A molecular sieve organic oxide adsorbent, its preparation method and use

Abstract

The application provides a molecular sieve organic oxide adsorbent and a preparation method and application thereof, and the preparation method comprises the following steps: preparing seeds by controlling pH value and a two-section crystallization process, taking a molecular sieve material as raw material, and preparing a mother liquor by dissolving aluminum and silicon and mixing the two; and then through aging treatment and hydrothermal crystallization treatment, a 13X molecular sieve with high silicon-aluminum ratio, excellent specific surface area and pore volume is prepared; through carbon modification treatment on the 13X molecular sieve, organic silicon is introduced into the 13X molecular sieve by reaction with an organic silicon coupling agent and calcination treatment; through copper salt solution immersion treatment, titanium precursor sol immersion treatment and secondary calcination treatment, an adsorbent with excellent adsorption performance for organic oxides is obtained, and the problems of low adsorption capacity of molecular sieves for organic oxides in hydrocarbons, poor selective adsorption performance of organic oxides and narrow application range in the prior art are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adsorption materials, in particular to a molecular sieve organic oxide adsorbent and a preparation method and application thereof. BACKGROUND

[0002] Adsorption method separates substances in petroleum cracking and refinery catalytic cracking have been widely used, the current adsorption separation process research is mainly used in the removal of C4 and above hydrocarbons containing oxygen compounds; in addition, the hydrocarbon products of coal by fischer-tropsch synthesis have different carbon number distribution, the oxygen-containing compounds in different carbon number products, their molecular weight and molecular structure are quite different, therefore, there is no adsorbent commonly used for oxygen-containing compounds in different carbon number products. Molecular sieve is a kind of silicate, which has rich pore system, large specific surface area and good thermal stability, and is considered as the preferred adsorbent material for removing oxygen-containing compounds in olefins. Among them, the FAU type (X, Y type) molecular sieve, the pore size is about 0.74 nm, especially the X type molecular sieve can better remove the oxygen-containing compound impurities in olefins, and is studied more, and is also applied in industrial practice, but when used for hydrocarbon purification, its adsorption heat is high, the adsorption capacity is weak, in addition, a part of hydrocarbons will be adsorbed in 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 selectivity for organic oxide adsorption. SUMMARY

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

[0004] In order to achieve the above purpose, according to one aspect of the present application, a preparation method of a molecular sieve organic oxide adsorbent is provided, comprising 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 by 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℃, and the crystallization temperature of the second-stage hydrothermal crystallization is 80-120℃;

[0006] Step S2, the molecular sieve-containing material is mixed with sodium carbonate at a mass ratio of 1:0.5-1:5, and then calcined at 550-800°C for 60-120 min; the calcined product is dissolved with a monobasic acid having a mass fraction of 10%-35%, and then filtered to obtain an aluminum-rich liquid and a residue; the residue is mixed with sodium hydroxide and water at a mass ratio of 5-100:40-60:50-400 to dissolve the residue, and then filtered to obtain a silicon-rich liquid; and the aluminum-rich liquid and the silicon-rich liquid are mixed to obtain a second gelatinous mother liquor;

[0007] Step S3, the solution containing 13X molecular sieve seeds is mixed with the second gelatinous mother liquor, and then subjected to aging treatment and hydrothermal crystallization treatment at 60-105°C to obtain the 13X molecular sieve;

[0008] Step S4, the 13X molecular sieve is subjected to immersion treatment with a carbon precursor solution to obtain the 13X molecular sieve impregnated with the carbon precursor solution; and the 13X molecular sieve impregnated with the carbon precursor solution is subjected to heat treatment at 600-900°C in an inert gas atmosphere to obtain the carbon-modified 13X molecular sieve.

[0009] Step S5, the carbon-modified 13X molecular sieve and an organosilicon coupling agent are reacted in an organic alcohol solvent to obtain the organosilicon-modified 13X molecular sieve; the organosilicon-modified 13X molecular sieve is subjected to first calcination treatment, and then subjected to immersion treatment with a copper salt solution to obtain the 13X molecular sieve impregnated with the copper salt solution; the 13X molecular sieve impregnated with the copper salt solution is mixed with a titanium precursor sol to obtain a mixture; the mixture is subjected to drying treatment and then second calcination treatment to obtain the molecular sieve organooxide 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.

[0010] Further, in step S1, the silicon source is selected from one or more of silica sol, tetraethyl orthosilicate, coarse-pored 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.

[0011] Preferably, in step S1, the mass fraction of the silicon source in the silicon-containing material is 2%-50%.

[0012] Preferably, in step S1, the silicon 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 mass fraction of the aluminum source in the aluminum-containing material is 15%-60%.

[0014] 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.

[0015] Preferably, in step S1, the mixture is stirred at 20-100℃ for 0.1-24h to obtain the first gel-like mother liquor.

[0016] Further, the pH value of the first gel-like mother liquor is 11.8-12.5.

[0017] 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.

[0018] Preferably, the crystallization temperature in the second-stage crystallization treatment is higher than that in the first-stage crystallization treatment by 40℃ or more, more preferably by 50-60℃.

[0019] More preferably, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40-60℃ and the crystallization time is 4-24h, more preferably 11-24h.

[0020] More preferably, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 90-100℃ and the crystallization time is 6-48h, more preferably 18-48h.

[0021] Preferably, the molar ratio of the components in the solution containing 13X molecular sieve seeds is SiO2 / Al2O3=(0.01-6):1, Na2O / SiO2=(0.01-4.0):1, and H2O / SiO2=(1.0-50.0):1.

[0022] Further, in step S2, the molecular sieve-containing material is selected from one or more of waste Z-5 molecular sieve catalyst, waste MTO catalyst, waste molecular sieve adsorbent, fly ash, waste FCC catalyst, and waste VOC adsorbent.

[0023] Preferably, in step S2, the molecular sieve-containing material is ground to 200 mesh or less and then mixed with sodium carbonate.

[0024] Preferably, the monobasic acid is selected from at least one of hydrochloric acid, acetic acid, and nitric acid.

[0025] Preferably, in step S2, the molar ratio of the components in the second gel-like mother liquor is SiO2 / Al2O3=0.5-6.0:1, Na2O / SiO2=0.5-6.0:1, and H2O / SiO2=10-100:1.

[0026] Further, in step S3, the mass of the solution containing 13X molecular sieve seeds added is 5-20% based on 100% of the mass of the second gel-like mother liquor.

[0027] Preferably, in step S3, the aging treatment is performed under stirring, the temperature of the aging treatment is 20-100℃, and the time of the aging treatment is 0.1-24h.

[0028] Preferably, in step S3, the time of the hydrothermal crystallization treatment is 0.1-36h.

[0029] Preferably, in step S3, after the hydrothermal crystallization product is filtered, it is washed to neutral, and then dried at 80-120℃ to constant weight to obtain the 13X molecular sieve.

[0030] Further, the carbon source in the carbon precursor solution is selected from one of benzene, furan or furfural, and the solvent in the carbon precursor solution is selected from one of N,N-dimethylformamide, acetone, ethanol, tetrahydrofuran.

[0031] Preferably, the concentration of the carbon source in the carbon precursor solution is 5-25% by mass.

[0032] Preferably, in step S4, the time of stirring is 6-48h.

[0033] Preferably, in step S4, the time of heat treatment is 2-4h.

[0034] Further, in step S5, the organosilicon coupling agent is selected from one or more of methyltriethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane, ethylsilicate, ethoxysilane, ethyl silicate, 3-aminopropyltriethoxysilane, and the organic alcohol solvent is selected from one or more of ethanol, propanol, butanol.

[0035] Preferably, in step S5, the mass ratio of the carbon-modified 13X molecular sieve, the organosilicon coupling agent and the organic alcohol solvent is 1:(0.002-0.05):(0.8-2).

[0036] Preferably, in step S5, the temperature of the reaction is 15-40℃, and the time of the reaction is 1-10h.

