In the step S1, the mixture is stirred and mixed at a stirring temperature of 20 to 100° C. for 0.1 to 24 hours to obtain the first gel mother solution.

8. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: The pH value of the first gel-like mother solution is 11.8-12.

5.

9. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S1, the pH value of the first gel mother solution is adjusted by adding solid sodium hydroxide or an aqueous solution of sodium hydroxide.

10. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the first stage of hydrothermal crystallization treatment, the crystallization temperature is 40 to 60° C. and the crystallization time is 4 to 24 hours.

11. The method for preparing an organic oxide adsorbent according to claim 10, characterized in that: In the first hydrothermal crystallization treatment, the crystallization time is 11 to 24 hours.

12. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the second hydrothermal crystallization treatment, the crystallization temperature is 90-100° C. and the crystallization time is 6-48 hours.

13. The method for preparing an organic oxide adsorbent according to claim 12, characterized in that: In the second hydrothermal crystallization treatment, the crystallization time is 18 to 48 hours.

14. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S2, the aging treatment is performed under stirring conditions, the temperature of the aging treatment is 20 to 100° C., and the time of the aging treatment is 0.1 to 24 hours.

15. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S2, the hydrothermal crystallization treatment time is 0.1 to 36 hours.

16. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S2, the hydrothermal crystallization product is filtered and washed to neutrality, and then dried at 80-120° C. to constant weight to obtain the 13X molecular sieve.

17. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In step S3, the organic silicon coupling agent is selected from one or more of methyltriethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane, ethyl orthosilicate, ethoxysilane, ethyl orthosilicate, and 3-aminopropyltriethoxysilane, and the organic alcohol solvent is selected from one or more of ethanol, propanol, and butanol.

18. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the mass ratio of the 13X molecular sieve, the organic silicon coupling agent and the organic alcohol solvent is 1: (0.002-0.05): (0.8-2).

19. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the reaction temperature is 15 to 40° C., and the reaction time is 1 to 10 hours.

20. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the first calcination treatment is performed for 0.5 to 4 hours.

21. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In step S3, the copper salt is selected from one or more of copper nitrate, copper chloride, and copper acetate.

22. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the concentration of the copper salt is 0.1 to 2 mol / L, and the soaking treatment time is 6 to 48 hours.

23. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the titanium source in the titanium precursor sol is selected from one or more of tetrabutyl titanate, titanium orthosilicate or diisopropoxy diacetylacetonate titanium.

24. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the titanium precursor sol is formed by mixing a titanium source, ethanol and water.

25. The method for preparing an organic oxide adsorbent according to claim 24, characterized in that: In the step S3, the titanium source, the ethanol and the water are stirred and mixed at 50 to 70° C. for 1 to 6 hours to form the titanium precursor sol.

26. The method for preparing an organic oxide adsorbent according to claim 24, characterized in that: In the step S3, the ethanol and the water are first mixed to form a mixed solvent, and then the titanium source is added and mixed.

27. The method for preparing an organic oxide adsorbent according to claim 24, characterized in that: In the step S3, the titanium source, the ethanol, and the water are mixed in a mass ratio of 1:(3-7):(0.5-1.5).

28. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the temperature of the drying process is 90 to 110° C., and the time of the drying process is 6 to 18 hours.

29. The method for preparing an organic oxide adsorbent according to any one of claims 1 to 7, characterized in that: In the step S3, the second calcination treatment is performed for 0.5 to 4 hours.

30. An organic oxide adsorbent, characterized in that: The organic oxide adsorbent is prepared according to the method for preparing the organic oxide adsorbent according to any one of claims 1 to 29.

31. Use of the organic oxide adsorbent according to claim 30 in removing organic oxides from hydrocarbons.

32. Use of the organic oxide adsorbent according to claim 31 in removing organic oxides from hydrocarbons, characterized in that: The hydrocarbons are hydrocarbon products produced by Fischer-Tropsch synthesis of coal, or olefin products produced by petroleum cracking.

33. Use of the organic oxide adsorbent according to claim 31 in removing organic oxides from hydrocarbons, characterized in that: The organic oxide is selected from one or more of alcohols, aldehydes, ketones and carboxylic acids having 1 to 21 carbon atoms.

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