CN109095493B - Two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material and preparation method and application thereof - Google Patents
Two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material and preparation method and application thereof Download PDFInfo
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Abstract
The two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material is 1-30 nanometers in thickness, has a crystal structure of an SAPO-34 molecular sieve, and has a silicon/aluminum atomic ratio of 0.15-0.25 and a Cu mass content of 0.5-5%. The invention has the beneficial effects that: the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve material is prepared by taking cheap and easily-obtained aluminum phosphate, a silicon source and organic amine as reactants and stripping a layered precursor by a chemical method to further perform gas phase crystallization, wherein the contents of copper and silicon are adjustable within a certain range. It has huge external surface area, large amount of molecular sieve cage exposure windows and unique reaction performance. The two-dimensional ultrathin CuO @ SAPO-34 molecular sieve material shows the best catalytic performance to date in the reaction of catalyzing the oxidation of cyclohexane to prepare adipic acid through oxygen. The material has many advantages and can be produced in large scale. The method has the advantages of less template agent consumption, low cost and little environmental pollution, and is suitable for industrial mass production. The invention discloses a preparation method of the compound.
Description
The technical field is as follows:
the invention relates to a two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material, a preparation method thereof and application thereof in reaction for preparing adipic acid by cyclohexane oxidation.
Background art:
the SAPO-34 molecular sieve with the CHA structure is the most important member of SAPO series molecular sieves (aluminophosphate silicon molecular sieves), and has good thermal stability, hydrothermal stability and ion exchange property. Furthermore, hetero atoms are introduced into the molecular sieve by doping, so that the catalytic activity of the molecular sieve can be expanded and improved. Wherein, Cu-SAPO-34 molecular sieve formed by introducing Cu is arranged at the tail of the automobileExhibit excellent catalytic activity in gas treatment, e.g., NOx and NH3Catalytic conversion of (2), etc.
Therefore, the Cu-SAPO-34 molecular sieve attracts a great deal of attention as a novel catalytic material. A large number of literature reports and patent applications relating to the synthesis of Cu-SAPO-34 molecular sieves are continuously published and published. For example, the literature reports: in 2017, a paper published by Chinese Journal of Catalysis by the people in Liu of the institute of Dalian chemistry reports that Cu-SAPO-34 molecular sieve is used for catalyzing reduction reaction of NOx; in 2016, a paper published by Chinese Journal of Catalysis by the Liu Ji province subject group of China at the university of Petroleum reports that mesoporous Cu-SAPO-34 molecular sieve is used for ammonia selective catalytic reduction reaction; SAPO-5 molecular sieve nanosheets of (a); in 2018, a paper published by the morning topic group of Tianjin university at Journal of Catalysis reports that Cu-SAPO-34 molecular sieve is used for treating automobile exhaust; the 2012 patent applications include: direct synthesis of Cu-SAPO-34 (application number: 01280072685. X); patent applications in 2014 include: a Cu-SAPO-34 molecular sieve catalyst, a preparation method and application thereof (application number: 201410495419.9), an assistant-doped Cu-SAPO-34 catalyst and a preparation method and application thereof (application number: 201410455295.1); 2016, patent applications: Cu/SAPO-34 molecular sieve catalyst, and a preparation method and application thereof (application number: 201610741146.0); patent applications in 2017 include: a preparation method of a Cu-SAPO-34 molecular sieve catalyst (application number: 201711329689.2). Among these reports, the research can be mainly attributed to: (1) a novel synthesis method of the Cu-SAPO-34 molecular sieve, (2) application of the Cu-SAPO-34 molecular sieve in catalytic reaction, particularly in the aspect of automobile exhaust treatment, and (3) control of the crystal morphology of the SAPO molecular sieve.
Summarizing the literature results of Cu-SAPO-34 molecular sieve preparation for many years, no flaky CuO @ SAPO-34 molecular sieve material with adjustable silicon-aluminum ratio and thickness of less than 30 nanometers and application thereof in catalytic reaction for preparing adipic acid by cyclohexane oxidation can be found.
The nitric acid oxidation process currently used industrially is a two-step process, i.e. oxidation of cyclohexane to cyclohexanol and cyclohexanone, followed by oxidation of cyclohexanol and cyclohexanone to adipic acid. The process is complex and not environment-friendly.