[0037] Preferably, in step S5, the time of the first calcination treatment is 0.5-4h.

[0038] Further, in step S5, the copper salt is selected from one or more of copper nitrate, copper chloride, copper acetate.

[0039] Preferably, in step S5, the concentration of the copper salt is 0.1-2mol / L, and the time of the soaking treatment is 6-48h.

[0040] Preferably, in step S5, the titanium source in the titanium precursor sol is selected from one or more of tetrabutyl titanate, titanium orthosilicate or diisopropoxy titanium diacetylacetone.

[0041] More preferably, in step S5, the titanium precursor sol is formed by mixing the titanium source, ethanol and water.

[0042] Further more preferably, in step S5, the titanium source, ethanol and water are mixed at 50-70℃ for 1-6h to form the titanium precursor sol.

[0043] Further more preferably, in step S5, the ethanol and water are mixed to form a mixed solvent, and then the titanium source is added and mixed.

[0044] Further more preferably, in step S5, the titanium source, ethanol and water are mixed at a mass ratio of 1:(3-7):(0.5-1.5).

[0045] Preferably, in step S5, the drying treatment is performed at a temperature of 90-110℃ for 6-18h.

[0046] Preferably, in step S5, the second calcination treatment is performed for 0.5-4h.

[0047] By controlling the pH value and preparing the seed crystal through a two-stage crystallization process, the 13X molecular sieve with high silica-alumina ratio, excellent specific surface area and pore volume is prepared by using the molecular sieve-containing material as the raw material, and through the aluminum dissolution, silicon dissolution and mother liquor preparation by mixing the two, and then through the aging treatment and hydrothermal crystallization treatment. The prepared 13X molecular sieve has high silica source utilization rate and can provide more adsorption sites. Then the surface and structure of the 13X molecular sieve are modified to obtain the molecular sieve organic oxide adsorbent with high silica-alumina ratio, high specific surface area and high pore volume. The surface and structure modification includes: the carbon modification treatment of the 13X molecular sieve in the carbon precursor solution to form a carbon layer to increase the specific surface and pore volume, and increase the dispersity of the organic silicon coupling agent molecular sieve in the subsequent step to improve the adsorption performance; the introduction of the organic silicon into the 13X molecular sieve through the reaction with the organic silicon coupling agent and the calcination treatment to improve the dispersity and stability of the adsorbent; the increase of the adsorption sites through the copper salt solution immersion treatment, the titanium precursor sol immersion treatment and the secondary calcination treatment to improve the adsorption capacity and selectivity of the adsorbent for the organic oxide, so that the adsorbent with excellent adsorption performance for the organic oxide is obtained. The application uses the molecular sieve-containing material as the main raw material, and the waste molecular sieve-containing material can be recycled.

[0048] The adsorbent prepared by the method of the application has high silica-alumina ratio, high specific surface area and high pore volume, and excellent adsorption performance for the organic oxide, and can realize the efficient adsorption and removal of the organic oxide in the Fischer-Tropsch synthesis alkene product or the organic oxide in the hydrocarbon fuel or chemical product. DETAILED DESCRIPTION

[0049] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other in the case of no conflict. The present application will be described in detail below with reference to the embodiments.

[0050] As described in the background, the prior art has the problems of low adsorption capacity of the molecular sieve for organic oxygenates in hydrocarbons, poor selective adsorption performance of the molecular sieve for organic oxygenates, and narrow application range. In order to solve the above problems, the present application provides a preparation method of a molecular sieve organic oxygenate adsorbent, comprising the following steps:

[0051] In step S1, a silicon source and water are mixed to obtain a silicon-containing material, an aluminum source and water are mixed to obtain an aluminum-containing material, the aluminum-containing material and the silicon-containing material are stirred and mixed to obtain a first gel-like mother liquor, sodium hydroxide is used to adjust the pH value of the first gel-like mother liquor to 8.5-12.5, and then two-stage hydrothermal crystallization treatment is performed to obtain a solution containing 13X molecular sieve seeds; wherein the crystallization temperature of the first-stage hydrothermal crystallization treatment is 20-60℃, and the crystallization temperature of the second-stage hydrothermal crystallization is 80-120℃.

[0052] In step S2, the molecular sieve-containing material is mixed with sodium carbonate at a mass ratio of 1:0.5-1:5, and then calcination is performed at 550-800℃ for 60-120min, a monobasic acid with a mass fraction of 10%-35% is used to dissolve the calcination product, and filtration is performed to obtain an aluminum-rich liquid and a residue, the residue is stirred and mixed with sodium hydroxide and water at a mass ratio of 5-100:40-60:50-400 to dissolve the residue, and filtration is performed to obtain a silicon-rich liquid, and the aluminum-rich liquid and the silicon-rich liquid are mixed to obtain a second gel-like mother liquor.

[0053] In step S3, the solution containing 13X molecular sieve seeds is mixed with the second gel-like mother liquor and then aging treatment is performed, and then hydrothermal crystallization treatment is performed at 60-105℃ to obtain 13X molecular sieve.

[0054] In step S4, the 13X molecular sieve is soaked with a carbon precursor solution to obtain 13X molecular sieve impregnated with the carbon precursor solution, and the 13X molecular sieve impregnated with the carbon precursor solution is heat-treated at 600-900℃ under an inert gas atmosphere to obtain carbon-modified 13X molecular sieve.

[0055] Step S5, the carbon modified 13X molecular sieve and the organosilicon coupling agent are reacted in an organic alcohol solvent to obtain an organosilicon modified 13X molecular sieve, the organosilicon modified 13X molecular sieve is subjected to a first calcination treatment, the first calcination treatment product is subjected to an immersion treatment after being treated with a copper salt solution to obtain a 13X molecular sieve immersed with a copper salt solution, the 13X molecular sieve immersed with the copper salt solution is stirred and mixed with a titanium precursor sol to obtain a mixture, the mixture is subjected to a drying treatment and then a second calcination treatment to obtain a molecular sieve organic oxide adsorbent; wherein the temperature of the first calcination treatment is 400-500 DEG C, and the temperature of the second calcination treatment is 450-550 DEG C.

[0056] In order to obtain a high-performance organic oxide adsorbent, the application provides a preparation method of a molecular sieve organic oxide adsorbent, a 13X molecular sieve with a high silicon-aluminum ratio, excellent specific surface area and pore volume is prepared by controlling the pH value, a seed crystal is prepared through a two-stage crystallization process, a mother liquor is prepared by dissolving aluminum and silicon in a material containing a molecular sieve and mixing the two, and then 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 a molecular sieve organic oxide adsorbent with a high silicon-aluminum ratio, high specific surface area and high pore volume, the surface and structure modification includes: carbon modification treatment is performed by immersing the 13X molecular sieve in a carbon precursor solution to form a carbon layer to increase the specific surface and pore volume, and increase the dispersibility of the organosilicon coupling agent molecular sieve in the subsequent step and improve the adsorption performance; organosilicon is introduced into the 13X molecular sieve by reaction with an organosilicon coupling agent and calcination treatment to improve the dispersibility and stability of the adsorbent; the adsorption sites are increased by copper salt solution immersion treatment, titanium precursor sol immersion treatment and secondary calcination treatment to improve the adsorption capacity and selectivity of the adsorbent for organic oxides, so that an adsorbent with excellent adsorption performance for organic oxides is obtained; and the application uses a material containing a molecular sieve as the main raw material, and the waste material containing a molecular sieve can be recycled.

[0057] To obtain the organic oxide adsorbent with high silica-alumina ratio and specific surface area, in a preferred embodiment, in step S1, the silica source is selected from one or more of silica sol, tetraethyl orthosilicate, coarse-pore silica gel, silicon powder, fly ash, and white carbon black, the alumina source is selected from one or more of sodium aluminate, pseudo-boehmite, aluminum sulfate, and aluminum nitrate, and the weight ratio of the silica source to the alumina source is (0.01-1.25):1; to ensure sufficient reaction of the two and to generate the organic oxide adsorbent with high silica-alumina ratio and specific surface area, preferably in step S1, the mass fraction of the silica source in the silica-containing material is 2%-50%; preferably in step S1, the silica source and water are stirred at 20-60°C for 0.1-12h to obtain the alumina-containing material; preferably in step S1, the mass fraction of the alumina source in the alumina-containing material is 15%-60%; preferably in step S1, the alumina source and water are stirred at 20-60°C for 0.1-12h to obtain the alumina-containing material; and preferably in step S1, the stirring and mixing are performed at 20-100°C for 0.1-24h to obtain the first gel-like mother liquor.

[0058] In a preferred embodiment, the pH value of the first gel-like mother liquor is 11.8-12.5, and by further precisely adjusting the pH value to 11.8-12.5, the silica source and the alumina source are facilitated to react and further generate the crystal seeds with high crystallinity and stable crystal form and structure in the two-stage hydrothermal crystallization treatment, so as to further generate the 13X molecular sieve with high silica-alumina 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; preferably, the crystallization temperature in the second-stage crystallization treatment is higher than the crystallization temperature in the first-stage crystallization treatment by 40°C or more, more preferably by 50-60°C, and the two-stage hydrothermal crystallization treatment is adopted, wherein the 13X molecular sieve crystal seeds with high silica-alumina ratio generated in the first-stage crystallization treatment are further grown in the first-stage crystallization treatment to form a solution of the 13X molecular sieve crystal seeds with complete structure, uniformity, and high specific surface area, and the above-mentioned higher temperature difference is advantageous for obtaining the organic oxide adsorbent with higher specific surface area; more preferably, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40-60°C, and the crystallization time is 4-24h, preferably 11-24h; more preferably, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 90-100°C, and the crystallization time is 6-48h, more preferably 18-48h; preferably, in the solution containing the 13X molecular sieve crystal seeds, the molar ratio of the components is SiO2 / Al2O3=(0.01-6):1, Na2O / SiO2=(0.01-4.0):1, and H2O / SiO2=(1.0-50.0):1, which is advantageous for the subsequent growth to form the 13X molecular sieve with high adsorption performance; and preferably, both the first-stage and the second-stage hydrothermal crystallization treatments are performed in a hydrothermal reaction kettle.

[0059] In a preferred embodiment, in step S2, the molecular sieve-containing material is selected from one or more of waste Z-5 molecular sieve catalyst, waste MTO catalyst, waste molecular sieve adsorbent, fly ash, waste FCC catalyst, and waste VOC adsorbent; preferably, in step S2, the molecular sieve-containing material is ground to 200 mesh or less, and then mixed with sodium carbonate; preferably, the monobasic acid is selected from at least one of hydrochloric acid, acetic acid, and nitric acid; preferably, in step S2, the molar ratio of the components in the second gel-like mother liquor is: SiO2 / Al2O3 = 0.5-6.0:1, Na2O / SiO2 = 0.5-6.0:1, and H2O / SiO2 = 10-100:1, and by adjusting the component ratio in the mother liquor, a 13X molecular sieve with a higher specific surface area and pore volume can be obtained, and the 13X molecular sieve exhibits higher adsorption activity.

[0060] In a preferred embodiment, in order to obtain a 13X molecular sieve with a more regular and uniform structure, in step S3, the mass of the solution containing 13X molecular sieve seeds added is 5-20% based on 100% of the mass of the second gel-like mother liquor; preferably, in step S3, the aging treatment is carried out under stirring, 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 S3, the time of the hydrothermal crystallization treatment is 0.1-36 h; preferably, in step S3, after the hydrothermal crystallization product is filtered, it is washed to neutral, and then dried at 80-120°C to constant weight to obtain the 13X molecular sieve.

[0061] In a preferred embodiment, the carbon source in the carbon precursor solution is selected from one of benzene, furan, or furfural, and the solvent in the carbon precursor solution is selected from one of N,N-dimethylformamide, acetone, ethanol, and tetrahydrofuran, and the above-mentioned organic solvent and carbon source are used to form a stable and uniform carbon precursor solution, and the carbon precursor solution can fully contact and infiltrate the 13X molecular sieve, which is conducive to the formation of a carbon layer and the expansion of the surface area and pore volume of the 13X molecular sieve; preferably, the concentration of the carbon source in the carbon precursor solution is 5-25% based on the mass percentage of the carbon precursor solution; preferably, in step S4, the soaking treatment is carried out under stirring, and the stirring time is 6-48 h; preferably, in step S4, the time of the heat treatment is 2-4 hours.

[0062] In a preferred embodiment, in order to obtain higher coupling efficiency and coupling effect, in step S5, the organosilicon coupling agent is selected from one or more of methyltriethoxysilane, isopropyltrimethoxysilane, vinyltrimethoxysilane, ethylsilicate, ethoxysilane, tetraethyl orthosilicate, 3-aminopropyltriethoxysilane, and the organic alcohol solvent is selected from one or more of ethanol, propanol, butanol; preferably in step S5, the mass ratio of the carbon-modified 13X molecular sieve, the organosilicon coupling agent and the organic alcohol solvent is 1:(0.002-0.05):(0.8-2); preferably in step S5, the reaction temperature is 15-40°C, and the reaction time is 1-10h; preferably in step S5, the first calcination treatment time is 0.5-4h.

[0063] In a preferred embodiment, in step S5, the copper salt is selected from one or more of copper nitrate, copper chloride, copper acetate; preferably in step S5, the concentration of the copper salt is 0.1-2mol / L, and the soaking treatment time is 6-48h, so as to obtain higher adsorption capacity and selectivity of the organic oxide and improve the utilization rate of the copper salt raw material; preferably in step S5, the titanium source in the titanium precursor sol is selected from one or more of tetrabutyl titanate, titanium orthosilicate or diisopropoxy titanium acetylacetonate; more preferably in step S5, the titanium precursor sol is formed by mixing the titanium source, ethanol and water, and the uniform titanium precursor sol can be formed by using ethanol and water as solvents, and the solvents are green and environmentally friendly; still more preferably in step S5, the titanium source, ethanol and water are mixed and stirred at 50-70°C for 1-6h to form the titanium precursor sol; still more preferably in step S5, the ethanol and water are first mixed to form a mixed solvent, and then the titanium source is added for mixing; still more preferably in step S5, the titanium source, ethanol and water are mixed in a mass ratio of 1:(3-7):(0.5-1.5); preferably in step S5, the drying treatment temperature is 90-110°C, and the drying treatment time is 6-18h; preferably in step S5, the second calcination treatment time is 0.5-4h.

[0064] According to another aspect of the present application, a molecular sieve organic oxide adsorbent is provided, which is prepared according to the preparation method of the molecular sieve organic oxide adsorbent as above. The prepared molecular sieve 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, etc.

[0065] According to another aspect of the present application, there is provided use of the molecular sieve organic oxide adsorbent as defined above for removing organic oxides from hydrocarbons; preferably the hydrocarbons are hydrocarbon products from Fischer-Tropsch synthesis of coal, or olefin products from cracking of petroleum; preferably the organic oxides are selected from one or more of alcohols, aldehydes, ketones, carboxylic acids having 1-21 carbon atoms; the resulting molecular sieve organic oxide adsorbent has high adsorption capacity and selectivity for organic oxides, especially for organic oxides in various carbon number hydrocarbon products from Fischer-Tropsch synthesis or various carbon number olefin products from cracking of petroleum, especially C1-C15 organic oxides, has high adsorption efficiency, high adsorption capacity and high selectivity.

[0066] The application will be further described in conjunction with specific examples which should not be construed as limiting the scope of the application.