The invention content is as follows:
the problems to be solved are as follows: the invention aims at the problems to provide a two-dimensional ultrathin film
The CuO @ SAPO-34 molecular sieve flake material, the preparation method thereof and the application thereof in the reaction of preparing adipic acid by cyclohexane oxidation have good catalytic action and are environment-friendly.
The technical scheme of the invention is as follows:
the two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material has a sheet thickness of 1-30 nanometers, and a molecular sieve crystal structure of SAPO-34, wherein the atomic ratio of silicon to aluminum is 0.15-0.25, and the mass content of Cu is 0.5-5%.
A method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve flake material comprises the following steps of:
step 1, preparing the aluminum phosphate nano-coil powder material with a laminated structure. The preparation method is based on the literature (chem. Commun.,2009, 3443-3445). The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
The synthesis method of the aluminum phosphate nanocolloid comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
And 2, adding an ethanol solution of tetraethyl orthosilicate and copper salt into the aluminum phosphate nano coil powder material obtained in the step 1, wherein the adding amount of the tetraethyl orthosilicate is 30-40% of the mass of the aluminum phosphate nano coil, the adding amount of the copper salt is 5-20% of the mass of the aluminum phosphate nano coil, stirring at room temperature to form a paste, and then standing for 24 hours.
And 3, adding 25 percent of tetraethyl ammonium hydroxide solution into the paste obtained in the step 2, wherein the adding amount of the tetraethyl ammonium hydroxide solution is 30 to 40 percent of the mass of the aluminum phosphate nanocolloid, stirring the mixture at room temperature to form a paste, and then standing the paste for 24 hours.
And 4, adding water, 25 percent of tetraethyl ammonium hydroxide solution and alkylamine into the polytetrafluoroethylene lining of the hydrothermal kettle, wherein the adding amount of the tetraethyl ammonium hydroxide solution, the tetraethyl ammonium hydroxide solution and the alkylamine is 25 to 40 percent, 60 to 80 percent and 100 to 160 percent of the mass of the aluminum phosphate nanocoil in sequence.
And 5, transferring the paste obtained in the step 3 into the polytetrafluoroethylene lining in the step 4, sealing, and performing hydrothermal treatment at 160-200 ℃ for 20-72 hours. Then, the mixture was naturally cooled to room temperature, filtered to obtain a precipitate, and the precipitate was washed with water and absolute ethanol several times and dried at 60 ℃ for 24 hours to obtain a dry blue powder.
And 6, putting the blue powder obtained in the step 5 into a muffle furnace, and heating the blue powder to 550 ℃ from room temperature in an air atmosphere, and keeping the blue powder for 5 hours. After that, the mixture was naturally cooled to room temperature, and a blue sample powder was obtained.
The copper salt in step 2 of the above preparation method is preferably copper nitrate or copper acetate.
In the above-mentioned production process, the alkylamine described in step 4 is preferably diethylamine, triethylamine or tripropylamine.
The two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material is used for catalyzing the reaction of preparing adipic acid by oxidizing cyclohexane.
The specific operation is as follows: (1) mixing molecular sieve powder, cyclohexane and acetone according to the proportion of 1:20: 20; (2) transferring into a high-pressure reaction kettle with an inflation valve and stirring, sealing, and introducing O2Gas, and the pressure is kept to be 1.5 MPa; (3) heating the high-pressure reaction kettle to 120-150 ℃, and reacting for 10-24 hours; (4) after the reaction is finished and the temperature is cooled to room temperature, the O in the reaction product is discharged2The gas pressure is reduced to normal pressure; (5) opening the reaction kettle, centrifugally separating, precipitating the lower layer as a molecular sieve catalyst, and takingSupernatant liquor is obtained; (6) distilling the supernatant to obtain viscous liquid; (7) washing the obtained viscous liquid with hot water at 90 ℃; (8) and (4) taking the supernatant, cooling and filtering to obtain solid crystals, namely the adipic acid product.