[0067] Example 1

[0068] A method for preparing a molecular sieve organic oxide adsorbent, the specific steps are as follows:

[0069] Step one, 21.0g of silica sol (mass fraction of silica is 30%) is dissolved in 36.0g of deionized water, and after pretreatment at 25℃, 500rpm for 1 hour in a closed reaction kettle, a silica-containing material is obtained;

[0070] 24g of aluminum sulfate is dissolved in 18.0g of deionized water, and stirred at 25℃, 500rpm for 1h to obtain an aluminum-containing material;

[0071] The aluminum-containing material is added dropwise to the silica-containing material, and stirring is continued at 60℃ for 8h to obtain a gel solution;

[0072] 6.74g of sodium hydroxide is dissolved in 36g of deionized water to form an aqueous sodium hydroxide solution, and the gel solution is added until the pH value is 12, to obtain a gel solution;

[0073] The gel solution is placed in a hydrothermal reaction kettle, and subjected to two-stage hydrothermal crystallization treatment, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40℃, and the crystallization time is 12 hours, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95℃, and the crystallization time is 24 hours, to obtain a solution containing 13X molecular sieve seeds, wherein in the solution containing 13X molecular sieve seeds, the molar ratio of each component is: SiO2 / Al2O3=1.5:1, Na2O / SiO2=1.6:1, H2O / SiO2=32:1.

[0074] Step two, the fly ash is ground to 200 mesh, the ground fly ash is mixed with NaCO3 in a mass ratio of 1:2.5, and then is calcined at 700℃ for 90min, the calcined product is dissolved with 25% hydrochloric acid, and the aluminum-rich liquid and the residue are obtained by filtration;

[0075] The residue is mixed with NaOH and H2O in a mass ratio of 50:50:200, and then is filtered to obtain the silicon-rich liquid;

[0076] The silicon-rich liquid and the aluminum-rich liquid are weighed and matched to obtain a gel-like mother liquor, and the molar ratio of each component in the gel-like mother liquor is: SiO2 / Al2O3=3.5:1, Na2O / SiO2=2.8:1, and H2O / SiO2=80:1.

[0077] Step three, in the prepared gel-like mother liquor, a solution containing 13X molecular sieve seeds is added in an amount of 15% based on the mass of the gel-like mother liquor, and then is stirred and aged at 60℃ for 12h, and then is hydrothermally crystallized at 80℃ for 12h, and then is filtered, washed to neutral, and dried at 100℃ to constant weight to obtain 13X molecular sieve.

[0078] Step four, the 13X molecular sieve is immersed in a carbon precursor solution and stirred for 24h, and then is heated to 750℃ under an inert gas atmosphere for 3h to obtain carbon-modified 13X molecular sieve; wherein the carbon source in the carbon precursor solution is benzene, and the solvent is ethanol, and the concentration of the carbon source is 15% based on the mass percentage of the carbon precursor solution.

[0079] Step five, 50g of carbon-modified 13X molecular sieve and 0.5g of methyltriethoxysilane are added to 49.5g of anhydrous ethanol, and then is stirred at room temperature for 4h, and then is filtered, and the filtered molecular sieve is calcined at 450℃ for 2h;

[0080] The calcined 13X molecular sieve is immersed in a 1mol / L copper nitrate aqueous solution at room temperature for 24h;

[0081] 10g of tetrabutyl titanate is added dropwise to a mixed solvent of 50g of ethanol and 10g of distilled water, and then is stirred at 60℃ for 3h to obtain a titanium precursor sol;

[0082] The 13X molecular sieve immersed in the copper salt solution is added to the titanium precursor sol, and then is stirred uniformly, and then the mixture is dried at 100℃ for 12h, and then is heated to 500℃ at a heating rate of 5℃ / min in a kiln, and then is calcined for 2h;

[0083] The calcined product is dried in a vacuum drying device for 12 hours to obtain a molecular sieve organic oxide adsorbent.

[0084] Example 2

[0085] A preparation method of a molecular sieve organic oxide adsorbent, the specific steps are as follows:

[0086] Step one, dissolve 1g of silicon powder in 18g of deionized water, and after pretreatment at 25℃ and 500rpm for 1 hour in a sealed reaction kettle, obtain a silicon-containing material;

[0087] Dissolve 12g of aluminum nitrate in 18.0g of deionized water, and stir at 35℃ and 500rpm for 1 hour to prepare an aluminum-containing material;

[0088] Drop the aluminum-containing material into the silicon-containing material, and continue to stir at 50℃ for 6 hours to prepare a gel solution;

[0089] Add 2g of sodium hydroxide dissolved in 36g of deionized water to the gel solution to obtain a gel solution with a pH value of 11.8;

[0090] Transfer the gel solution to a hydrothermal reaction kettle, and perform two-stage hydrothermal crystallization treatment, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 50℃, and the crystallization time is 14 hours, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 100℃, and the crystallization time is 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 is: SiO2 / Al2O3=0.6:1, Na2O / SiO2=3:1, H2O / SiO2=20:1.

[0091] Step two, grind the Z-5 molecular sieve catalyst to 200 mesh or less, mix the ground Z-5 molecular sieve catalyst with NaCO3 according to a mass ratio of 1:0.5, and calcine at 550℃ for 60min, then dissolve the calcined product with 35% acetic acid by mass fraction, and filter to obtain an aluminum-rich liquid and a residue;

[0092] Mix the residue with NaOH and H2O according to a mass ratio of 5:40:50, and filter to obtain a silicon-rich liquid;

[0093] Weigh the silicon-rich liquid and the aluminum-rich liquid to obtain a gel-like mother liquor, and the molar ratio of each component in the gel-like mother liquor is: SiO2 / Al2O3=6:1, Na2O / SiO2=0.5:1, H2O / SiO2=100:1.

[0094] Step three, in the prepared gel mother liquor, 5% of the prepared solution containing 13X molecular sieve seed crystals was added, stirring and aging treatment was carried out at 20℃ for 0.1h, and then hydrothermal crystallization treatment was carried out at 60℃ for 0.1h, the hydrothermal crystallization product was filtered, washed to neutral, and dried at 80℃ to constant weight, to obtain 13X molecular sieve.

[0095] Step four, the 13X molecular sieve was immersed in a carbon precursor solution, stirred for 6h, and then heated to 600℃ under an inert gas atmosphere for 2h to obtain carbon-modified 13X molecular sieve; the carbon source in the carbon precursor solution was furan, and the solvent was acetone, and the concentration of the carbon source was 5% based on the mass percentage of the carbon precursor solution.

[0096] Step five, 50g of carbon-modified 13X molecular sieve and 0.1g of isopropyl trimethoxysilane were added to 40g of anhydrous ethanol, stirred at 15℃ for 1h, and then filtered, and the filtered molecular sieve was calcined at 400℃ for 0.5h;

[0097] The calcined 13X molecular sieve was soaked in a 0.1mol / L aqueous copper chloride solution at room temperature for 24h;

[0098] 10g of titanium silicate was added dropwise to a mixed solvent of 30g of ethanol and 5g of distilled water, stirred at 50℃ for 1h to obtain a titanium precursor sol;

[0099] The 13X molecular sieve soaked in the copper salt solution was added to the titanium precursor sol, and after uniform stirring, the mixture was dried at 90℃ for 6h, and then heated to 450℃ at a heating rate of 5℃ / min in a kiln, and calcined for 0.5h;

[0100] The calcined product was dried in a vacuum drying device for 12h to obtain a molecular sieve organic oxidant adsorbent.

[0101] Example 3

[0102] A preparation method of a molecular sieve organic oxidant adsorbent, the specific steps are as follows:

[0103] Step one, 0.17g of silicon powder was dissolved in 6g of deionized water, and after pretreatment at 25℃ and 200rpm in a sealed reaction kettle for 1h, a silicon-containing material was obtained;

[0104] 12g of aluminum nitrate was dissolved in 18.0g of deionized water, and stirred at 35℃ and 200rpm for 1h to prepare an aluminum-containing material;

[0105] The aluminum source solution was added to the silicon-containing material, and stirring was carried out at 100℃ for 24h to obtain a gel solution;

[0106] 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, and then the prepared gel was poured into an autoclave for two-stage crystallization, first crystallization at 60°C for 24 hours, and then the temperature was increased to 120°C for crystallization for 48 hours to obtain a solution containing 13X molecular sieve seeds, wherein in the solution containing 13X molecular sieve seeds, the molar ratio of each component was: SiO2 / Al2O3=0.1:1, Na2O / SiO2=4:1, H2O / SiO2=1:1.

[0107] Step two, the waste MTO catalyst was ground to 200 mesh, and the ground waste MTO catalyst was uniformly mixed with NaCO3 at a mass ratio of 1:5, and then calcined at 800°C for 120 min, and the calcined product was dissolved with 10% nitric acid, and the residue was filtered to obtain an aluminum-rich liquid and a residue;

[0108] The residue was uniformly mixed with NaOH and H2O at a mass ratio of 100:60:400, and filtered to obtain a silicon-rich liquid; the silicon-rich liquid and the aluminum-rich liquid were weighed and matched to obtain a gel-like mother liquor, wherein the molar ratio of each component in the gel-like mother liquor was SiO2 / Al2O3=0.5:1, Na2O / SiO2=6.0:1, and H2O / SiO2=10:1.

[0109] Step three, in the prepared gel-like mother liquor, 20% of the prepared solution containing 13X molecular sieve seeds was added, the mixture was stirred and aged at 100°C for 24h, and then hydrothermal crystallization treatment was carried out at 105°C for 36h, and the hydrothermal crystallization product was filtered, washed to neutral, and dried at 120°C to constant weight to obtain 13X molecular sieve.

[0110] Step four, the 13X molecular sieve was immersed in a carbon precursor solution and stirred for 48h, and then the immersed 13X molecular sieve was heated to 900°C under an inert gas atmosphere for 4 hours to obtain carbon-modified 13X molecular sieve; wherein the carbon source in the carbon precursor solution is furfural, the solvent is tetrahydrofuran, and the concentration of the carbon source is 25% based on the mass percentage of the carbon precursor solution.

[0111] Step five, 50g of carbon-modified 13X molecular sieve and 2.5g of tetraethyl orthosilicate were added to 100g of anhydrous ethanol, and the mixture was stirred and reacted at 40°C for 10 hours, and then filtered, and the filtered molecular sieve was calcined at 500°C for 4 hours;

[0112] The calcined 13X molecular sieve was soaked in a 2 mol / L aqueous copper acetate solution at room temperature for 24 hours;

[0113] 10 g of titanium diisopropoxy bisacetylacetone was added dropwise into a mixed solvent of 70 g of ethanol and 15 g of distilled water, and stirred at 70 °C for 6 hours to obtain a titanium precursor sol;

[0114] The 13X molecular sieve after soaking the copper salt solution was added to the titanium precursor sol, and after stirring uniformly, the mixture was dried at 110 °C for 18 hours, and then heated to 550 °C at a heating rate of 5 °C / min in a kiln, and calcined for 4 hours;

[0115] The calcined product was dried for 12 hours by a vacuum drying device to obtain a molecular sieve organic oxide adsorbent.

[0116] Example 4

[0117] The difference from Example 1 is only that Step one is different, specifically, Step one is as follows:

[0118] 14.65 g of tetraethyl orthosilicate was mixed with 36 g of deionized water, and after pretreatment at 25 °C and 800 rpm in a closed reaction kettle for 1 hour, a silicon-containing material was obtained;

[0119] 12 g of aluminum nitrate was dissolved in 18.0 g of deionized water, and stirred at 35 °C and 800 rpm for 1 hour to obtain an aluminum-containing material;

[0120] The aluminum-containing material was gradually added to the silicon-containing material, and mixed and stirred at 20 °C for 0.1 hours to prepare a gel solution;

[0121] 0.56 g of sodium hydroxide was dissolved in 6 g of deionized water to prepare a sodium hydroxide aqueous solution, which was poured into the gel solution until the pH value was 8.5, and the prepared gel was introduced into a hydrothermal reaction kettle to perform a staged crystallization reaction: first set the crystallization temperature to 20 °C for 4 hours, and then raise it to 80 °C and keep it for 6 hours to obtain a solution containing 13X molecular sieve seeds, wherein the molar ratio of each component in the solution containing 13X molecular sieve seeds is: SiO2 / Al2O3 = 2.5:1, Na2O / SiO2 = 0.1:1, H2O / SiO2 = 40:1.

[0122] Example 5

[0123] The difference from Example 1 is only that the methyltriethoxysilane in Step five is replaced by 3-aminopropyltriethoxysilane.

[0124] Example 6

[0125] The difference from Example 1 is only that the crystallization temperature in the second stage of hydrothermal crystallization treatment is 70 °C.

[0126] Example 7

[0127] The difference between it and Example 1 is only that the crystallization temperature in the second-stage hydrothermal crystallization treatment is 120°C.

[0128] Example 8

[0129] The difference between it and Example 1 is only that the pH value of the gel solution in step (1) is adjusted to 8.5.

[0130] Comparative Example 1

[0131] The difference between it and Example 1 is only that step one is only a first-stage hydrothermal crystallization treatment, specifically, step one is as follows:

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

[0133] 24 g of aluminum sulfate is 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 is added dropwise to the silicon-containing material, and stirring is continued at 60°C for 8 h to obtain a gel solution;

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

[0136] The gel solution is placed in a hydrothermal reaction kettle, and a hydrothermal crystallization treatment is performed at a crystallization temperature of 40°C and a crystallization time of 12 hours to obtain a solution containing 13X molecular sieve seeds.

[0137] Comparative Example 2

[0138] The difference between it and Example 1 is only that step one is only a second-stage hydrothermal crystallization treatment, specifically, step one is as follows:

[0139] Step one, 21.0 g of silica sol (30% by mass of silicon dioxide) is dissolved in 36.0 g of deionized water, and after pretreatment at 25°C and 500 rpm for 1 hour in a sealed reaction kettle, a silicon-containing material is obtained;

[0140] 24 g of aluminum sulfate is 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;

[0141] The aluminum-containing material is added dropwise to the silicon-containing material, and stirring is continued at 60°C for 8 h to obtain a gel solution;

[0142] A solution of 6.74 g of sodium hydroxide in 36 g of deionized water was prepared and added to the gel solution until the pH value was 12, to obtain a gel solution;

[0143] The gel solution was placed in a hydrothermal reactor and subjected to hydrothermal crystallization treatment at a crystallization temperature of 95℃ and a crystallization time of 24 hours, to obtain a solution containing 13X molecular sieve seeds.

[0144] Comparative Example 3

[0145] The difference between it and Example 1 is only that step four is not performed, and the specific steps are as follows:

[0146] Step one, 21.0 g of silica sol (30% by mass of silicon dioxide) was dissolved in 36.0 g of deionized water, and after 1 hour of pretreatment at 25℃ and 500 rpm in a sealed reactor, a silicon-containing material was obtained;

[0147] 24 g of aluminum sulfate was dissolved in 18.0 g of deionized water, and stirred at 25℃ and 500 rpm for 1 hour to obtain an aluminum-containing material;

[0148] The aluminum-containing material was added dropwise to the silicon-containing material, and stirring was continued at 60℃ for 8 hours to obtain a gel solution;

[0149] A solution of 6.74 g of sodium hydroxide in 36 g of deionized water was prepared and added to the gel solution until the pH value was 12, to obtain a gel solution;

[0150] The gel solution was placed in a hydrothermal reactor and subjected to two-stage hydrothermal crystallization treatment, in the first stage, the crystallization temperature was 40℃ and the crystallization time was 12 hours, and in the second stage, the crystallization temperature was 95℃ and the crystallization time was 24 hours, to obtain a solution containing 13X molecular sieve seeds, wherein the molar ratio of each component in the solution containing 13X molecular sieve seeds was SiO2 / Al2O3 = 1.5:1, Na2O / SiO2 = 1.6:1, and H2O / SiO2 = 32:1.