Advantageous effects
The two-dimensional ultrathin CuO @ SAPO-34 molecular sieve flake material provided by the invention is obtained by preparing the structure system for the first time, and the two-dimensional ultrathin CuO @ SAPO-34 molecular sieve flake material shows excellent catalytic performance in the preparation method and the application in the reaction of preparing adipic acid by oxidizing cyclohexane, so that the best catalytic performance is achieved. The material has many advantages and can be produced in large scale. The preparation method of the invention has the advantages of less template agent consumption, low cost and little environmental pollution, and is suitable for industrial mass production.
Compared with the prior art, the material has the advantages that:
(1) the catalytic efficiency is high. The conversion rate of cyclohexane can reach more than 40 percent, and the selectivity of adipic acid can reach 75 percent; the current industrial nitric acid oxidation process has a total cyclohexane conversion of less than 10% and adipic acid selectivity of about 70%.
(2) Environmental protection and no pollution. The oxidant used in the invention is oxygen, so that the pollution problem is avoided; at present, the nitric acid oxidation method used in industry uses nitric acid as oxidant, at least 3.6 kg of nitric acid is used for producing 1 kg of adipic acid, and a large amount of nitric acid waste water and nitrogen dioxide waste gas are generated, so that serious environmental pollution is caused.
(3) The process flow is simple. The invention is a one-step method, which directly oxidizes cyclohexane into adipic acid; the nitric acid oxidation process currently used industrially is a two-step process, i.e., oxidation of cyclohexane into cyclohexanol and cyclohexanone, followed by oxidation of cyclohexanol and cyclohexanone into adipic acid.
Description of the drawings:
FIG. 1 is an X-ray powder diffraction pattern of a flaky CuO @ SAPO-34 molecular sieve material prepared in example 1 of the present invention.
FIG. 2 is a TEM transmission electron micrograph of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 1 of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of a flaky CuO @ SAPO-34 molecular sieve material prepared in example 2 of the present invention.
FIG. 4 is a TEM transmission electron micrograph of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 2 of the present invention.
FIG. 5 is an X-ray powder diffraction pattern of a flaky CuO @ SAPO-34 molecular sieve material prepared in example 3 of the present invention.
FIG. 6 is a TEM transmission electron micrograph of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 3 of the present invention
FIG. 7 is an X-ray powder diffraction pattern of a flaky CuO @ SAPO-34 molecular sieve material prepared in example 4 of the present invention.
FIG. 8 is a TEM transmission electron micrograph of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 4 of the present invention.
FIG. 9 is an X-ray powder diffraction pattern of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 5 of the present invention.
FIG. 10 is a TEM transmission electron micrograph of the flaky CuO @ SAPO-34 molecular sieve material prepared in example 5 of the present invention.
FIG. 11 is a photograph of adipic acid crystals prepared in example 6 of the present invention.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples.
Example 1:
taking 0.500 g of aluminum phosphate nano-roll powder, adding 0.150 g of tetraethyl orthosilicate, 0.450 g of ethanol and 0.025 g of copper nitrate, stirring at room temperature to form a uniform paste, and standing for 24 hours; then, 0.150 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to a polytetrafluoroethylene liner of a hydrothermal reactor to which 0.125 g of water, 0.300 g of a tetraethylammonium hydroxide (25% strength) solution and 0.500 g of diethylamine were added, and sealed; then, carrying out hydrothermal treatment at 160 ℃ for 72 hours; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dried blue powder; thereafter, the obtained blue powder was put into a muffle furnace, and heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a blue sample powder.
The product is identified as CuO @ SAPO-34 molecular sieve by X-ray powder diffraction (see figure 1), the appearance of the product is detected as a sheet with the thickness of 1 nanometer by a TEM electron microscope (see figure 2), X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.15, and plasma inductance coupling mass spectrometry shows that the mass content of Cu in the sample is 0.5%.
The synthesis method of the aluminum phosphate nanocolloid is based on the literature (chem.Commun.,2009, 3443-3445). The method specifically comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
Example 2:
taking 1.000 g of aluminum phosphate nano-roll powder, adding 0.350 g of tetraethyl orthosilicate, 0.850 g of ethanol and 0.150 g of copper acetate, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.360 g of tetramethylammonium hydroxide (25%) solution is added, stirred into uniform paste and placed for 24 hours; then, the mixture was transferred to a polytetrafluoroethylene liner of a hydrothermal reactor to which 0.325 g of water, 0.750 g of tetramethylethylammonium hydroxide (25% in concentration) solution and 1.500 g of triethylamine were added, and sealed; then, the mixture is heated for 30 hours under 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dried blue powder; thereafter, the obtained blue powder was put into a muffle furnace, and heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a blue sample powder.