[0151] Step two, the fly ash was ground to 200 mesh, and the ground fly ash was stirred and mixed uniformly with NaCO3 at a mass ratio of 1:2.5, then calcined at 700℃ for 90 min, and the calcined product was dissolved with 25% by mass of hydrochloric acid to obtain an aluminum-rich liquid and a residue;

[0152] The residue was stirred and mixed uniformly with NaOH and H2O at a mass ratio of 50:50:200, and filtered to obtain a silicon-rich liquid;

[0153] The silicon-rich liquid and the aluminum-rich liquid are weighed and proportioned to obtain a gelatinous mother liquor, and the molar ratio of each component in the gelatinous mother liquor is SiO2 / Al2O3 = 3.5:1, Na2O / SiO2 = 2.8:1, and H2O / SiO2 = 80:1;

[0154] In step three, 15% of the prepared solution containing 13X molecular sieve seeds is added to the prepared gelatinous mother liquor, which is 100% in mass, and the mixture is stirred and aged at 60°C for 12 hours, and then subjected to hydrothermal crystallization treatment at 80°C for 12 hours. The hydrothermal crystallization product is filtered, washed to neutral, and dried at 100°C to constant weight to obtain 13X molecular sieve.

[0155] In step four, 50g of 13X molecular sieve and 0.5g of methyltriethoxysilane are added to 49.5g of anhydrous ethanol, and the mixture is stirred at room temperature for 4 hours, and then filtered. The filtered molecular sieve is calcined at 450°C for 2 hours.

[0156] The calcined 13X molecular sieve is soaked in a 1 mol / L aqueous copper nitrate solution at room temperature for 24 hours.

[0157] 10g of tetrabutyl titanate is added dropwise to a mixed solvent of 50g of ethanol and 10g of distilled water, and the mixture is stirred at 60°C for 3 hours to obtain a titanium precursor sol.

[0158] The 13X molecular sieve soaked in the copper salt solution is added to the titanium precursor sol, and the mixture is stirred uniformly and then dried at 100°C for 12 hours. Subsequently, the mixture is heated to 500°C at a heating rate of 5°C / min in a kiln, and calcined for 2 hours.

[0159] The calcined product is dried in a vacuum drying device for 12 hours to obtain a molecular sieve organic oxide adsorbent.

[0160] Comparative Example 4

[0161] The difference between Example 1 and Comparative Example 4 is that step five is not performed, and the specific steps are as follows:

[0162] In step one, 21.0g of silica sol (30% of silica by mass) is dissolved in 36.0g of deionized water, and a silicon-containing material is obtained by pre-treating the mixture in a sealed reaction kettle at 25°C and 500rpm for 1 hour.

[0163] In step two, 24g of aluminum sulfate is dissolved in 18.0g of deionized water, and the mixture is stirred at 25°C and 500rpm for 1 hour to obtain an aluminum-containing material.

[0164] In step three, the aluminum-containing material is added dropwise to the silicon-containing material, and the mixture is stirred at 60°C for 8 hours to obtain a gel solution.

[0165] An aqueous solution of sodium hydroxide was prepared by dissolving 6.74 g of sodium hydroxide in 36 g of deionized water, and the solution was added to the gel solution until the pH value was 12, to obtain a gel solution;

[0166] The gel solution was placed in a hydrothermal reactor, and two-stage hydrothermal crystallization treatment was performed. In the first-stage hydrothermal crystallization treatment, the crystallization temperature was 40℃, and the crystallization time was 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature was 95℃, and the crystallization time was 24 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 SiO2 / Al2O3 = 1.5:1, Na2O / SiO2 = 1.6:1, and H2O / SiO2 = 32:1.

[0167] In step two, the fly ash was ground to 200 mesh or less. The ground fly ash and NaCO3 were stirred and mixed uniformly at a mass ratio of 1:2.5, and then calcined at 700℃ for 90 min. The calcined product was dissolved with 25% hydrochloric acid by mass fraction, and filtration was performed to obtain an aluminum-rich liquid and a residue.

[0168] The residue, NaOH, and H2O were stirred and mixed uniformly at a mass ratio of 50:50:200, and filtration was performed to obtain a silicon-rich liquid.

[0169] The silicon-rich liquid and the aluminum-rich liquid were weighed and matched to obtain a gel-like mother liquor. In the gel-like mother liquor, the molar ratio of each component was SiO2 / Al2O3 = 3.5:1, Na2O / SiO2 = 2.8:1, and H2O / SiO2 = 80:1.

[0170] In step three, based on 100% of the mass of the gel-like mother liquor, 15% of the prepared solution containing 13X molecular sieve seeds was added to the prepared gel-like mother liquor. Stirring and aging treatment were performed at 60℃ for 12 h, and then hydrothermal crystallization treatment was performed at 80℃ for 12 h. The hydrothermal crystallization product was filtered, washed to neutral, and dried at 100℃ to constant weight to obtain 13X molecular sieve.

[0171] In step four, the 13X molecular sieve was immersed in a carbon precursor solution and stirred for 24 h. The 13X molecular sieve immersed in the carbon precursor solution was heated to 750℃ under an inert gas atmosphere for 3 hours to obtain carbon-modified 13X molecular sieve. In the carbon precursor solution, the carbon source was benzene, and the solvent was ethanol. The concentration of the carbon source was 15% based on the mass percentage of the carbon precursor solution.

[0172] Comparative Example 5

[0173] The difference between it and Example 1 is only that no copper salt solution soaking treatment is performed in step five. The specific steps are as follows:

[0174] Step one, 21.0 g of silica sol (mass fraction of 30% of silicon dioxide) is dissolved in 36.0 g of deionized water, and after 1 hour of pretreatment at 25℃ and 500 rpm in a closed reaction kettle, a silicon-containing material is obtained;

[0175] 24 g of aluminum sulfate is dissolved in 18.0 g of deionized water, and after 1 hour of stirring at 25℃ and 500 rpm, an aluminum-containing material is obtained;

[0176] The aluminum-containing material is added dropwise to the silicon-containing material, and stirring is continued at 60℃ for 8 hours to obtain a gel solution;

[0177] 6.74 g of sodium hydroxide is dissolved in 36 g of deionized water to form an aqueous sodium hydroxide solution, and the gel solution is added until the pH value is 12 to obtain a gel solution;

[0178] The gel solution is placed in a hydrothermal reaction kettle, and two-stage hydrothermal crystallization treatment is carried out, in the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40℃, and the crystallization time is 12 hours, in the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95℃, and the crystallization time is 24 hours, to obtain a solution containing 13X molecular sieve seeds, wherein the molar ratio of each component in the solution containing 13X molecular sieve seeds is SiO2 / Al2O3 = 1.5:1, Na2O / SiO2 = 1.6:1, and H2O / SiO2 = 32:1.

[0179] Step two, the fly ash is ground to 200 mesh or less, and the ground fly ash is uniformly mixed with NaCO3 at a mass ratio of 1:2.5, then calcined at 700℃ for 90 min, and the calcined product is dissolved with 25% hydrochloric acid to obtain an aluminum-rich liquid and a residue;

[0180] The residue is uniformly mixed with NaOH and H2O at a mass ratio of 50:50:200, and filtered to obtain a silicon-rich liquid;

[0181] The silicon-rich liquid and the aluminum-rich liquid are weighed and matched to obtain a gel-like mother liquor, and the molar ratio of each component in the gel-like mother liquor is SiO2 / Al2O3 = 3.5:1, Na2O / SiO2 = 2.8:1, and H2O / SiO2 = 80:1;

[0182] Step three, based on 100% of the mass of the gel-like mother liquor, 15% of the prepared solution containing 13X molecular sieve seeds is added to the prepared gel-like mother liquor, and stirring and aging treatment is carried out at 60℃ for 12 hours, then hydrothermal crystallization treatment is carried out at 80℃ for 12 hours, the hydrothermal crystallization product is filtered, washed to neutral, and dried at 100℃ to constant weight to obtain 13X molecular sieve.