The product is identified as CuO @ SAPO-34 molecular sieve by X-ray powder diffraction (see figure 3), the appearance of the product is detected as a sheet with the thickness of 5 nanometers by a TEM electron microscope (see figure 4), X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.22, and plasma inductance coupling mass spectrometry analysis shows that the mass content of Cu in the sample is 1.4%.
The synthesis method of the aluminum phosphate nanocolloid is based on the literature (chem.Commun.,2009, 3443-3445). The method specifically comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
Example 3:
taking 2.000 g of aluminum phosphate nano-roll powder, adding 0.800 g of tetraethyl orthosilicate, 1.600 g of ethanol and 0.240 g of copper nitrate, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.800 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to a polytetrafluoroethylene liner of a hydrothermal reactor to which 0.800 g of water, 1.600 g of a tetraethylammonium hydroxide (25% strength) solution and 3.200 g of tripropylamine were added, and sealed; then, the mixture is heated for 44 hours at 180 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dried blue powder; thereafter, the obtained blue powder was put into a muffle furnace, and heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a blue sample powder.
The product is identified as CuO @ SAPO-34 molecular sieve by X-ray powder diffraction (see figure 5), the appearance of the product is detected as a sheet with the thickness of 30 nanometers by a TEM electron microscope (see figure 6), X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.25, and plasma inductance coupling mass spectrometry analysis shows that the mass content of Cu in the sample is 1.0%.
The synthesis method of the aluminum phosphate nanocolloid is based on the literature (chem.Commun.,2009, 3443-3445). The method specifically comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
Example 4:
taking 3.000 g of aluminum phosphate nanocoil powder, adding 1.050 g of tetraethyl orthosilicate, 2.550 g of ethanol and 0.240 g of copper nitrate, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 0.960 g of tetrabutylammonium hydroxide (25%) solution is added, stirred into uniform paste and placed for 24 hours; then, it was transferred to a polytetrafluoroethylene liner of a hydrothermal reactor to which 0.900 g of water, 2.200 g of tetrabutylammonium hydroxide solution (25% concentration) and 3.600 g of ethylenediamine were added, and sealed; then, heating the mixture for 20 hours at 200 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dried blue powder; thereafter, the obtained blue powder was put into a muffle furnace, and heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a blue sample powder.
The product is identified as CuO @ SAPO-34 molecular sieve by X-ray powder diffraction (see figure 7), the appearance of the product is 18-nanometer-thick slices (see figure 8) by TEM (transmission electron microscope) detection, X-ray fluorescence spectrum analysis shows that the silicon/aluminum atomic ratio of the sample is 0.25, and plasma-inductance coupling mass spectrometry shows that the mass content of Cu in the sample is 3.2%.
The synthesis method of the aluminum phosphate nanocolloid is based on the literature (chem.Commun.,2009, 3443-3445). The method specifically comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
Example 5:
taking 4.000 g of aluminum phosphate nano-roll powder, adding 1.000 g of tetraethyl orthosilicate, 3.800 g of ethanol and 0.740 g of nickel nitrate, stirring at room temperature to form uniform paste, and standing for 24 hours; then, 1.360 g of tetraethylammonium hydroxide (25%) solution is added, stirred into a uniform paste and placed for 24 hours; then, it was transferred to a polytetrafluoroethylene inner liner of a hydrothermal reactor to which 1.000 g of water, 2.800 g of tetraethylammonium hydroxide solution (25% concentration) and 5.200 g of triethylamine were added, and sealed; then, the mixture is heated for 30 hours at 200 ℃; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate for multiple times by using water and absolute ethyl alcohol, and drying at 60 ℃ for 24 hours to obtain dried blue powder; thereafter, the obtained blue powder was put into a muffle furnace, and heated from room temperature to 550 ℃ under an air atmosphere, and held for 5 hours. Finally, the mixture was naturally cooled to room temperature to obtain a blue sample powder.