[0183] Step four, 13X molecular sieves are immersed in a carbon precursor solution, stirred for 24 h, and then heated to 750°C under an inert gas atmosphere for 3 h to obtain carbon-modified 13X molecular sieves; wherein the carbon source in the carbon precursor solution is benzene, the solvent is ethanol, and the concentration of the carbon source is 15% by mass percentage of the carbon precursor solution.

[0184] Step five, 50 g of carbon-modified 13X molecular sieves and 0.5 g of methyl triethoxysilane are added to 49.5 g of anhydrous ethanol, stirred at room temperature for 4 h, and then filtered, and the filtered molecular sieves are calcined at 450°C for 2 h;

[0185] 10 g of tetrabutyl titanate is added dropwise to a mixed solvent of 50 g of ethanol and 10 g of distilled water, stirred at 60°C for 3 h, and a titanium precursor sol is obtained;

[0186] The calcined 13X molecular sieves are added to the titanium precursor sol, stirred uniformly, and then the mixture is 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;

[0187] The calcined product is dried in a vacuum drying device for 12 h to obtain a molecular sieve organic oxide adsorbent.

[0188] Comparative Example 6

[0189] The difference between it and Example 1 is only that no titanium precursor sol treatment is performed in Step five, and the specific steps are as follows:

[0190] Step one, 21.0 g of silica sol (30% by mass fraction of silicon dioxide) is dissolved in 36.0 g of deionized water, and after pre-treatment in a sealed reaction kettle at 25°C and 500 rpm for 1 h, a silicon-containing material is obtained;

[0191] 24 g of aluminum sulfate is 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;

[0192] The aluminum-containing material is added dropwise to the silicon-containing material, and stirring is continued at 60°C for 8 h to obtain a gel solution;

[0193] 6.74 g of sodium hydroxide is dissolved in 36 g of deionized water to obtain an aqueous sodium hydroxide solution, and added to the gel solution until the pH value is 12 to obtain a gel solution;

[0194] The gel solution is placed into a hydrothermal reactor, and two-stage hydrothermal crystallization treatment is performed. In the first-stage hydrothermal crystallization treatment, the crystallization temperature is 40℃, and the crystallization time is 12 hours. In the second-stage hydrothermal crystallization treatment, the crystallization temperature is 95℃, and the crystallization time is 24 hours. A solution containing 13X molecular sieve seeds is obtained. In the solution containing 13X molecular sieve seeds, the molar ratio of each component is SiO2 / Al2O3 = 1.5:1, Na2O / SiO2 = 1.6:1, and H2O / SiO2 = 32:1.

[0195] In step two, the fly ash is ground to 200 mesh or less. The ground fly ash is uniformly mixed with NaCO3 in a mass ratio of 1:2.5, and then calcined at 700℃ for 90 minutes. The calcined product is dissolved with 25% hydrochloric acid by mass fraction, and a filtrate rich in aluminum and a residue are obtained.

[0196] The residue is uniformly mixed with NaOH and H2O in a mass ratio of 50:50:200, and a filtrate rich in silicon is obtained.

[0197] The filtrate rich in silicon and the filtrate rich in aluminum are weighed and matched to obtain a gel mother liquor. In the gel mother liquor, the molar ratio of each component is SiO2 / Al2O3 = 3.5:1, Na2O / SiO2 = 2.8:1, and H2O / SiO2 = 80:1.

[0198] In step three, 15% of the prepared solution containing 13X molecular sieve seeds is added to the prepared gel mother liquor, which is taken as 100% by mass. The mixture is stirred and aged at 60℃ for 12 hours, and then subjected to hydrothermal crystallization treatment at 80℃ for 12 hours. The hydrothermal crystallization product is filtered, washed to neutral, and dried at 100℃ to constant weight to obtain 13X molecular sieve.

[0199] In step four, the 13X molecular sieve is immersed in a carbon precursor solution and stirred for 24 hours. The 13X molecular sieve immersed in the carbon precursor solution is heated to 750℃ under an inert gas atmosphere for 3 hours to obtain carbon-modified 13X molecular sieve. In the carbon precursor solution, the carbon source is benzene, and the solvent is ethanol. The concentration of the carbon source is 15% by mass percentage of the carbon precursor solution.

[0200] In step five, 50g of carbon-modified 13X molecular sieve and 0.5g of methyltriethoxysilane are added to 49.5g of anhydrous ethanol, and the mixture is stirred at room temperature for 4 hours. Then, the mixture is filtered, and the filtered molecular sieve is calcined at 450℃ for 2 hours.

[0201] The calcined 13X molecular sieve is immersed in a 1 mol / L aqueous copper nitrate solution at room temperature for 24 hours.

[0202] The 13X molecular sieve after soaking in the copper salt solution is 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;

[0203] The calcined product is dried in a vacuum drying device for 12 hours to obtain a molecular sieve organic oxide adsorbent.

[0204] I. The silicon-aluminum ratio and specific surface area of the organic oxide adsorbents prepared in the examples and comparative examples are tested, and the results are shown in Table 1.

[0205] II. The adsorption performance of the organic oxide adsorbents prepared in the examples and comparative examples is tested, and the specific steps are as follows: taking a Fischer-Tropsch synthesis product as the adsorption object, passing it through a fixed bed containing the adsorbent, and monitoring the changes in product concentration and oxygen-containing compound impurity concentration before and after passing through the bed, to calculate the removal rate of organic oxide impurities and the product loss rate, wherein the adsorption temperature is 55°C, the pressure is 1 atm, the weight ratio of adsorbent to Fischer-Tropsch synthesis product is 1:10, the adsorbent loading is 1 g, the sample enters the fixed bed reactor at a flow rate of 10 ml / min, the adsorption time is 2 hours, and the content of each component in the Fischer-Tropsch synthesis product before treatment is shown in Table 2.

[0206] Table 1

[0207]

[0208]

[0209] Table 2

[0210]

[0211] As shown in Table 1, the molecular sieve organic oxide adsorbents prepared in Examples 1 to 8 have high silicon-aluminum ratio, high specific surface area and high pore volume. Specifically, the silicon-aluminum ratio is 2.2-2.9, the pore volume is between 0.39 cm 3 / g-0.5 cm 3 / g, and the specific surface area is between 800 m 2 / g-950 m 2 / g. Among them, compared with Comparative Example 1 and Comparative Example 2 which use a single-stage crystallization process and Comparative Example 3 which is not subjected to carbon modification treatment, Example 1 which uses a two-stage crystallization process and carbon modification treatment significantly improves the specific surface area of the adsorbent; and as shown by the data of Example 1 and Comparative Examples 4 to 6, organic silicon modification treatment, copper salt solution immersion treatment, titanium precursor sol immersion treatment and secondary calcination treatment can increase the adsorption sites of organic oxides and reduce product loss.

[0212] From Table 2, it can be seen that the molecular sieve organic oxygenate adsorbents prepared in Examples 1 to 8 have better adsorption effect on organic oxygen compounds in different carbon number products of Fischer-Tropsch synthesis, and almost no adsorption on alkane and alkene products of Fischer-Tropsch synthesis, and have high adsorption capacity and good selectivity on organic oxygen compounds.