The product is identified as CuO @ SAPO-34 molecular sieve by X-ray powder diffraction (see figure 9), the appearance of the product is detected as a sheet with the thickness of 25 nanometers by a TEM electron microscope (see figure 10), the silicon/aluminum atomic ratio of the sample is 0.18 by X-ray fluorescence spectrum analysis, and the Cu mass content in the sample is 5% by plasma inductance coupling mass spectrum analysis.
The synthesis method of the aluminum phosphate nanocolloid is based on the literature (chem.Commun.,2009, 3443-3445). The method specifically comprises the following steps: 20 ml of an ethanol solution containing 4.165 g of dodecylamine and 0.500 g of hexadecylamine were slowly added to a solution containing 1.690 g of AlCl at 50 deg.C3·6H2O and 1.404 g NaH2PO4·2H2And (3) obtaining a white suspension in the O solution, transferring the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at 120 ℃ for 48 hours. After cooling, the white precipitate was filtered off, washed repeatedly with water and ethanol and dried overnight under vacuum at 40 ℃.
The aluminum phosphate nano coil is similar to roll paper in appearance, and has an inner diameter of about 80 nm, a thickness of about 120 nm and a height of about 100 nm to 120 nm. The microstructure of the aluminum phosphate nanocolloid is an inorganic-organic composite layered structure, and the interlayer spacing of the aluminum phosphate nanocolloid is about 2.9 nanometers.
Example 6:
mixing 0.350 g molecular sieve powder, 7.000 g cyclohexane and 7.000 g acetone, transferring into 50 ml high-pressure reaction kettle with charging valve and stirring, sealing, and introducing O2Gas, and the pressure is kept to be 1.5 MPa; then, heating the high-pressure reaction kettle to 135 ℃ for reaction for 20 hours; then cooling to room temperature, and discharging O in the solution2When the gas pressure reaches the normal pressure, opening the reaction kettle, performing centrifugal separation, precipitating the lower layer to be a molecular sieve catalyst, and taking out the supernatant; then, the supernatant was distilled to obtain a viscous liquidA body; then, the obtained viscous liquid was washed with hot water at 90 ℃; finally, the supernatant was taken, cooled and filtered to obtain solid crystals as adipic acid product (see fig. 11). The cyclohexane conversion was 44% and the adipic acid selectivity was 76% by analysis.
Example 7:
mixing 0.350 g molecular sieve powder, 7.000 g cyclohexane and 7.000 g acetone, transferring into 50 ml high-pressure reaction kettle with charging valve and stirring, sealing, and introducing O2Gas, and the pressure is kept to be 1.5 MPa; then, heating the high-pressure reaction kettle to 150 ℃ for reaction for 10 hours; then cooling to room temperature, and discharging O in the solution2When the gas pressure reaches the normal pressure, opening the reaction kettle, performing centrifugal separation, precipitating the lower layer to be a molecular sieve catalyst, and taking out the supernatant; then, distilling the supernatant to obtain viscous liquid; then, the obtained viscous liquid was washed with hot water at 90 ℃; and finally, taking the supernatant, cooling and filtering to obtain solid crystals, namely the adipic acid product. The cyclohexane conversion was 42% and the adipic acid selectivity was 70% by analysis.
Example 8
Mixing 0.350 g molecular sieve powder, 7.000 g cyclohexane and 7.000 g acetone, transferring into 50 ml high-pressure reaction kettle with charging valve and stirring, sealing, and introducing O2Gas, and the pressure is kept to be 1.5 MPa; then, heating the high-pressure reaction kettle to 120 ℃ for reaction for 24 hours; then cooling to room temperature, and discharging O in the solution2When the gas pressure reaches the normal pressure, opening the reaction kettle, performing centrifugal separation, precipitating the lower layer to be a molecular sieve catalyst, and taking out the supernatant; then, distilling the supernatant to obtain viscous liquid; then, the obtained viscous liquid was washed with hot water at 90 ℃; and finally, taking the supernatant, cooling and filtering to obtain solid crystals, namely the adipic acid product. The cyclohexane conversion was 45% and the adipic acid selectivity was 73% by analysis.