[0213] The preferred embodiments of the present application have been described above with the preferred embodiments, but the present application is not limited to the above examples, and can be variously changed and modified by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a molecular sieve organooxidizer adsorbent, characterized by, The method comprises the following steps: 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 by 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 treatment is 80-120°C; Step S2, mixing a molecular sieve-containing material and sodium carbonate according to a mass ratio of 1:0.5-1:5, calcining at 550-800°C for 60-120 min, dissolving the calcined product with a monobasic acid with a mass fraction of 10%-35%, filtering to obtain an aluminum-rich liquid and a residue, stirring and mixing the residue with sodium hydroxide and water according to a mass ratio of 5-100:40-60:50-400 to dissolve the residue, filtering to obtain a silicon-rich liquid, and mixing the aluminum-rich liquid and the silicon-rich liquid to obtain a second gel-like mother liquor; the molecular sieve-containing material is selected from one or more of waste MTO catalysts, waste molecular sieve adsorbents, waste FCC catalysts, and waste VOC adsorbents; Step S3, mixing the solution containing 13X molecular sieve seeds and the second gel-like mother liquor, performing aging treatment, and then performing hydrothermal crystallization treatment at 60-105°C to obtain 13X molecular sieve; Step S4, performing immersion treatment on the 13X molecular sieve by using a carbon precursor solution to obtain 13X molecular sieve impregnated with the carbon precursor solution, and performing heat treatment on the 13X molecular sieve impregnated with the carbon precursor solution at 600-900°C in an inert gas atmosphere to obtain carbon-modified 13X molecular sieve; Step S5, reacting the carbon-modified 13X molecular sieve and an organosilicon coupling agent in an organic alcohol solvent to obtain organosilicon-modified 13X molecular sieve, performing first calcination treatment on the organosilicon-modified 13X molecular sieve, performing immersion treatment on the first calcination treatment product by using a copper salt solution to obtain 13X molecular sieve impregnated with the 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, performing drying treatment on the mixture, and then performing second calcination treatment to obtain the molecular sieve organooxide 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 of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: In the step S1, 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, 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 of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: In the step S1, the mass fraction of the silicon source in the silicon-containing material is 2%-50%.

4. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: In the step S1, the silicon source and the water are stirred at 20-60°C for 0.1-12 h to obtain the silicon-containing material. In the step S1, the silicon source and the water are stirred at 20-60°C for 0.1-12 h to obtain the silicon-containing material.

5. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The mass fraction of the aluminum source in the aluminum-containing material is 15% to 60% in the step S1.

6. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The aluminum source and the water are stirred at 20 to 60 ℃ for 0.1 to 12 h to obtain the aluminum-containing material in the step S1.

7. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The first gelatinous mother liquor is obtained by stirring and mixing at 20 to 100 ℃ for 0.1 to 24 h in the step S1.

8. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The pH value of the first gelatinous mother liquor is 11.8 to 12.

5.

9. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The pH value of the first gelatinous mother liquor is adjusted by adding solid sodium hydroxide or adding an aqueous solution of sodium hydroxide in the step S1.

10. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization temperature in the second-stage hydrothermal crystallization treatment is higher than that in the first-stage hydrothermal crystallization treatment by 40 ℃ or more.

11. The method of claim 10, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization temperature in the second-stage hydrothermal crystallization treatment is higher than that in the first-stage hydrothermal crystallization treatment by 50 to 60 ℃.

12. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization temperature in the first-stage hydrothermal crystallization treatment is 40 to 60 ℃, and the crystallization time is 4 to 24 h.

13. The method of claim 12, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization time in the first-stage hydrothermal crystallization treatment is 11 to 24 h.

14. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization temperature in the second-stage hydrothermal crystallization treatment is 90 to 100 ℃, and the crystallization time is 6 to 48 h.

15. The method of claim 14, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The crystallization time in the second-stage hydrothermal crystallization treatment is 18 to 48 h.

16. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The molar ratio of each component in the solution containing 13X molecular sieve seeds is SiO2 / Al2O3= (0.01 to 6) : 1, Na2O / SiO2= (0.01 to 4.0) : 1, and H2O / SiO2= (1.0 to 50.0) :

1.

17. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The molecular sieve-containing material is ground to 200 mesh or less and then mixed with the sodium carbonate in the step S2.

18. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The monobasic acid is selected from at least one of hydrochloric acid, acetic acid, and nitric acid.

19. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The molar ratio of each component in the second gelatinous mother liquor in the step S2 is SiO2 / Al2O3= 0.5 to 6.0 : 1, Na2O / SiO2= 0.5 to 6.0 : 1, and H2O / SiO2= 10 to 100 :

1.

20. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The mass of the solution containing 13X molecular sieve seeds added in the step S3 is 5% to 20% based on 100% of the mass of the second gelatinous mother liquor.

21. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The aging treatment in the step S3 is performed under stirring, the temperature of the aging treatment is 20 to 100 ℃, and the time of the aging treatment is 0.1 to 24 h.

22. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The time of the hydrothermal crystallization treatment in the step S3 is 0.1 to 36 h.

23. The method for preparing the molecular sieve organic oxide adsorbent according to claim 1, characterized in that, The product after the hydrothermal crystallization treatment in the step S3 is filtered, washed to neutral, and then dried at 80 to 120 ℃ to constant weight to obtain the 13X molecular sieve.

24. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The carbon source in the carbon precursor solution is selected from one of benzene, furan, and furfural, and the solvent in the carbon precursor solution is selected from one of N, N-dimethylformamide, acetone, ethanol, and tetrahydrofuran.

25. The method for preparing the molecular sieve organic oxide adsorbent according to claim 1, characterized in that, The concentration of the carbon source in the carbon precursor solution is 5% to 25% based on the mass percentage of the carbon precursor solution.

26. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The soaking treatment in the step S4 is performed under stirring, and the stirring time is 6 to 48 h.

27. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The time of the heat treatment in the step S4 is 2 to 4 h.

28. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The organic silicon coupling agent in the step S5 is selected from one or more of methyl triethoxysilane, isopropyl trimethoxysilane, vinyl trimethoxysilane, ethyl silicate, 3-aminopropyl triethoxysilane.

29. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The mass ratio of the carbon-modified 13X molecular sieve, the organic silicon coupling agent and the organic alcohol solvent in the step S5 is 1: (0.002-0.05): (0.8-2).

30. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The temperature of the reaction in the step S5 is 15-40℃, and the reaction time is 1-10h.

31. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The time of the first calcination treatment in the step S5 is 0.5-4h.

32. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The copper salt in the step S5 is selected from one or more of copper nitrate, copper chloride, copper acetate.

33. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The concentration of the copper salt solution in the step S5 is 0.1-2mol / L, and the time of the soaking treatment is 6-48h.

34. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The titanium source in the titanium precursor sol in the step S5 is selected from one or more of tetrabutyl titanate, titanium orthosilicate or diisopropoxy titanium diacetylacetone.

35. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The titanium precursor sol in the step S5 is formed by mixing the titanium source, ethanol and water.

36. The method of claim 35, wherein the molecular sieve organooxidate adsorbent is prepared by the process comprising: The titanium source, the ethanol and water in the step S5 are mixed at 50-70℃ for 1-6h to form the titanium precursor sol.

37. The method for preparing the molecular sieve organic oxide adsorbent according to claim 35, characterized in that, In the step S5, the ethanol and the water are first mixed to form a mixed solvent, and then the titanium source is added for mixing.

38. The method for preparing the molecular sieve organic oxide adsorbent according to claim 35, characterized in that, The titanium source, the ethanol and the water in the step S5 are mixed at a mass ratio of 1: (3-7): (0.5-1.5).

39. The method of claim 1, wherein the molecular sieve organooxidate adsorbent is prepared by the steps of: The temperature of the drying treatment in the step S5 is 90-110℃, and the time of the drying treatment is 6-18h.

40. The method for preparing the molecular sieve organic oxide adsorbent according to claim 1, characterized in that, The time of the second calcination treatment in the step S5 is 0.5-4h.

41. A molecular sieve organooxygenate adsorbent characterized by, The molecular sieve organic oxide adsorbent is prepared according to the preparation method of the molecular sieve organic oxide adsorbent in any one of claims 1-40.

42. The use of the molecular sieve organic oxide adsorbent in claim 41 in removing organic oxides in hydrocarbons.

43. Use of a molecular sieve organic oxide adsorbent according to Claim 42 for removing organic oxides from hydrocarbons, characterized in that, The hydrocarbon is a hydrocarbon product of coal through Fischer-Tropsch synthesis, or an olefin product of petroleum cracking.

44. Use of a molecular sieve organic oxide adsorbent according to Claim 42 for removing organic oxides from hydrocarbons, characterized in that, The organic oxide is selected from one or more of alcohol, aldehyde, ketone and carboxylic acid with 1-21 carbon atoms.

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