Claims (9)
1. The two-dimensional ultrathin CuO @ SAPO-34 molecular sieve sheet material has a sheet thickness of 1-30 nanometers, and a molecular sieve crystal structure of SAPO-34, wherein the atomic ratio of silicon to aluminum is 0.15-0.25, and the mass content of Cu is 0.5-5%.
2. The method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step 1, preparing an aluminum phosphate nano coil powder material with a laminated structure;
step 2, adding an ethanol solution of tetraethyl orthosilicate and copper salt into the aluminum phosphate nano coil powder material obtained in the step 1, wherein the adding amount of the tetraethyl orthosilicate is 30-40% of the mass of the aluminum phosphate nano coil, the adding amount of the copper salt is 5-20% of the mass of the aluminum phosphate nano coil, stirring at room temperature to form a paste, and then standing for 24 hours;
step 3, adding tetraethyl ammonium hydroxide solution into the paste obtained in the step 2, wherein the adding amount of tetraethyl ammonium hydroxide solution is 30-40% of the mass of the aluminum phosphate nanocolloid, stirring at room temperature to form a paste, and then standing for 24 hours;
step 4, adding water, tetraethyl ammonium hydroxide solution and alkylamine into the polytetrafluoroethylene lining of the hydrothermal kettle, wherein the adding amount of the water, the tetraethyl ammonium hydroxide solution and the alkylamine is 25-40%, 60-80% and 100-160% of the mass of the aluminum phosphate nanocoil in sequence;
step 5, transferring the paste obtained in the step 3 into the polytetrafluoroethylene lining in the step 4, sealing, and performing hydrothermal treatment at 160-200 ℃ for 20-72 hours; then naturally cooling to room temperature, filtering to obtain a precipitate, washing the precipitate by using water and absolute ethyl alcohol, and drying to obtain dry blue powder;
and 6, putting the blue powder obtained in the step 5 into a muffle furnace, raising the temperature from room temperature to 550 ℃ in an air atmosphere, keeping the temperature, and naturally cooling to room temperature to obtain blue sample powder.
3. The method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material according to claim 2, wherein the method comprises the following steps: the copper salt in the step 2 is copper nitrate or copper acetate.
4. The method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material according to claim 2, wherein the method comprises the following steps: the alkylamine in the step 4 is diethylamine, triethylamine or tripropylamine.
5. The method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material according to claim 2, wherein the method comprises the following steps: the tetraethyl ammonium hydroxide solution is a 25% aqueous solution.
6. The method for preparing the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material according to claim 2, wherein the method comprises the following steps: the drying temperature in the step 5 is 60 ℃, the drying time is 24 hours, and the temperature in the step 6 is increased from room temperature to 550 ℃ and then is kept for 5 hours.
7. The use of a two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material of claim 1, wherein: the catalyst is used for catalyzing the reaction of preparing adipic acid by oxidizing cyclohexane.
8. The use of a two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material of claim 7, wherein the reaction steps for catalyzing the oxidation of cyclohexane to adipic acid are as follows:
(1) mixing two-dimensional ultrathin CuO @ SAPO-34 molecular sieve powder, cyclohexane and acetone according to the mass ratio of 1:20: 20;
(2) transferring into a high-pressure reaction kettle with an inflation valve and stirring, sealing, introducing oxygen, and keeping the pressure at 1.5 MPa;
(3) heating the high-pressure reaction kettle to 120-150 ℃, and reacting for 10-24 hours;
(4) after the reaction is finished and the temperature is cooled to room temperature, discharging the oxygen in the reaction until the pressure is reduced to normal pressure;
(5) opening the reaction kettle, performing centrifugal separation, precipitating the lower layer to be a molecular sieve catalyst, and taking out the supernatant;
(6) distilling the supernatant to obtain viscous liquid;
(7) washing the obtained viscous liquid;
(8) and (4) taking the supernatant, cooling and filtering to obtain solid crystals, namely the adipic acid product.
9. The use of the two-dimensional ultra-thin CuO @ SAPO-34 molecular sieve sheet material of claim 8, wherein said washing solution in (7) is hot water at 90 ℃.
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